Advances in Petrochemicals

Edited by Vivek Patel

 Advances in Petrochemicals

Edited by Vivek Patel

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 Contents

Preface

Chapter 1 Cashew Nut Shell Oil — A Renewable and Reliable

Petrochemical Feedstock
by Elijah A. Taiwo

Chapter 2 Natural Gas Geochemistry in the Offshore Nile Delta, Egypt

by Mohamed Abdel-Aziz Younes

Chapter 3 Synthesis of Nano-structured materials for storing hydrogen

as an alternative source to fossil fuels derivatives.
by Omar Reyes-Martínez and José Luis Velázquez-Ortega

Chapter 4 Crude Oil Desalting Process

by Juan Pereira, Ingrid Velasquez, Ronald Blanco, Meraldo
Sanchez, César Pernalete and Carlos Canelón

Chapter 5 Overview about Different Approaches of Chemical

Treatment of NORM and TE-NORM Produced from Oil Exploitation
by N.S. Awwad, M.F. Attallah, E.M. El-Afifi, H.A. Ibrahium and
H.F. Aly

Chapter 6 Simulation and Optimization of Multi-period Steam Cracking

Process
by Lei Zhang, Hangzhou Wang, Tong Qiu and Bingzhen Chen
Preface

The petrochemical industry is an important area in our pursuits for

economic growth, employment generation, and basic needs. It is a
huge field that encompasses many commercial petrochemical and
polymer-enabled products.

The book is designed to help the reader, particularly students and

researchers of petroleum science and engineering, to understand
synthesis, processing, mechanics, and simulation of the petroleum
processes.

The selection of topics addressed and the examples, tables, and

graphs used to illustrate them are governed, to a large extent, by
the fact that this book is aimed primarily at petroleum science and
engineering technologists.

Undoubtedly, this book contains must read materials for students,

engineers, and researchers working in the area of petrochemicals
and petroleum and provides valuable insights into the related
synthesis, processing, mechanisms, and simulation. This book is
concise, self-explanatory, informative, and cost-effective.
 Chapter 1

Cashew Nut Shell Oil — A Renewable and Reliable

Petrochemical Feedstock

Elijah A. Taiwo

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/61096

Abstract

This study evaluates the occurrence of cashew plant, extraction processes and
composition of cashew nut shell liquid (CNSL), modification and conversion
processes, as well as environmental impact and controls of the liquid as petrochemical
feedstock. The goal of this study is to bring the alternative usage of CNSL to the
limelight and to mitigate the serious problems posed by the depleting petroleum
reserves.

Cashew nut shell (CNS) was obtained fresh from the wild, pulverized and then
extracted by pyrolysis and solvent extraction methods using n-hexane. The liquid
obtained was characterized. Experimental results corroborated the fact that CNSL
contains mainly phenolic compounds such as cardanol, cardol, anacardic acid and 6-
methyl cardol. CNSL obtained by pyrolysis has a higher density with less moisture
content, while solvent-extracted CNSL had higher contents of cardol and anacardic
acid.

CNSL offers innumerable applications due to the phenolic nature of its constituents,
with enshrined features for transformation into high-value specialty chemicals.
Varied CNSL composition with varying extraction processes are a vantage opportu‐
nity with multiple application potentials as a valuable petrochemical feedstock.

Keywords: Cashew nut shell Liquid (CNSL), Petrochemical feedstock, Solvent ex‐
traction, Renewable resources, Characterization, Supercritical fluid
4 Advances in Petrochemicals

1. Introduction

Cashew Nut Shell Oil (CNSO) is a versatile component of the Cashew fruits’ nut. The oil which
is a dark reddish-brown in colour is resident in a soft honeycomb shell, that is the pericarp of
the nut. It is a natural resin that could serve as a valuable raw material for multiple applications.
Rapid growth in the world population and increasing standard of living has overstretched
petroleum resources as petrochemical feedstock. This among other factors, has culminated in
the fast depletion of global petroleum reserves. Therefore, to maintain the standard of living
and continuity of industrial sector which is paramount to human survival this decade and
beyond, there is a need to find alternative sources of fuel and petrochemical feedstock. Cashew
nut shell, a by-product of the cashew industry, is an embodiment of a useful chemical serving
as a raw material for the petrochemical industry.
Cashew (Anacardium Occidentale L.), a well-known species of the Anacardiceae family [1], is a
tropical plant (shrub) found within the region between 23°N and 23°S of the equator. It is a
drought resistant tree crop grown successfully in areas with annual rainfall of 50–350 cm. Its
height is above 12 m and has a spread of about 25 m. It has an extensive root system which
makes it adaptable to a wide range of moisture levels and soil types [2]. On the commercial
scale, it is best grown on well-drained, sandy loam soils. Today, it is an economically valuable
tree crop in Nigeria, with evergreen leaves, all year round.
The cashew tree consists of the cashew nut fruit (which is a curved edible seed, housed in a
honeycomb-like shell), the apple, leaf and bark. The fruit consists of an outer shell, inner shell
and the kernel. The thickness of the cashew nut shell is about 1/8 in. (0.32 cm). The soft
honeycomb matrix, in between the outer and inner shell, contains a dark brown liquid, which
is known as cashew nut shell liquid (CNSL) [3].
The Cashew plant is of great economic significance to Nigeria and other tropical countries due
to its valuable products. These products are utilized in food, medicine, chemical and allied
industries. In addition to providing shade, the cashew tree is an embellished ornamental plant
that suitably controls soil erosion.
Usually, it takes about 3-4 years from planting time before fruiting. Thereafter, the tree can
live up to 40 years and more. The cashew fruit (figures 1 and 2) is unusual in comparison with
other tree nuts since the nut is outside the fruit. The cashew apple which is about 10 cm long
is an edible false fruit, attached to the externally born nut by a stem. Its color ranges from
yellow to red, fibrous in nature, very juicy, sweet, pungent and high in vitamins A and C. In
its raw state, cashew nut shell (CNS), which is leathery in nature, contains the vesicant oily
liquid (CNSL). The shell is separated from the kernel by the testa which is a thin skin sur‐
rounding the kernel.

1.1. Growth and development of cashew in Nigeria

The world production of cashew crop, according to the Food and Agriculture Organization
(FAO), was around 2.7 million tons per annum. The major raw cashew producing countries
with their production figures in 2005 (as per the United Nation's Food and Agriculture
 Cashew Nut Shell Oil — A Renewable and Reliable Petrochemical Feedstock 5
http://dx.doi.org/10.5772/61096

Cashew 
apple
Cashew 
apple

Cashew 
nut 
Cashew 
  nut 

 
Figure 1.The Cashew fruit. 

Figure 1. The Cashew

  fruit.
Figure 1.The Cashew fruit. 

 
nut shell

nut shell
testa

testa
kernel

  kernel

Figure 2. The cashew nut cross section  

Figure 2. The cashew nut cross section 

Organization) were Vietnam (960,800 tons), Nigeria (594,000 tons), India (460,000 tons), Brazil
Figure 2. The cashew nut cross section 
 
(147,629 tons) and Indonesia (122,000 tons). India ranks first in area utilized for cashew
production, though
  its yields are relatively low. Collectively, Vietnam, India and Brazil
1.1 Growth and Development of Cashew in Nigeria 
account for more than 90% of all cashew kernel exports [4,5].
1.1 Growth and Development of Cashew in Nigeria 
The world production of cashew crop, according to the Food and Agriculture Organization
Cashew production in Nigeria dates back to the 15th century when it was introduced by
(FAO), was around 2.7 million tons per annum. The major raw cashew producing countrie
Portuguese explorers [4,5]. The plant was then, purposefully planted for afforestation schemes
The world production of cashew crop, according to the Food and Agriculture Organization
with  their  production  figures  in  2005  (as  per  the  United  Nationʹs  Food  and  Agricultur
in the now defunct Eastern Nigeria. Cashew became a popular commercial crop in 1953, when
(FAO), was around 2.7 million tons per annum. The major raw cashew producing countrie
Organization)  were  Vietnam  (960,800  tons),  Nigeria  (594,000  tons),  India  (460,000  tons)
planted on a large scale principally
with  their  production  forfigures 
the nuts, afforestation
in  2005  and United 
(as  per  the  erosionNationʹs 
prevention pro‐
Food  and  Agriculture
Brazil (147,629 tons) and Indonesia (122,000 tons). India  ranks  first  in  area  utilized  fo
grammes in theOrganization) 
escarpment areas of Dui, Mbala, Oghe, Oji, Isuochi and Kingie in Eastern
were  Vietnam  (960,800  tons),  Nigeria  (594,000  tons),  India  (460,000  tons)
cashew  production,  though  its  yields  are  relatively low. Collectively, Vietnam, India and
Nigeria by the defunct Eastern Nigeria Development Corporation. In Western Nigeria, the first
Brazil (147,629 tons) and Indonesia (122,000 tons). India  ranks  first  in  area  utilized  fo
Brazil account for more than 90% of all cashew kernel exports [4,5]. 
planting of cashew started in the 16th century at Agege in Lagos [4]. Commercial cultivation
cashew  production,  though  its  yields  are  relatively low. Collectively, Vietnam, India and
actually startedBrazil account for more than 90% of all cashew kernel exports [4,5]. 
in the 1950s at Iwo, Eruwa and upper Ogun in the defunct Western Nigeria
Cashew  production  in  Nigeria  dates  back  to  the  15th  century  when  it  was  introduced  b
by the then Western Nigeria Development Corporation.
Portuguese  explorers  [4,5].    The      plant  was  then,  purposefully  planted  for  afforestation
Cashew  production 
Cashew was thereafter, introduced into in  Nigeria 
the Middle dates Belt
back 
andto Northern
the  15th  century  when Eastern
Nigeria from it  was  introduced  by
schemes in the now defunct Eastern Nigeria. Cashew became a popular commercial crop in
Portuguese 
and Western Nigeria. explorers 
These cashew [4,5]. 
nuts   The      plant  was  then,  purposefully  planted  for  afforestation
1953,  when    planted  on were mainly
a  large  scale ofprincipally 
the mediumfor  nut-size biotype,
the  nuts,  which
afforestation  and  erosion
schemes in the now defunct Eastern Nigeria. Cashew became a popular commercial crop in
according to ISO-6477 standards, fall within
prevention  programmes  in thethe W320 category.areas 
escarpment  This cashew
of  Dui, biotype
Mbala, therefore
Oghe,  Oji,  Isuochi  and
1953, cashew
constitutes the main when   species
planted inon  a  large 
Nigerian scale  principally 
cashew plantations.for 
Thisthe  nuts,  afforestation 
biotype, which was and  erosion
prevention  programmes  in  the  escarpment  areas 
from the Asian continent, attracts low premium in the international market. However, of  Dui,  Mbala,  Oghe, 
Cocoa Oji,  Isuochi  and
6 Advances in Petrochemicals

Research Institute of Nigeria (CRIN) which was established in 1962, commenced research on
the cultivation, uses and economy of cashew around 1972. The crop then rapidly spread to all
agro-ecologies of Nigeria [6]. This brought about the cultivation for erosion control and the
afforestation schemes of the Brazilian cashew biotype (jumbo nut-size), which is now being
grown by cashew farmers [6]. This species mature within a year in contrast to the local wild
varieties which take about 3 to 5 years to mature.

Today, cashew grows almost everywhere in Nigeria but its cultivation is concentrated
primarily in the south and middle belt regions both in small holder farms and plantations [2].
Major cashew growing areas in Nigeria include Abia, Abuja, Anambra, Benue, Cross river,
Enugu, Ebonyi, Ekiti, Kogi, Kwara, Kebbi, Nasarawa, Niger, Oyo, Osun, Ondo, Ogun, Sokoto,
and Taraba states. High quality cashew nuts, suitable for export, are produced from the south
west and south east regions of Nigeria. Figure 3 shows the spread of cashew production in
Nigeria as published by National Cashew Association of Nigeria.

Establishment of the Premier Cashew Processing Factory in Oghe, Enugu State early in the
1980s marks the turning point in industrial processing of cashew in Nigeria. The primary
objective of government then was to process the harvest from the government-owned 650 ha
cashew plantation as well as to serve other small land holding farmers in and around the States
of Kogi and Benue.

Figure 3. The spread of cashew cultivation in Nigeria

In 2002, Nigeria produced about 30,000 tons of cashew nut from the total holdings of 50,000
ha, which were mostly under small holdings. The average growth of cashew nut production
 Cashew Nut Shell Oil — A Renewable and Reliable Petrochemical Feedstock 7
http://dx.doi.org/10.5772/61096

increased to 55,000 tons in 2004. In 2010, Nigeria ranked third among the top 10 world cashew
nut-producing countries with a total production of 594,000 tons [7]. This stride improved to
second worldwide in 2011 with a production of 835,000 metric tons, constituting 19.5% of the
world’s production according to FAOSTAT data 2013 [7]. The world production of cashew
nuts is presented in Figure 4.

Others
Mozambique
Guinea ‐Bissau 
Tanzania
Phillipines
Cote d’ Ivoire
Indonesia
Brazil
India
Nigeria
Vietnam

0 200,000 400,000 600,000 800,000 1,000,000

production (tonnes)

Figure 4. Main producer countries of cashew nuts  

Recently, a cashew export programme was initiated in Lagos, Nigeria by the Nigerian Export
Figure  4.  Main producer countries of cashew nuts
Promotion
  Council (NEPC), the National Cashew Association of Nigeria (NCAN) and USAID/
Nigeria Expanded Trade and Transport (NEXTT). The move is to expand further the produc‐
Recently,  a  cashew  export  programme  was  initiated  in  Lagos,  Nigeria  by  the  Nigerian 
tion of cashew nut for export purposes. The National Cashew Association of Nigeria (NCAN)
Export  Promotion  Council  (NEPC),  the  National  Cashew  Association  of  Nigeria  (NCAN) 
is the umbrella body for the Nigerian cashew industry. It is actively involved in developing a
and  USAID/Nigeria  Expanded  Trade  and  Transport  (NEXTT).  The  move  is  to  expand 
strategy and action plan to improve the quality of raw nuts, to increase the coordination in the
further the production of cashew nut for export purposes. The National Cashew Association 
sector and to improve the business climate for processing.
of  Nigeria  (NCAN)  is  the  umbrella  body  for  the  Nigerian  cashew  industry.  It  is  actively 
India is a leading
involved  in exporting country
developing  of cashew
a  strategy  nuts. Its
and  action  production
plan  volume
to  improve  stems from
the  quality  thenuts,  to 
of  raw 
skilledincrease the coordination in the sector and to improve the business climate for processing. 
labour force and technology deployed at the processing stage. The popularity of cashew
nuts arose from its applicability as natural vitamin pills [(balita.ph/.../cashew-nuts-gain-
India is a leading exporting country of cashew nuts. Its production volume stems from the 
popularity-as-natures-vitamin-pill/)]. Cashew kernels on the other hand, have high protein
skilled  labour  force  and  technology  deployed  at  the  processing  stage.  The  popularity  of 
content (about 19.5%), which accounted for its use in place of soybean meal in broiler chickens
cashew nuts arose from its applicability as natural vitamin pills [(balita.ph/…/cashew‐nuts‐
[8], whereas the nuts serve a major source of alkenyl phenolic compounds [9].
gain‐popularity‐as‐natures‐vitamin‐pill/)].  Cashew  kernels  on  the  other  hand,  have  high 
protein  content  (about  19.5%),  which  accounted  for  its  use  in  place  of  soybean  meal  in 
1.2. Processing
broiler chickens [8], whereas the nuts serve a major source of alkenyl phenolic compounds 
[9]. 
Basic physical operations before extraction are required on the samples of cashew nuts to
ensure a high degree of purity and the quality of the product. These operations constitute the
1.2 Processing 

Basic  physical  operations  before  extraction  are  required  on  the  samples  of  cashew  nuts  to 
ensure  a  high  degree  of  purity  and  the  quality  of  the  product.  These  operations  constitute 
the basic pretreatment on samples and include washing, drying, shelling and size reduction. 
Sometimes, washing may involve the use of detergents to remove likely contaminants. 
8 Advances in Petrochemicals

basic pretreatment on samples and include washing, drying, shelling and size reduction.
Sometimes, washing may involve the use of detergents to remove likely contaminants.

Drying is purposely to make the nuts moisture-free. Both sun- and oven-drying have been
found effective. Size reduction creates a better contacting surface area for the shell and solvent
to enhance removal of the CNSL.

Traditionally, the kernel is removed for the CNS manually. However, to improve the deshel‐
ling process, several methods have been adopted [1,8,10], which include, among others,
soaking the nuts in water to improve the moisture content thereby reducing the scorching and
cracking tendencies during roasting. Roasting the nuts makes the shell brittle and loosens the
kernel from the shell easily. Also, CNSL is released during the roasting [10]. Figure 5 shows
the nut-processing stages.

1.3. Extraction of CNSL

Several methods are available in the literature for the extraction of CNSL. Oil extraction
efficiency varies with the method adopted. Raw CNS has been reported to contain over 20%
oil. The oil bath process leaves about 10% of the oil as a by-product in the spent shell. However,
using an expeller extraction process, further quantities of oil may be recovered from the spent
CNS.

The extraction processes can be classified into two basic types: those that involve heating and
those that are done in cold or room temperature. The heating process (roasting) can be achieved
by open recipients or drums [11]. In a thermomechanic (hot oil) process, the cashews can be
heated by the actual CNSL [12]. In the cold process, the CNSL can be obtained by extrusion in
solvents or by pressing. The cashew’s liquid so obtained is denoted as natural CNSL and that
extracted by the hot method is called technical CNSL [13].

Various hot methods reported in the literature for the extraction of CNSL from cashew nut
shells (CNS) include, open pan roasting, drum roasting and hot oil roasting, while cold
extrusion, solvent extraction, etc. are cold methods. References [14] and [15] reported CNSL
extraction through pyrolysis. The extraction of CNSL using supercritical carbon dioxide has
also been reported by [16,17]. Solute extracted using supercritical carbon dioxide in the
extraction process is generally significantly different from those obtained by other conven‐
tional alternative processes.

Extraction methods affect the selectivity towards various compounds in CNS [18]. High
concentrations of mono-unsaturated cardanol were extracted with Supercritical water (SCW)
and soxhlet extraction methods (See Table 1).

Extraction fluid, substrate and operating conditions affect the extract composition (Table 2).
CNSL directly obtained from CNS by SC extraction contains traces of acids whereas the same
obtained from CNSL through heat exchanger mainly contains cardanol along with acids and
alkanes. The oil composition of CNSL obtained through pyrolysis of CNS includes phenols
and substituted phenols along with cardanol. For resin production, the CNSL obtained
through pyrolysis route is the most suitable feed for extraction by SC method [3].
 and those that are done in cold or room temperature. The heating process (roasting) can be 
achieved  by  open  recipients  or  drums  [11].  In  a  thermomechanic  (hot  oil)  process,  the 
cashews  can  be  heated  by  the  actual  CNSL  [12].  In  the  cold  process,  the  CNSL  can  be 
obtained by extrusion in solvents or by pressing. The cashew’s liquid so obtained is denoted 
Cashew Nut Shell Oil — A Renewable and Reliable Petrochemical Feedstock 9
http://dx.doi.org/10.5772/61096
as natural CNSL and that extracted by the hot method is called technical CNSL [13]. 

 
  Cleaning
 
  Soaking
 
  Roasting
 
Open Pan Roasting   Drum Roasting Hot Oil Roasting  
 
 
  Shelling
 
  Manual   Mechanical 
 
  CNSL Extraction
 
  Pre‐grading
 
 
Drying
 
  Sun Drying   Solar Drying Furnace Drying 
 
 
  Peeling
 
  Grading
 
  Packaging
 
 
Figure
  5. Flow diagram of cashew nut shell processing
Figure 5. Flow diagram of cashew nut shell processing
 
Constituents Soxhlet extraction Two-step extraction
SCW
SC-CO2 extraction Methanol-
Hexane Methanol extraction Hexane-SCW
SCW

Monounsaturated cardanol 26.64 27.19 68.93 1.09 48.84 49.22

Saturated cardanol 1.22 1.45 2.4 1.52 1.04 1.84

Unknown hydrocarbon – – 3.42 – 1.57 1.42

Unknown hydrocarbon – – 3.29 – 1.51 1.37

Octacosene – – 4.91 – 2.25 2.04

Stigmasterol – – 3.44 – 1.57 1.43

10 Advances in Petrochemicals

Constituents Soxhlet extraction Two-step extraction

SCW
SC-CO2 extraction Methanol-
Hexane Methanol extraction Hexane-SCW
SCW

Monounsaturated anacardic
27.90 19.06 9.47 52.24 18.64 11.4
acid

β-Sitosterol 1.38 1.86 1.63 1.63 0.75 1.76

Monounsaturated cardol 1.05 – – – 0.57 –

Saturated cardol 20.31 34.88 1.85 29.58 9.76 12.64

Di-unsaturated cardol 7.62 10.39 – 6.72 4.13 6.07

Unknown hydrocarbon 5.7 – – – – 3.33

Triacontene 3.33 3.41 – 4.31 1.85 5.45

Others 4.85 1.76 0.66 2.91 7.52 2.03

Source: [18]

Table 1. Compound distribution of CNSL obtained by various extraction methods.

SC-CNSL from CNS

Operating Parameter SC-CNSL from Pyrolysis
SC-CNSL from CNS Obtained through Heat
(P bar/T°C) CNSL
Exchanger Unit

Penthadecane (0.67)
Hexadecane (0.67)
Heptadecane (0.77)
Hexadecanoic acid (0.71)
2,6,10,14 tetra methyl 3-ethyl phenol (7.64)
Oleic acid (0.62)
pentadecane (0.65) 2-methyl benzaldehyde (20.51)
200/60 Cardanol-C13 (0.69)
8 methyl heptadecane (0.70) 3-butyl phenol (1.39)
Cardanol-C15 (84.20)
Hexadecanoic acid (0.61) Cardanol diene (48.61)
Methyl Cardanol (2.83)
Elicosane (0.47)
Cardanol (62.31)
Cardanol diene (31.24)

3-ethyl phenol (3.31)

Hexadecanoic acid (0.56)
Azulene (1.89)
Oleic acid (0.684
Ethyloxybenzene (11.21)
225/60 Cardanol-C13 (0.65)
Acenaphthylene (7.12)
Cardanol-C15 (86.26)
3-butyl phenol (2.28)
Methyl Cardanol (3.11)
Cardanol diene (66.82)

Hexadecanoic acid (0.58) Penthadecane (0.04) 4-ethyl phenol (5.01)

250/60 Cardanol-C13 (7.42) Heptadecane (0.08) Propyl benzene (11.96)
Cardanol-C15 (64.89) tetradecanal (1.99) Acenaphthylene (2.83)
 Cashew Nut Shell Oil — A Renewable and Reliable Petrochemical Feedstock 11
http://dx.doi.org/10.5772/61096

SC-CNSL from CNS

Operating Parameter SC-CNSL from Pyrolysis
SC-CNSL from CNS Obtained through Heat
(P bar/T°C) CNSL
Exchanger Unit

cardanol 13 (1.62)
Hexadecanoic acid (1.27) 3-pentyl phenol (3.18)
Methyl Cardanol (3.03)
Cardanol (81.54) 3-butyl phenol (1.35)
Diethyl Phthalate (12.34)
2 methyl Cardanol diene Cardanol (64.91)
(2.97)

Hexadecanoic acid (0.80)

Hexadecanoic acid (1.01)
Oleic acid (0.67)
Oleic acid (0.98) 2-ethyl phenol (4.89)
Cardanol-C13 (2.32)
300/60 Cardanol diene (81.94) 2-methyl benzaldehyde (8.73)
Cardanol-C15 (61.34)
2 methyl Cardanol diene Cardanol (80.50)
Cardanol c17 (2.06)
(2.97)
Diethyl Phthalate (13.35)

Source: [3]

Table 2. Chemical characterization of CNSL extracted by SCFE

Purification or refining of CNSL involves vacuum distillation of raw CNSL. However,

supercritical fluid extraction SFE of CNSL can offer selective separation of the components
present in CNSL by varying the operating parameters [19].

2. Experimental materials and methods

2.1. Sample collection and pretreatment

Cashew was obtained from local markets in Ile-Ife, Osun State and a commercial farm in Owu-
Ijebu in Ogun state. The shell was detached from the apple, washed and sun-dried prior to
deshelling the nut. The cashew nut shell was further oven-dried and milled using a ball mill
at the Petrochemical laboratory of the Department of Chemical Engineering, Obafemi Awo‐
lowo University, Ile-Ife. The milled CNS was sieved to obtain a particle size range of 5 mm.
The ground sample was stored at 4°C in a refrigerator for further experimentation.

2.2. Extraction of the CNS oil

The pyrolysis of the cashew nut shells was carried out in the pyrolysis reactor designed and
fabricated at the Chemical Engineering Department of Obafemi Awolowo University, Ile-Ife.
About 150 g of the ground and dried CNS sample was placed in the reactor and heated. The
reactor is connected to a condensing unit which has several condensers in series, in order to
effectively recover the exhaust gases. The experimental rig is as shown in figure 6.
 The pyrolysis of the cashew nut shells was carried out in the pyrolysis reactor designed and 
fabricated at the Chemical Engineering Department of Obafemi Awolowo University, Ile‐Ife. 
12 About 150 g of the ground and dried CNS sample was placed in the reactor and heated. The 
Advances in Petrochemicals
reactor is connected to a condensing unit which has several condensers in series, in order to 
effectively recover the exhaust gases. The experimental rig is as shown in figure 6. 

  1
2 
3 
1 
  6 6 
7
4 
 
8 
5  10 
  4 1. Vent 
2. Pressure gauge 
  3. Thermometer 
4. Valve 
9
  5. Reactor vessel 
6. Condenser 
  7. To condensate collector 
8. Cooling water inlet 
  9. Heat electric cord  
  10. Heating plate 

 
Figure 6. The experimental rig set-up.
Figure 6.The experimental rig set-up.

The temperature
  of the reactor tank and that of the exhaust gas stream were measured and
recorded at regular intervals. The volatiles which condensed at the condensing Unit were
collected in several glass bottles. The heating was stopped when no significant changes in
The temperature of the reactor tank and that of the exhaust gas stream were measured and 
temperature and
recorded  gas condensates
at  regular  wasvolatiles 
intervals.  The  observed. Thecondensed 
which  reactor was then
at  the  allowed to
condensing  cool
Unit  for about
were 
6 h; the ash and char were separated, weighed and recorded. The mass of pyrolysis
collected  in  several  glass  bottles.  The  heating  was  stopped  when  no  significant  changes  in  oil
produced was determined by mass balance calculation of the whole recovery system, before
temperature  and  gas  condensates  was  observed.  The  reactor  was  then  allowed  to  cool  for 
about 6 h; the ash and char were separated, weighed and recorded. The mass of pyrolysis oil 
and after the experiment. For the purpose of comparison, 10 g of the CNS sample was extracted
produced was determined by mass balance calculation of the whole recovery system, before 
by soxhlet extraction using n-hexane as a solvent.

2.3. Characterization of the extracted CNSL samples

Moisture content was determined by standard Dean and Stark apparatus as outlined by the
Association of Official Analytical Chemists [20]. Viscosity was determined using a capillary
viscometer in water bath maintained at 40°C. A pH meter model PYE 290 was calibrated and
used to determine the pH of the samples. Specific Gravity was measured using a pycnometer
at 25°C. Iodine value was obtained by the method of [21].

An oxygen bomb calorimeter (model 6400) was used to determine the calorific value of the
CNSL samples under adiabatic condition. The heat of the system was regulated by using an
electrolyte. The calorific values of CNS and its spent cake were measured by placing them in
a capsule, which was then put in the calorimeter crucible. The calorific value is given by
equation 1.

(W + w ) (T1 - T2 )
calorific value ( kcal / kg ) = (1)
X
 Cashew Nut Shell Oil — A Renewable and Reliable Petrochemical Feedstock 13
http://dx.doi.org/10.5772/61096

where
W = weight of water in calorimeter (kg),
w = water equivalent of apparatus,
T1 = initial temperature of water (0C),
T2 = final temperature of water (0C),
X = weight of fuel sample taken (kg)

3. Results and discussion

Table 3 shows the physicochemical characteristics of CNSL obtained including the decarboxy‐
lated CNSL. The quantity and characteristics of the CNSL extract varies with the extraction
method.

CNSL CNSL CNSL

Parameter
(pyrolysis) (hexane extracted) (decarboxylated)

Colour Dark brown Dark brown Dark brown

Moisture content 4.1 6.4 3.2

Refractive index 1.693 1.688 1.698

Specific gravity 0.943 0.926 0.928

Viscosity (centipoise) 57 40 38

Ash (%) 1.22 1.53 1.50

Saponification value (mgKOH/g) 58.5 47.2 56.3

Iodine value (mg/100g) 212 236 227

Acid value (mgKOH/g) 12.4 15.6 12.9

Free fatty acid (mgKOH/g) 6.5 7.9 8.2

pH 4.8 4.5 5.2

Calorific value (kJ/g) 47.62

Table 3. Physico-chemical characteristics of CNSL obtained including the decarboxylated CNSL.

CNSL obtained by pyrolysis although a little less in quantity than the soxhlet extraction, is
denser (943 kg/m3) with less moisture content (4.1%) and higher saponification value (58.5%).
Solvent-extracted CNSL presented higher contents of cardol and anacardic acid and a lower
percentage of cardanol than thermally extracted CNSL (Table 4). The higher content of
cardanol, viscosity and impurity were the significant differences in CNSL obtained through
pyrolysis. This gave credence to the report of Rodrigues et al. [22].
14 Advances in Petrochemicals

CNSL CNSL CNSL

Components
(pyrolysis) (hexane extracted) (decarboxylated)

Cardol (%) 27 30 31

Cardanol (%) 54 20 65

Anacardic acid (%) 5 43 2

Others (%) 14 7 2

Table 4. Composition of the extracted CNSL

Decarboxylation of raw CNSL involves loss of a carbon dioxide molecule from anacardic acid.
The anacardic acid in the oil was converted to cardanol. This is reflected in the composition
variation of the components reported in table 4. It is also significant that the pyrolysis of the
CNS results in loss of the carboxylic acid content of the cashew nut shell to the process. The
decarboxylated anacardic acid is termed CNSL biodiesel. The biodiesel obtained from CNSL
does not require further processing like Trans esterification.

CNSL biodiesel is considered as offering many advantages, including sustainability, decrease

of HC, CO, NOx gas emissions and many harmful pollutants [23]. Reference [24] explains the
pyrolysis procedure of CNSL. The decarboxylation of CNSL is responsible for the trend in the
pH obtained for the extracts.

Most of the characteristics evaluated gave similar results as those already reported in the
literature. In the present findings, the highest occurrence of cardanol was in the decarboxylated
CNSL while anacardic acid and cardol occur most in the hexane-extracted and pyrolysis CNSL,
respectively. This gave credence to the report of [25].

Heating CNSL decomposed the anacardic acid into cardanol and CO2. Decarboxylation of
CNSL to convert anacardic acid into cardanol could be done by heating, with an optimum
heating temperature of 140°C for 1 h.

4. CNSL as petrochemical feedstock

As a substituted phenol which can take part in a variety of reactions, naturally occurring
cashew nut shell liquid (CNSL), a renewable product, offers advantages over synthetics. Its
innumerable application stems from the phenolic nature of its constituents, with enshrined
features for transformation into high value specialty chemicals [26].

The industrial applications of CNSL-based products are numerous and include fungicide,
pesticide, insecticide, brake linings, paints and primers, foundry chemicals, lacquers, cements,
specialty coatings and resin. The application of CNSL component in bacteriostatic antibiotics
is recently gaining attention. Their effect on plant growth, acid activity, wood preservative and
pressure treatment activity are being explored. From the literature [27 - 29], much of the
biological activity of CNSL has been attributed to anacardic acid: a major constituent of CNS.
 Cashew Nut Shell Oil — A Renewable and Reliable Petrochemical Feedstock 15
http://dx.doi.org/10.5772/61096

Conversely, technical CNSL, as obtained by roasting or oil bath method contained mainly
cardols and cardanols [27].

CNSL reduces the extent of the electrochemical processes taking place on carbon steel surface
undergoing corrosion. The inhibition tendency is excellent for both static and dynamic
conditions. CNSL and its derivatives have antioxidative characteristics [28 - 30]. This antioxi‐
dative tendency is related to the electron-donating nature and steric effect of the substituents.
The electron-donating effect usually enhances the electron density at the phenolic oxygen of
the cashew nut oil, resulting in the trapping of the radicals which normally propagates
oxidation reaction. CNSL is a mixture of hindered phenols with long alkyl substitution at the
meta position. The unsaturation on the long side chain substituents is an important factor
enhancing higher anti-oxidant activity of CNSL. CNSL films are thermally stable. This stability
increases in the presence of thiophosphate ester additives.

Olefin metathesis (OM) reaction on cardanol is an important class of reactions that allows for
the synthesis of new olefins that are sometimes impossible to prepare via other methods [31].
Cardanol- a renewable, low cost, main constituent (about 85%) of CNSL possesses character‐
istic long alkyl chains in meta position of its phenol ring [12] that promotes this OM reaction,
and also influences several chemical transformations leading to novel functionalities [31].

Cardanol based polyhydrins improve the photo-catalytic activity of bare TiO2. The porphyrins
are brown-red sticky solids, very soluble in CHCl3 or CH2Cl2 [32]. This substituted cardanol-
based porphyrin and their metallic complexes have been used extensively in photo degrada‐
tion of toxic, bio-refractory 4-nitro phenol in water, which is dangerous for the ecosystem and
for human health [32]. CNSL is also useful in fuel blends and fuel mixtures [33] and for
producing diesel oil [34]. Cracking of CNSL with a molecular sieve at 500° C for 2 h generates
brown coloured liquid product. This is diesel fuel.

Cashew Nut Shell Liquid (CNSL) was used as an alternative fuel for diesel engine. The viscosity
of CNSL is 30 - 35 times higher than diesel; hence different blends of CNSL would have
different properties and application. Also, modification of the oil and its application condition
such as, injection pressure, injection timing and preheating the oil also optimizes the perform‐
ance of the engine. There were indications that preheating of CNSL25 blends at 200 kg/cm2
injection pressure and 28° injection timing gives encouraging results suitable for commercial
purposes [35]. CNSL as a bioadditive in engines increases the durability of the equipment.
Hence, the application of CNSL as a bioadditive will reduce the dependency on petroleum
products besides preserving the environment by lowering pollutant residues from fuel
combustion products. Some of the properties of diesel, biofuel and ethanol are presented
against CNSL in Table 5.

CNSL has higher density than diesel. It can be reduced by degumming and trans esterification.
Cetane for CNSL is expected to be poor due to the presence of aromatic compounds. The usual
C:H:O ratio for vegetable oils is 78:12:10 whereas for CNSL it is 80:12:8; hence, it justifies the
higher calorific value of CNSL (47 MJ/kg), whereas for diesel it is 42 MJ/kg. Also, ash content
is well within the limits for CNSL. The water content of CNSL is quite high. The sulphur content
does not exceed 0.006% for any vegetable oil. Thus it is anticipated that CNSL has no sulphur
16 Advances in Petrochemicals

content. The flash point for CNSL is 164°C; this is higher than the flash point for diesel and
represents the higher starting ignition temperatures and compression of CNSL [35].

Properties Diesel* Ethanol* CNSL

Density (kg/m3) 0.84 0.789 0.9326
Kinematic viscosity (cost) 2-5 1.19 17.2
Calorific value (kJ/kg) 42000 30000 47600
Flash point (°C) 62 16 193
Auto-ignition temperature (°C) 210 362 206

*Source: [28]

Table 5. Fuel properties

The physicochemical properties of cashew nut shell liquid (CNSL) make it potentially useful
for improved adhesion between bitumen and aggregates. Thus, the asphalt resulting from
bitumen modified with CNSL has better stripping resistance and satisfactory mechanical
properties compared with conventional asphalts. The CNSL, as an additive, prevents stripping
in the asphalts, thereby contributing to its moisture damage resistance [36].

CNSL has also been used in production of asbestos with free friction composition for brake
linings [37]. In combination with cardanol, it is used extensively in automotive break-lining
applications [38]. CNSL/cardol-based surface coatings possess excellent gloss and surface
finish with a high level of toughness and elasticity.

Valuable chemicals result from the pyrolysis of CNSL at high temperatures (450°C to 750°C)
and at short residence times [39]. The products of pyrolysis include tar, phenols, hydrocarbons
and gases with high petrochemical values.

On the other hand, cardanol which is highly resistant to softening action of mineral oil, acids,
alkalis, microbes, termites and insects is widely used in the coating and resin industry.
Reference [40] reported that technical CNSL may also contain phytosterol, such as stigma sterol
and β-sitosterol, which have cholesterol-lowering properties.

Cardanol polysulfide (CPS) has been used as a vulcanizing agent for natural rubber as reported
by [41]. Coordination bond linkage in cardanol-aldehyde condensation polymers improved
its physicomechanical properties. This positively influences the anticorrosive properties and
stability of the polymeric compound at high temperature [42]. The blend of cardanol-based
novolac-type phenolic resins, with commercial epoxy or isocynate monomers produces
thermoset polymers [43]. Also, in [44], the conversion of CNSL-based cardols (6-alkenylresor‐
cinols) into lasiodiplodin, a naturally occurring 12-membered orsellinic acid type macrolide,
exhibits plant growth-regulating and antileukemic properties.

Immature CNSL (iCNSL) has excellent protective activities in strains of S. cerevisiae against
oxidative damage induced by hydrogen peroxide and inhibits acetyl cholinesterase activity
[45]. The high in vitro antibacterial activity of cashew nut shell liquid (CNSL) has been
 Cashew Nut Shell Oil — A Renewable and Reliable Petrochemical Feedstock 17
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attributed to its anacardic acid content [46]. Both anacardic acid and cardol were reported to
have antitumor [47-49], antimicrobial [48], urease inhibitory [50] and lipoxygenase activities
[51]. Gram positive bacteria, which cause tooth decay, acne, tuberculosis, Streptococcus
pneumonia, Francisella tularensis, and leprosy are killed by anacardic chemicals [52].
Anacardic acid has also been found to reduce the expression of survivin and X-linked inhibitor
of apoptosis protein, anti apoptotic proteins associated with cellular survival and radio
resistance, and radio-sensitized pituitary adenoma cells [53]. Also, these acids have been used
effectively against tooth abscesses due to their lethality to bacteria.
The monophenolics of CNSL have been found to form stable quaternary nitrogen compounds
which are soluble in water, odourless and act as surface-active agents [54]. These properties
including their high bacterial activity, have made them significantly useful as germicides,
disinfectants and sanitizing agents in food and dairy industries. Also, sodium salts of anacardic
acid, for example disodium anarcadates, are anionic surfactant and could be used as bacteri‐
cidal surfactant while sodium anarcadate is useful for the control of vector mosquitoes which
are responsible for causing dengue fever [55].
Energy studies established that cashew nut by-products CNSL, its isolates and spent CN Shell
compare quite favourably with conventional fuels in terms of energy content. CNSL, cardanol
and cardol, which are liquid by-products, were superior to conventional liquid and solid fuels
while spent CN shell was more superior to a number of liquid fuels, e.g. ethanol and methanol,
as well as fire wood in terms of energy content. This material is advocated for use by cashew
nut processors and other industries as fuel to reduce environmental pollution. This material
is not only a cleaner fuel but also has low ash and is renewable [56].
Substitution of phenol with CNSL in both resol and novolacs decreased the tensile strength,
but improved the impact strength of wood flour-based laminate of these resins. Thermal
properties of phenol-cardanol-based resin depletes with increasing cardanol content in the
resin [57, 58].
The synthesis of polymers from renewable resources has attracted considerable attention
worldwide due to its potential attribute as a substitute for petrochemical feedstock. CNSL may
act as a potential raw material for the manufacture of polymers in the 21st century [58] due to
its components and depletion in petroleum production which increasingly faces exhaustion.
Long-chain, m-substituted phenol in CNSL is highly reactive. Thus a wide variety of resins are
synthesized from CNSL, such as polyesters, phenolic resins, epoxy resins, polyurethanes,
acrylics, vinyls and alkyds to mention a few [59].
CNSL contains four major components: 3-pentadecenyl phenol (cardanol), 5-pentadecenyl
resorcinol (cardol), 6-pentadecenyl salicylic acid (anacardic acid) and 2-methyl 5-pentadecenyl
resorcinol (2-methyl cardol), which can be good replacement for synthetic resins, owing to the
current climate of diminishing petroleum reserves. Cardanol, which is a phenol derivative,
has a meta substitute of a C15 unsaturated hydrocarbon chain with one to three double bonds
[31, 32, 60, 61]. Being a major component of CNSL, its abundant production promised renew‐
able feedstock for the petrochemical industry with a total production of CNS approaching 2.6
million tons annually [1].
18 Advances in Petrochemicals

Resoles and novolacs resins are the major products of reaction of CNSL with formaldehyde.
While novolac results from acid-catalyzed reactions, resoles are a product of base-catalyzed
reactions.

CNSL can be polymerized by different methods. This includes addition polymerization

through the side-chain double-bonds using cationic initiators such as diethylsulphate,
condensation polymerization through the phenolic rings with aldehydic compound, e.g.
formaldehyde, oxidative polymerization, polymerization after chemical modification to
produce specialty properties, etc. The most common method is condensation reaction with
formaldehyde. The CNSL-based polymers offer advantages such as improved flexibility and
reduced brittleness, solubility in organic solvents, improved process ability, compatibility with
other polymers, high performance and resistance to microbes, insects and termites.

CNSL were successfully applied as a thermosetting wood adhesive for wood panels to reduce
formaldehyde emission. These renewable phenolic compounds give excellent adhesive
performance, good moisture resistance and tend to give a lower formaldehyde emission than
UF resin [62, 63].

4.1. Environmental impact

CNSL may be a weak promoter of carcinogenesis but no mutagenic or carcinogenic activity

has been reported [64]. Epidemiological studies suggested that CNSL may contribute to oral
sub-mucous fibrosis [65]. In addition, its phenolic components exerted several biological
activities, including antioxidative properties [66, 67], inhibition of acetyl cholinesterase and
membrane perturbation [68, 69].

There is no direct evidence regarding the toxicity of CNSL or its major phenolic components.
However, the effluent generated during the processing of the cashew nut could be considered
potentially harmful to the environment due to its high phenol content. The hazardous effects
of phenolic compounds have been extensively studied. According to [70], a concentration
above 1 mg/L can affect aquatic life, while [71] recognizes deleterious effects at concentrations
as low as 1 µg/mL.

As previously mentioned, data on the chemical composition of the cashew nut industry
effluent are scarce, but preliminary analysis showed high phenol content due to the cardol,
cardanol and anacardic acid of CNSL. The high toxicity observed for the isolated phe‐
 Cashew Nut Shell Oil — A Renewable and Reliable Petrochemical Feedstock 19
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nols, cardol and cardanol potentially contribute to the toxicity of the cashew nut industry
effluent [72].

5. Conclusion

The report has highlighted various chemicals obtainable from CNSL both directly and
indirectly. This inexhaustible listing presents CNSL as a very important, reliable source of raw
material for petrochemical industry. It is a good, promising supplement and/or alternate to
petroleum, which is currently facing depletion globally.

Varied CNSL compositions with varying modes of extraction are a vantage opportunity with
potential for multiple applications.

Though CNSL contains phenolics, its products are highly environmental friendly. However,
efficient treatment strategy may be inevitable to reduce environmental impact associated with
the production industry.

Acknowledgements

The author is grateful to the laboratory and technical staff of the Department of Chemical
Engineering, Obafemi Awolowo University, Ile-Ife, Nigeria, for the support rendered in
carrying out the work.

Author details

Elijah A. Taiwo*

Address all correspondence to: [email protected],[email protected]

Department of Chemical Engineering, Obafemi Awolowo University, Ile-Ife, Osun State,

Nigeria

References

[1] Subbarao Ch N V, Krishna Prasad K M M, Prasad V S R K. Review on applications,

extraction, isolation and analysis of cashew nut shell liquid (CNSL). The Pharma Re‐
search Journal. 2011; 6(1): 21- 41. DOI:10.1007/s11095-015-1664-8
20 Advances in Petrochemicals

[2] Olife I C, Jolaoso M A, Onwualu A P. Cashew processing for econonic development

in Nigeria. Agricultural Journal. 2013; 8(1), 45 - 50. DOI: 10.3923/aj.2013.45.50.

[3] Patela R.N, Bandyopadhyayb S, Ganesh A. Selective extraction of cardanol and phe‐
nols from cashew nut shell liquid obtained through pyrolysis of cashew nut shells.
In: Proceedings of the Indian Chemical Engineering Congress, Novel Separation
Processes Session (CHEMCON-2005) 14 -17 December 2005; New Delhi, India.

[4] Akinhanmi T F, Atasie V N, Akintokun P O. Chemical composition and physico‐

chemical properties of cashew nut (Anacardium occidentale) oil and cashew nut
shell liquid. Journal of Agriculture, Food and Environmental Sciences. 2008; 2(1),
10pp

[5] Pushparaj T, Ramabalan S. Influence of CNSL biodiesel with ethanol additive on die‐
sel engine performance and exhaust emission. International Journal of Mechanical
Engineering and Technology (IJMET). 2012; 3(2), 665 - 674

[6] Hammed L A, Antique J C, Adedeji A.R. Cashew nuts and production development
in Nigeria. American-Eurasian Journal of Scientific Research. 2008; 3(1): 54 - 61

[7] FAOSTAT data, 2013 (last accessed by www.top5of anything.com: December 2014).

[8] Ojewola G S, Okoye F C, Agbakuru I. Performance value of cashew nut meal for soya
bean meal in finishing broiler chickens. International Journal of Poultry Science.
2004; 3(8): 513-516. DOI: 10.3923/ijps.2004.513.516.

[9] Kozubek A, Tyman J H P. Resorcinolic iipids, the natural non-isoprenoid phenolic

amphiphiles and their biological activity. Chemical Reviews. 1999, 99(1):1 - 25. DOI:
10.1021/cr970464o

[10] Sue Azam-Ali. Cashew nut processing–An overview of delicious cashew nut proc‐
essing and various choices in methods. Technical brief, Practical Action. Schlumacher
centre, bourton on Dunsmore, Rugby, Warwickshire, U.K. 2001, 9 pages.

[11] Patel R N, Bandyopadhyay S, Ganesh A. Extraction of cashew (Anacardium occiden‐

tale) nutshell liquid using supercritical carbon dioxide. Bioresource Technology. 2006;
97: 847–853

[12] Mazzetto S E, Lemonaco D, Mele G. Cashew nut oil: opportunities and challenges in
the context of sustainable industrial development. Química Nova. 2009; 32(3):
732-741. DOI:10.1590/S0100-40422009000300017

[13] Rodrigues F H A, França F C F, Souza J R R, Ricardo N M P S, Feitosa J P A. (2011)

Comparison Between Physico-chemical properties of the technical cashew nut shell
liquid (CNSL) and those natural extracted from solvent and pressing. Polímeros.
2011; 21(2): 156 -160. DOI: 10.1590/S0104-14282011005000028.
 Cashew Nut Shell Oil — A Renewable and Reliable Petrochemical Feedstock 21
http://dx.doi.org/10.5772/61096

[14] Das P, Sreelatha T, Ganesh A. Bio-oil from pyrolysis of cashew nut shell characteriza‐
tion and related properties. Biomass and Bioenergy. 2004; 27: 265 - 275. DOI: 10.1016/
S0961-9534(02)00182-4
[15] Tsamba A J, Yang W, Blasiak W. Pyrolysis characteristics and global kinetics of coco‐
nut and cashew nut shells. Fuel Processing Technology. 2006, 87: 523 - 530. DOI:
10.1016/j.fuproc.2005.12.002
[16] Shobha S V, Ravindranath B. Supercritical carbon dioxide and solvent extraction of
the phenolic lipids of cashew nut (Anacardium occidentale) shells. Journal of Agricul‐
tural and Food Chemistry. 1991; 39: 2214 - 2217. DOI: 10.1021/jf00012a022
[17] Smith R.L, Malaluan R.M, Setianto W.B, Inomata H, Arai K. Bio based manufacture
of alkyl phenols and polysaccharides from cashew nut with supercritical carbon di‐
oxide and water. Bioresource Technology. 2003; 88: 1 - 3.
[18] Yuliana M, Ngoc Yen Tran-Thi, Yi-Hsu Ju. Effect of extraction methods on character‐
istic and composition of Indonesian cashew nut shell liquid. Industrial Crops and
Products. 2012; 35(1): 230 – 236. DOI: 10.1016/j.indcrop.2011.07.007
[19] Patel R N, Bandyopadhyay S, Ganesh A. Economic appraisal of extraction of refined
cashew nut shell liquid through supercritical fluid extraction. Journal of chromatog‐
raphy A. 2006; 1124: 130 -136.
[20] AOAC. Official Methods of Analysis of the Association of Official Analytical Chem‐
ists, Edited by Keneth Helrich, 15th ed. 1990.
[21] Strong F M, Koch G H. Biochemistry laboratory manual. 2nd ed. Dubuque, IA:
W.M.C. Publishers. 1974.
[22] Rodrigues F H A, Feitosa J P A, Nágila M P S, Ricardo F C F, de França A, José O B,
Cario M. Antioxidant activity of cashew nut shell liquid (CNSL) derivatives on the
thermal oxidation of synthetic cis-1,4-polyisoprene. Journal of the Brazilian Chemical
Society. 2006; 17(2): 265 -271. DOI: 10.1590/S103-50532006000200008
[23] Raghavendra Prasada S A. A Review on CNSL biodiesel as an alternative fuel for
diesel engine. International Journal of Science and Research (IJSR). 2014; 3(7): 2028
-2038.
[24] Risfaheri T T I, Nur M A, and Sailah I. Isolation of cardanol from cashew nut shell
liquid using the vacuum distillation method. Indonesian Journal of Agriculture.
2009; 2(1): 11 -20.
[25] Gandhi T, Patel M, Dholakiya B.K. Studies on effect of various solvents on extraction
of cashew nut shell liquid (CNSL) and Isolation of major phenolic constituents from
extracted CNSL. Journal of Natural Product and Plant Resources. 2012; 2 (1): 135
-142.
[26] Buchweishaija J, Mkayula L L. The effect of rotation and temperature on the inhibi‐
tion performance of cashew (Anacardium occidentale L) nut shell liquid on corrosion
22 Advances in Petrochemicals

of carbon steel. Transactions of the Journal Engineering and Technology. 2008; 2(2):
121 -125.

[27] Sanger S H, Mohod A G, Khandetode Y P, Shrirame H Y, Deshmukh A S. Study of

carbonization for cashew nut shell. Research Journal of Chemical Sciences. 2011; 1(2):
43 -55

[28] Velmurugan A, loganathan M. Effect of ethanol addition with cashew nut shell liq‐
uid on engine combustion and exhaust emission in a DI diesel engine. International
Journal of Engineering Science and Technology. 2012; 4(7): 3316 -3328.

[29] Oliveira M S, Morais S M, Magalhães D V, Batista W P, Vieira I G, Craveiro A A, de

Manezes J E, Carvalho A F, de Lima G P. Antioxidant, larvicidal and anti-acetyl chol‐
inesterase activities of cashew nut shell liquid. Acta Tropica. 2011; 117(3): 165-170.
DOI: 10.1016/j.actatropica.2010.08.003

[30] Lomonaco D, Cangane F Y, Mazzetto S E. Thiophosphate esters of cashew nutshell

liquid derivatives as new antioxidants for poly(methyl) methacrylate. Journal of
Thermal Analysis and Calorimetry. 2011; 104(3): 1177 -1183.

[31] Vasapollo G, Mele G, Sole R D. Cardanol based material as natural precursors for
olefin metathesis. Molecules.2011; 16: 6871 -6882. DOI: 10.3390/molecules16086871

[32] Vasapollo G, Mele G, Sole R D, Pio I, Li J, Mazzetto S E. Use of novel cardanol-por‐

phyrin hybrids and their TiO2-based composites for the photodegradation of 4-nitro‐
phenol in water. Molecules. 2011; 16: 5769 -5784. DOI:10.3390/molecules16075769

[33] Fernando José Araújo da Silva and José Everardo Xavier de Matos. A note on the po‐
tential of CNSL in fuel blends for engines in Brazil. Revista Tecnologia. 2009; 30 (1):
89 -96.

[34] Paisal Nakpipat and Hiroo Niiyama Diesel oil from cashew nut shell liquid. Regional
Symposium on Chemical Engineering. 1999.

[35] Solanki J H, Javiya T V. Cashew nut shell liquid fuel a substitute for diesel fuel to be
used in C.I. engine. International Journal of Advanced Research in Science, Engineer‐
ing and Technology. 2012; 1 (2): 8 -12

[36] Ribeiro E A, Fernando Felipe Lopes Antunes, Verônica Teixeira Franco Castelo Bran‐
co, Sandra Aguiar Soares, Jorge Barbosa Soares. Evaluation of moisture damage in
asphalt containing cashew nut Shell liquid (CNSL) modified bitumen. In: Proceed‐
ings of the 5th Euro asphalt & Euro bitumen Congress; 13 -15th June 2012, Istanbul.
10pages

[37] Ganguly A, Raji G. Asbestos free friction composition for brake linings. Bulletin of
Materials Science. 2008; 31(1), 19 -22. DOI: 10.1007/s12034-008-0004-6
 Cashew Nut Shell Oil — A Renewable and Reliable Petrochemical Feedstock 23
http://dx.doi.org/10.5772/61096

[38] Murthy B.G.K, Sivasamban M.A. Recent trends in CNSL utilization. Cashew Re‐
search and Development: Proceedings of the International Cashew Symposium, Co‐
chin, Kerala, India, 1985, 12 -15.
[39] de Lasa H I, Afara S. Processing of cashew nut shell liquid. Final Technical Report;
Mozambique. Chemical Reactor Engineering Centre, Faculty of Engineering Science,
University of Western Ontario, London. August 1, 1995.
[40] Andrade T J A S, Araújo B Q, Citó A M G L, Silva J, Saffi J, Richter M F, Fer-raz A B F.
Antioxidant properties and chemical composition of technical cashew nut shell liq‐
uid (tCNSL). Food Chemistry. 2011; 126(3): 1044–1048. DOI: 10.1016/j.foodchem.
2010.11.122
[41] Leerawan K, Narumon S, Nanthita K, Jumreang T, Sophon R. Cardanol polysulfide
as a vulcanizing agent for natural rubber. Journal of Scientific Research, Chulalong‐
korn University. 2005; 30(1): 23 - 40.
[42] Jinhuo L, Bingham H U. Study on the cardinal-aldehyde condensation polymer con‐
taining boron-nitrogen coordinate bond. Chinese Journal of Polymer Science. 1998;
16(3): 219 -225.
[43] D'Amico D, Martina F, Ingrosso G, Mele G, Maffezzoli A, Tarzia A, Stifani C. Devel‐
opment and characterization of jute reinforced natural matrix composites. Interna‐
tional Journal of Materials and Product Technology. 2009; 36(1 - 4):155 -165. DOI:
10.1504/IJMPT.2009.027827
[44] Santos M L, Magalhães G C. Utilization of cashew nut shell liquid from Anacardium
occidentale as starting material for organic synthesis: A novel route to lasiodiplodin
from Cardols. Journal of the Brazilian Chemical Society. 1999; 10(1): 13-20. DOI:
10.1590/S0103-50531999000100003
[45] De Lima S.G, Feitosa C.M, Citó A.M.G.L, Neto J.M., Lopes J.A.D, Leite A.S, Brito
M.C, Dantas S.M.M, Melo Cavalcante A.A. Effects of immature cashew nut-shell liq‐
uid (Anacardium occidentale) against oxidative damage in Saccharomyces cerevisiae and
inhibition of acetyl cholinesterase activity. Genetics and Molecular Research. 2008;
7(3): 806 -808.
[46] Eichbaum F. Biological properties of anacardic acid and related compounds. Memó‐
rias do Instituto de Butantan. Sao Paulo. 1946; 19:69 -96.
[47] Kozubek A, Zamowski R, Stasiuk M, Gubernator J. Natural amphiphilic phenols as
bioactive compounds. Cellular and Molecular Biology Letters. 2001; 6: 351–355. DOI:
10.2478/s11756-012-0030-0 0.70
[48] Kubo I, Ochi M, Viera P. C, Komatsu S. Antitumor agent from the cashew (Anacardi‐
um occidentale) apple juice. Journal of Agricultural and Food Chemistry. 1993; 41:
1012 -1015. DOI: 10.1021/jf000309035
[49] Melo Cavalcante A A, Rübensam G, Erdtmann B, Brendel M, Henriques J A P. Cash‐
ew (Anacardium occidentale) apple juice lowers mutagenicity of aflatoxin B1 in S. typhi‐
24 Advances in Petrochemicals

murium TA102. Genetics and Molecular Biology. 2005; 28: 328 – 333. DOI: 10.1590/
S1415-47572005000200025.

[50] Kubo J, Lee J R, Kubo I. Anti-Helicobacter pylori agents from the cashew apple. Journal
of Agricultural and Food Chemistry. 1999; 47(2): 533 –537. DOI: 10.1021/jf9808980

[51] Ha T J, Kubo I. Lipoxygenase inhibitory activity of anacardic acids. Journal of Agri‐

cultural and Food Chemistry. 2005; 53(11): 4350 – 4354. DOI: 10.1021/jf048184e

[52] Himejima M, Kubo I. Antibacterial agents from the cashew Anacardium occidentale
(Anacardiaceae) nut shell oil. Journal of Agricultural and Food Chemistry. 1991;
39(2): 418-421. DOI: 10.1021/jf00002a039

[53] Sukumari-Ramesh S, Singh N, Jensen M A, Krishnan M. D, Vender J R. Anacardic

acid induces caspase independent apoptosis and radiosensitizes pituitary adenoma
cells; Laboratory investigation. Journal of Neurosurgery. 2011; 14(6) :1681 -1690.

[54] Gulati A S, Krishnamachar V.S, Subbarao B C. Supercritical carbon dioxide extraction

of Indian cashew nut shell. Indian Journal of Chemistry. 1964; 2: 114 -117.

[55] Farias D F, Cavalheiro M G, Viana S M, De Lima P G, Da Rocha-Bezerra C B, Ricardo

M.P.S, Carvalho F U. Insecticidal action of sodium anacardate from Brazilian cashew
nut shell liquid against Aedes aegypti. Journal of the American Mosquito Control As‐
sociation. 2009; 25(3): 386-389. DOI: 10.2987/08-5851.1

[56] Mwangi P M, Aule C, Thiong’o G T. Energy studies of some cashew nut by-products
in Kenya. International Journal of Advanced Research. 2013; 1(8): 880 -887.

[57] Reghunadhan Nair C P, Bindu R.L, Joseph V C. Cyanate esters based on cardanol
modified-phenol-formaldehyde resins: synthesis and thermal characteristics. Journal
of Polymer Science: Part A: Polymer Chemistry. 1995; 33(4): 621 -627.DOI: 10.1002/
pola.1995.080330403

[58] Bhunia H P, Nando G. B, Chaki T. K, Basak A, Lenka S, Nayak P. L. Synthesis and

characterization of polymers from cashew nut shell liquid (CNSL). European Poly‐
mer Journal. 1999; 35: 1381 -1391. DOI: 10.1016/S0014-3057(98)00225-0.

[59] Balgude D and Sabnis A. S. CNSL: an environment friendly alternative for the mod‐
ern coating industry. Journal of Coatings Technology and Research. 2014; 11(2):
169-18334. DOI: 10.1007/s11998-013-9521-3

[60] Kim Y H, An E. S, Park E. S, Song B K. Enzymatic epoxidation and polymerization of

cardanol obtained from a renewable resource and curing of epoxide-containing poly‐
cardanol. Journal of Molecular Catalysis B: Enzymatic. 2007; 45: 39 - 44. DOI: 10.1016/
j.molcatb.2006.11.004

[61] Bhunia H P, Jana R. N, Basak A., Lenka S, Nando G. B. Synthesis of polyurethane

from cashew nut shell liquid (CNSL), a renewable re-source. Journal of Polymer Sci‐
 Cashew Nut Shell Oil — A Renewable and Reliable Petrochemical Feedstock 25
http://dx.doi.org/10.5772/61096

ence Part A: Polymer Chemistry. 1998; 36(3): 391 - 400. DOI: 10.1002/(SI‐
CI)1099-0518(199802)36:3<391:: AID-POLA3>3.0.CO;2-V

[62] Kim S. The reduction of formaldehyde and VOCs emission from wood-based floor‐
ing by green adhesive using cashew nut shell liquid (CNSL). Journal of Hazardous
Materials. 2010; 182: 919 - 922. DOI:10.1016/j.jhazmat.2010.03.003

[63] Lee J H, Jeon J, Kim S. Green adhesives using tannin and cashew nut shell liquid for
environment-friendly furniture materials. Journal of the Korea Furniture Society. 201;
22(3): 219 -229

[64] George J, Kuttan R. Mutagenic, carcinogenic and cocarcinogenic activity of cashew

nut shell liquid. Cancer Letters. 1997; 112(1):11 -16. DOI: 10.1016/
S0304-3835(96)04540-5

[65] Varghese I, Rajendran R, Sugathan C K, Vijayakumar T. Prevalence of oral sub mu‐

cous fibrosis among the cashew workers of Kerala-South India. Indian Journal of
Cancer. 1986. 23: 101 - 104.

[66] Trevisan M T S, Pfundstein B, Haubner R, Wurtele G, Spiege D, Halder B, Bartsch H,

Owen R W. Characterization of alkyl phenols in cashew (Anacardium occidentale)
products and assay of their antioxidant capacity. Food and Chemical Toxicology.
2006; 44(2): 188-197. DOI: 10.1016/j.fct.2005.06.012

[67] Façanha M A, Mazzetto S A, Carioca J O, Barros G G. Evaluation of antioxidant prop‐

erties of a phosphorated cardanol compound on mineral oils (NH10 and NH20). Fuel
2007; 86(15): 2416 -2421. DOI: 10.1016/j.fuel.2007.01.034.

[68] Stasiuk M, Kozubek A. Membrane perturbing properties of natural phenolic and re‐
sorcinolic lipids. FEBS Letters. 2008; 582: 3607-3613. DOI: 10.1016/j.febslet.2008.09.039

[69] Stasiuk M, Bartosiewicz D, Kozubek A. Inhibitory effect of some natural and semi‐
synthetic phenolic lipids upon acetyl cholinesterase activity. Food Chemistry. 2008;
108: 996 -1001. DOI: 10.1016/j.foodchem.2007.12.011

[70] Veeresh G S, Kumar P, Mehrota I. Treatment of phenol and cresols in up flow anae‐
robic sludge blanket (UASB) process: a review. Water Research. 2005; 39(1): 154 - 170.
DOI: 10.1016/j.watres.2004.07.028

[71] Newman M C, Unger M A. Fundamentals of Ecotoxicology. 2nd ed. Lewis Publishers;

2003. 433 p.

[72] Pimentel M F, De Lima D P, Martins L R, Beatriz A, Santaella S T, Costa Lotufo L V.

Eco toxicological analysis of cashew nut industry effluents, specifically two of its ma‐
jor phenolic components, cardol and cardanol. Pan-American Journal of Aquatic Sci‐
ences. 2009; 4(3): 363 - 368
 Chapter 2

Natural Gas Geochemistry

in the Offshore Nile Delta, Egypt

Mohamed Abdel-Aziz Younes

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/60575

Abstract

The offshore Nile Delta basin is considered as one of the most promising province in
Egypt which has an excellent potential gas and condensate reserves for future
exploration. This study aimed to characterize the origin of natural gas and to
determine whether it is biogenic, thermogenic or mixed processes which are consid‐
ered the dominant generation pathways. Regional geochemical studies were
conducted on 20 test gas samples produced from the Miocene and Plio-Pleistocene
reservoirs of Abu Qir, N. Abu Qir, Temsah, Wakkar and Port Fouad fields represent‐
ing the western and the eastern Nile Delta province. The geochemical analyses
revealed that the main constituents of the natural gases are methane (96.2%–99.37%)
with minor contribution from ethane and propane. Methane carbon isotopic compo‐
sition ranges between _65.6‰ and _40.3 ‰ PDB displaying a strong indication for gas
mixing of thermogenic and early microbial methane. The gas chromatography_mass
spectrometry carried out on the produced natural gases exhibits high oleanane index
that ranges between 19% and 42%, the medium concentration of moretane index
between 11% and 16% and the absence of gammacerane index indicating that the
natural gases were derived from siliciclastic source rocks containing type III kerogen
of terrestrial origin and higher land plants input of Tertiary age. The calculated
maturity parameters of the studied natural gas proportions based on various sterane
isomerisation distributions, i.e. C29αßß/(αßß+ααα)_and C29ααα20S/(S+R) reached 0.6
and 0.5 respectively indicating a medium stage of thermal maturation equivalent to
the main peak of oil generation window (0.85 Ro%). The sterane isomerization ratios
may reflect the rapid rate of subsidence and sedimentation in the Nile Delta and
appear to have been generated during the early stage of source rock maturation.

Keywords: biogenic, thermogenic, Nile Delta, biomarkers, Egypt

28 Advances in Petrochemicals

1. Introduction

1.1. Location of the study area

The Nile Delta and the offshore Mediterranean Sea basin are hydrocarbon rich provinces that
have generated natural gas and condensate from siliciclastic reservoirs ranging in age from
Plio_Pleistocene to Miocene. Currently, these areas are the most active exploration and
development province in Egypt. The proven huge reserves of the Pliocene gas discoveries
made in the last decade firmly established the Pliocene sequence as a primary hydrocarbon
potential target for the exploration activities in the Nile Delta and offshore Mediterranean
region.

The study area lies in the offshore Mediterranean Sea to the north of Alexandria and Port Said
cities within the northern eastern Nile Delta between longitudes 30° 10´- and 32° 54´-E and
latitude 31° 25´- and 32° 00´- N. This area includes four giant natural gas fields namely; Abu
Qir Field located to the north of Alexandria city and Temsah, Wakkar and Port Fouad fields
located 65 kilometers to the north of Port Said in the offshore Mediterranean Sea, about 30 km
from the Egyptian coast (Figure 1).

Figure 1. Location map of the study gas fields, offshore Nile Delta, Egypt.

1.2. Geologic setting and lithostratigraphy

The present Nile Delta lies on the north_external margin of the African plate. Its structural
evolution is largely contemporaneous with the break–up of the African plate margin conse‐
quent to the opening of the Red Sea and the northward transition of the Arabian Peninsula [1,
2]. The northern part of the Nile Delta is characterized by a series of major tectonic features
 Natural Gas Geochemistry in the Offshore Nile Delta, Egypt 29
http://dx.doi.org/10.5772/60575

with different orientations. Some of them are active during the deposition of Tertiary section
while other flatten with depth, become horizontal and dies on top of the Rosetta Formation
affecting only through the Kafr El-Sheikh Formation.
The Nile Delta is characterized by asymmetric fold, overthrust faults and diapers. Its dates
back to the Syrian Arc system having an arcuate trend from northeast to southwest through
the northern part of the Nile Delta to the Western Desert of Egypt (Figure 2).
The regional subsurface stratigraphic succession of the Nile Delta has been represented in
Figure 3. This succession is discussed by many authors [3-11].
The lithostratigraphy of the Nile Delta is represented by Miocene sediments:
Moghra, Sidi Salem and Abu Madi formations (from bottom to top). In addition, the Pliocene–
Pleistocene sequences are represented mainly by shale or clay with sandstone interbeds. The
Miocene sequence is summarized as follows:

Figure 2. Regional structural setting, north Nile Delta from Mosconi et al. [38] and Hemdan et al. [39].

1.2.1. Moghra formation (Early miocene)

Moghra Formation consists of marine to fluvio–marine deposits (shale and sandstone) of
presumed deltaic origin, although it is associated with marine carbonate intervals. This
formation is unconformably overlain by Sidi Salem Formation.

1.2.2. Sidi Salem formation (Middle miocene)

The lower limit of this formation is not known in the central part of the Nile Delta where it
overlies the Moghra Formation to the west and south. Sidi Salem Formation is composed
mainly of mudstone with interbeds of marls, sandstones and siltstones. This formation
30 Advances in Petrochemicals

Figure 3. Lithostratigraphic succession of Northern Nile Delta, Egypt modified from Kamel et al. [8].

corresponds to a lower neritic slope environment. Sidi Salem Formation is unconformably

overlained by Abu Madi Formation.

1.2.3. Abu Madi formation (Late miocene)

Abu Madi Formation is composed of interbedded sandstones and mudstones. This formation
was deposited as an incised valley fill at the end of the Late Miocene. The depositional
environment of Abu Madi Formation changes from fluvial to lagoonal with marine influence
increasing upward.

The Plio- Pleistocene sequences are represented by the following formations.

1.2.4. Kafr El Sheikh formation (Early–middle pliocene)

Kafr El Sheikh Formation consists of mudstone sequence with thin limestone and sandstone
interbeds. This formation extends all over the Delta area. In the Nile Valley it is accumulated
at outer neritic to upper bathyal water depths, following a major lower Pliocene transgression
resulted in the flooding of the former Eonile canyon and transforming it into a long, narrow
gulf far south Aswan [12]. Rizzini et al. [4] suggested that-the Kafr El Sheikh Formation is
accumulated as neritic mudstones on the present onshore delta- and in a basinal setting
offshore. They suggested that the sands incorporated into this formation are essentially storm
sands. This formation is conformably overlain by El Wastani Formation.
 Natural Gas Geochemistry in the Offshore Nile Delta, Egypt 31
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1.2.5. El Wastani formation (Late pliocene)

El Wastani Formation consists of thick sand beds interbedded with thin clay beds which
become thinner toward the top of the formation. This formation is transitional between the
shelf facies of the underlying Kafr El Sheikh Formation and the coastal and continental sands
of the overlying Mit Ghamr Formation. It shows large forests due to the progradation and
could also contain deltaic deposits.

1.2.6. Mit Ghamr formation (Late pliocene)

Mit Ghamr Formation consists of thick layers of sand and pebbles which show clay interbed‐
dings of limited thickness. The depositional environment of this formation is probably shallow
marine to fluvial. It is a typical fill-up basin with coastal sands, coquina beds, clay and peat. It
conformably underlies the Bilqas Formation.

1.2.7. Bilqas formation (Holocene)

Bilqas Formation is the top sedimentary cover of the Nile Delta province. It consists of sand
interbedded with clay rich in pelecypod, gastropod and ostracod fragments. The clays contain
many fragments of vegetal matter and peat deposits. The deposition occurred most likely in
lagoons and brackish swamp, interrupted by beach sands.
During the last two decades, the Nile Delta and the offshore Mediterranean Sea have been
intensively investigated by the petroleum industry. Till now over 36 TCF of gas have been
discovered since drilling began in 1966 [13]. The geologic history of the Nile Delta created
multiple source, reservoir and seal combinations. Main source rocks are believed to occur in
Late Mesozoic and Oligocene to Miocene sedimentary succession.

2. Sampling and analytical techniques

A total of twenty gas samples were obtained through drill stem testing or modular dynamic
testing from 20 wells located in the offshore area of the eastern and western Nile Delta fields
namely, Abu Qir and North Abu Qir from the western Nile Delta while Temsah, Wakkar and
Port Fouad representing the eastern Nile Delta-province and the different reservoir strati‐
graphic ages namely Miocene and Plio-Pleistocene.
The isotopic composition of twenty gas samples was determined in BGR (Bundesanstalt für
Geowissnschaften und Rohstoffe) lab in Hannover. Gas chromatograph (GC Varian CP-3800)
was equipped with a Flame Ionization Detector and a Thermal Conductivity Detector for
separation of gas components (C1–C5) using three capillary columns (First, Silica PLOT 30
m×0.32 mm, Second, CP-Sil 5CB 30 m x 0.32 mm). Permanent gases (atmospheric gas compo‐
nents) were separated using three packed columns (Molsieve-12× 1.5 m ×1/8 in., Hayesep Q
0.5 m ×1/8 in. nickel, and a Hayesep T 0.5 m ×1/8 in. nickel). All six columns are placed in one
oven, heated to 50 °C at the start of the analysis. After 10 min, temperature was increased at
10 °C/ min up to 180 °C, which is held for another 10 min. Finally the oven temperature was
reduced to become 50 °C.
32 Advances in Petrochemicals

Measurements of δ 13C and δ D on the hydrocarbon gases were conducted with a Thermo
Finnigan Delta plus XL mass spectrometer. Gas components were separated on a gas chro‐
matograph and injected into the mass spectrometer. Isotope values are reported in the δ
notation in per mil (‰) relative to the common PDB and SMOW standards.

Data of analysis including gas chromatography, gas chromatography-mass spectrometry were

conducted through Stratochem and Corex Laboratories (New Maadi, Cairo).

3. Results and discussions

3.1. Bulk geochemical characteristics of natural gas

The abundant composition of the natural gases is dominated by methane ranging between
92.72% and 99.96%. The natural gas wetness denoted by the formula C2+/∑(C1_C5 ×100 and
cumulative contents of the higher hydrocarbons from ethane up to pentane range from 0.05%
to 6.76%. According to Schoell [14] the natural_gas may be classified as wet if it exhibits a
wetness index greater than 5%. The natural gas samples examined from the western Nile Delta
can therefore be classified as wet gas, while the major number of gas samples from the eastern
Nile Delta is classified as dry gas except the samples produced from the two wells PSE-1and
DEN-1. Wet gas is thermogenic in origin but associated with condensate in most cases while
the dry gas may have either a microbial or late mature thermal origin [14] or may be related
to that microbial alteration occurring within the reservoirs through the preferential removal
of the C3+ components [15].

Figure 4. Relationship between isoprenoids Pr/n-C17 versus Ph/n-C18 showing source and depositional environments of
the natural gas samples from the two provinces of the Nile Delta from Shanmugam[17]. All the study gas samples are
located within the terrestrial to peat coal source depositional environments.
 Natural Gas Geochemistry in the Offshore Nile Delta, Egypt 33
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The predominance of pristane over phytane (Pr/Ph) ratio was used as an indicator of source
rock depositional environments [16]. The ratio of Pr/Ph was ranged between 2 and 3 for the
natural gas produced from the eastern province indicating fluviomarine and coastal swamp
environment. The same ratio was found to be in the range between 6.4 and 9.4 which indicates
peat swamp depositional environment. Figure 4 summarizes the achieved results concerning
the nature of the source rock depositional environments is strongly supported by the plot of
the isoprenoid ratios Pr/n-C17 versus Ph/n-C18 [17]. It can be seen from this figure that both the
natural gases produced from the eastern and western provinces of the offshore Nile Delta and
Mediterranean Sea are located within the region of terrestrial to peat coal source depositional
environments. The high odd even carbon preference index (CPI > 1) for the studied natural
gas samples from the two provinces reflect the generation from source facies dominating
terrigenous and wax-rich components [18].

Figure 5. Genetic characterization of natural gases using carbon isotopes and C1 / C2 + C3 ratios modified after Ber‐
nard et al.[29] and Faber and Stahl [30].

3.2. Source and maturation dependent biomarker distributions

The results of organic geochemical analyses of twenty gas samples representing the western
Nile Delta province namely, Abu Qir and North Abu Qir fields and the eastern Nile Delta
province, namely Temsah, Wakkar and Port Fouad fields. The results of gas chromatogram
mass fragmentogram of the study gas samples show a predominance of C29 stereoisomers >
50% over C27 regular steranes between 20% and 27% suggestings a significant input of
terrestrial organic matter [19, 20]. Also, the achieved result is strongly supported by the relative
abundance of diasterane index that ranges between 55% and 69% of the study gas samples.
34 Advances in Petrochemicals

All the study gas samples that exhibit higher oleanane index ranging from 19% and 42%
strongly support the enrichment of angiosperm higher land plants input to the siliciclastic
source kerogen which is thought to be derived from Late Cretaceous to Tertiary age [21, 22].
The medium concentration of moretane index in all the study samples ranges between 11%
and 16% and the absence of gammacerane index strongly supports a terrestrial input [23, 24].

Biomarker maturity parameters, include the sterane isomerization ratios_C29 ααα20S/(S+R),

and C29 αßß/(αßß+ααα) which according to Seifert and Moldowan [25] are genetically related
to the effect of thermal maturity processes. The average sterane isomerization ratios C29ααα
20S/(S+R) and C29αßß/(αßß+ααα) of natural gas are 0.6 and 0.5 respectively indicating a
medium stage of thermal maturation equivalent to the main peak of oil generation window
(0.85 Ro%) [18]. The medium sterane isomerization ratios may reflect the rapid rates of
subsidence and sedimentation in the Nile Delta and appear to have been generated during the
early stage of source rock maturation from type-III kerogen [26].

Figure 6. Carbon and Hydrogen isotope ratios of natural gases. Genetic fields according to Schoell[27, 31] and Whiticar
et al. [32].

3.3. Relation between isotopic composition and origin of natural gas

The isotopic composition of natural gas depends on the type and maturity of source rock [27,
28]. Stable isotope geochemistry helps to differentiate the original gas derived from a single
source rock. The methane carbon isotope compositions range between _65.6 ‰ and _ 41.1‰.
Methane hydrogen isotope data ranges from _193 ‰ to _149‰. The isotopically lightest δ 13C
sample was obtained from the SEM-1 well, while the heaviest δ 13C value was received from
 Natural Gas Geochemistry in the Offshore Nile Delta, Egypt 35
http://dx.doi.org/10.5772/60575

AQ-16 well. Many of the δ 13C values have intermediate positions between these end members,
which are consistent with what is commonly interpreted as mixed microbial and thermogenic
gas [14, 28]. A general increase in the δ 13C values with depth from Miocene to Plio-Pleistocene
reservoir is consistent with the increasing thermal maturity and the decreasing relative
concentration of biogenic gas.
The wet gas (C2+) components also display a significant variability in their isotopic composi‐
tions. The δ 13C of ethane (δ 13C2) ranges from _37.5‰ to _27.9‰ but that of propane (δ 13C3)
ranges from _32.2‰ to _11.1‰.
Natural gases become isotopically heavier and contain relatively more methane with increas‐
ing thermal maturity. Thermogenic methane is generally enriched in δ 13C compared with
microbial methane [27].
Figure 5 represents the Bernard plot in which the molecular ratio C1/ (C2 + C3) is plotted versus
methane’s stable carbon isotope ratio according to Bernard et al.[29] and Faber and Stahl [30].
The relationship between these two parameters allows distinguishing microbially generated
methane from thermogenic hydrocarbon gases. The figure provides a strong indication for gas
mixing of thermogenic and early microbial methane.
The δ 13C methane versus δ D methane plot (Figure 6) represents a scheme for the carbon and
hydrogen isotope ratios of methane and their genetic implications. Although this diagnostic
plot was initially established for determining the thermogenic origin of methane [31] it is useful
for the discrimination of microbial methanogenesis, i.e. carbon dioxide (CO2) reduction versus
acetate fermentation [32]. The δ 13C values between _65.6 ‰ to _41.1‰ and δ D values between
_
193 ‰ and _149‰ obtained for the methane of the samples from this study classify methane
as mixtures between thermogenic and biogenic origin. Figure 7 gives a good matching with
the published regional gas data. The relatively heavy hydrogen isotopic compositions (Figure
7) suggest that the microbial gas proportions are probably generated through CO2 reduction
[31, 32].
In the offshore Nile Delta and Mediterranean Sea, the Oligocene to Early Miocene sedimentary
sequence is considered as the primary source of natural gas and condensate characterized as
mixed type II/III kerogen [8, 26].
The isotopic composition of the individual gas components is a function of thermal maturity
of the generated source rock kerogen. Stahl [33] proposed an empirical relationship between
methane carbon isotopic composition and vitrinite reflectance. Berner et al. [34] and Berner
and Faber [35] illustrated a model between the carbon isotopic compositions of methane,
ethane, and propane and source rock maturities represented by vitrinite reflectance measure‐
ments. In this study we used the isotope maturity models developed by Berner and Faber [35]
to estimate the type and maturity of the precursor (source) material (Figures 7and 8). The
geochemical characteristics of natural gas from the Nile Delta indicating a derivation from
source rocks rich in terrestrial precursors [8, 36, 37]. Consequently, the admixture of light
microbial methane to the thermogenic hydrocarbon gas takes place during secondary proc‐
esses, such as migration, microbial oxidation, or mixing. These processes usually affect the gas
properties within the reservoir [28, 40].
36 Advances in Petrochemicals

Figure 7. Isotopic composition of methane and ethane in natural gases of the western and eastern Nile Delta. The ma‐
turity line is according to Berner and Faber [35]. The terrestrial organic matters indicate the maturity of the source rock
in vitrinite reflectance measurements

Figure 8. Isotopic composition of ethane and propane in natural gases of the western and eastern Nile Delta. The ma‐
turity line is according to Berner and Faber [35].

Isotopic compositions of ethane and propane from the west and east Nile Delta samples proved
their mixing origin and derivation from terrestrial organic matter with a source rock maturity
between 0.1% and 2.0% Vitrinite Reflectance measurements.
 Natural Gas Geochemistry in the Offshore Nile Delta, Egypt 37
http://dx.doi.org/10.5772/60575

4. Summary and conclusions

The molecular and isotopic composition of twenty natural test gas samples produced from the
Miocene and Plio-Pleistocene reservoirs of Abu Qir, N. Abu Qir, Temsah, Wakkar and Port
Fouad fields representing the western and the eastern Nile Delta province were used to
examine the generation and alteration of natural gas and condensate accumulations. The
geochemical analyses revealed that the main constituents of the natural gases are methane
96.2–99.37% with minor contribution from ethane and propane. Methane carbon isotopic
composition ranges from _65.6‰ to _40.3‰ PDB displaying a strong indication for gas mixing
of thermogenic and early microbial methane. The gas chromatography_mass spectrometry
carried out to the produced natural gases exhibit high oleanane index that ranges between
(19% and 42%), a medium concentration of moretane index between 11% and 16% and the
absence of gammacerane index and predominance of C29 stereoisomers > 50% over C27 regular
steranes (between 20% and 27%) and a high diasterane index that ranges between 55% and
69%. The above mentioned results pointed out that the natural gases were derived from
siliciclastic source rocks containing type-III kerogen of terrestrial origin and higher land plants
input from Late Cretaceous to Tertiary age. The calculated maturity parameters based on
various sterane isomerisation ratios, i.e.C29αßß/(αßß+ααα)and C29ααα20S/(S+R) reached to 0.6
and 0.5 respectively indicating a medium stage of thermal maturation equivalent to the main
peak of oil generation window (0.85 Ro%). The medium sterane isomerization ratios may
reflect the rapid rates of subsidence and sedimentation in the Nile Delta and appears to have
been generated during the early stage of source rock maturation.

Acknowledgements

The author wish to express the deepest gratitude to the management of the Western Desert
Operating Petroleum Company (Wepco) and Belayim Petroleum Company (Petrobel) for
providing test gas and condensate samples to accomplish this work. Sincere thanks and
gratitudes are also due to the Egyptian General Petroleum Corporation (EGPC) for granting
the permission to publish this paper.

Author details

Mohamed Abdel-Aziz Younes*

Address all correspondence to: [email protected]

Geology Department (Moharrem Beck), Faculty of Science, Alexandria University,

Alexandria, Egypt
38 Advances in Petrochemicals

References

[1] Said R., (1962) The Geology of Egypt: Elsevier, Amsterdam, pp. 337

[2] Said R., (1981) The geology and evolution of the River Nile: Springer, New York,
N.Y., 151 p.

[3] Ross, D. A., and Uchupi E., (1977) Structure and sedimentary history of southern
Mediterranean Sea-Nile cone area: Am. Ass. Petrol. Geol. Bull., Vol. 61, p. 872–902.

[4] Rizzini, A., Vezzani, F., Cococcetta V., and Milad, G., (1978) Stratigraphy and Sedi‐
mentation of A Neogene-Quaternary section in the Nile Delta area, (A.R.E.). Mar. Ge‐
ol., vol. 27, p.327–348.

[5] Zaghloul Z. M., EL Shahat A., and Hegah, O., (1980) Mineralogy of the Tertiary–Qua‐
ternary subsurface sediments, West Nile Delta area. Egypt. Jour. of Geology, vol. 24,
p.177–188.

[6] Helmy, M., and Fouad, O., (1994) Prospectivity and play assessment of Abu Qir area,
Nile Delta, Egypt. EGPC, 12th Petroleum Exploration and Production Conference,
Cairo, vol. 1, 17, pp. 276–292.

[7] Sarhan, M., Talaat, M., Barsoum, K., Bertello, F., and Nobili, M., 1996. The Pliocene
play in the Mediterranean offshore: Structural setting and growth faults controlled
hydrocarbon accumulations in the Nile Delta basin. A comparison with the Niger
Delta basin. EGPC, 13th Petroleum Exploration and Production Conference, vol. 1,7,
p. 121–139.

[8] Kamel, H., Eita, T. and Sarhan, M., (1998) Nile Delta hydrocarbon potentiality. EGPC,
14th Petroleum Exploration and Production Conference, vol. 2, pp. 485–503.

[9] El Barkoky, A., and Helal, M., (2002) Some Neogene stratigraphic aspects of the Nile
Delta. Mediterranean offshore conference. MOC, 2002.

[10] Dewidar Kh. and Frihy, O. (2007) Pre- and post-beach response to engineering hard
structures using Landsat time-series at the northwestern part of the Nile Delta,
Egypt : Journal of Coast Conservation vol. 11: pp. 133–142.

[11] Dewidar Kh. and Frihy, O. (2010) Automated techniques for quantification of beach
change rates using Landsat series along the North-eastern Nile Delta, Egypt: Oceano‐
grapic and Mar. Sci., Vol. 1(2) pp. 028-039.

[12] Chumakov, I. S., (1967) Pliocene and Pleistocene deposits of the Nile Vally in Nubia
and Upper Egypt. Doki. Akad. Nauk. SSSR., p. 5–170.

[13] Dolson, J.C., Boucher, P.J., Dodd, T., Ismail, J., (2002) Petroleum potential of an
emerging giant gas province, Nile delta and Mediterranean Sea o. Egypt. Oil and Gas
Journal, 32–37.
 Natural Gas Geochemistry in the Offshore Nile Delta, Egypt 39
http://dx.doi.org/10.5772/60575

[14] Schoell, M., (1980) The hydrogen and carbon isotopic composition of methane from
natural gases of various origins. Geochimica et Cosmochimica Acta v.44, pp. 649–
662.

[15] James, A.T., Burns, B.J., (1984) Microbial alteration of subsurface natural gas accumu‐
lations. Am. Ass. Petr. Geol. Bulletin v. 68, pp.957–960.

[16] Lijambach, G.W., (1975) On the origin of petroleum. Proceeding of the 9th World Pe‐
troleum Congress, Applied Science Publisher, London. 2, 357-369.

[17] Shanmugam, G. (1985) Significance of coniferous rain forests and related oil, Gipps‐
land Basin, Australia. Am. Ass. Pet. Geol. Bulletin, 69, 1241-1254.

[18] Peters, K. E. Snedden, J. W., Sulaeman, A., Sarg, J. F. and Enrico, R. J. (2000) A new
geochemical sequence stratigraphic model for the Mahakam delta and Makassar
slope, Kalimantan, Indonesia: Am. Ass. Pet. Geol. Bulletin, 84, 12-44.

[19] Huang, W.Y. and Meinschein, W.G., (1979) Sterols and ecological indicators: Geo‐
chim. et Cosmochim. Acta, v. 43, p.739-745.

[20] Huang, H. P. (2000) The nature and origin of petroleum in the Chaiwopu Sub-Basin
(Jungar Basin) N. W. China. Journal of Petroleum Geology, v. 23, pp. 193-220.

[21] Ekweozor, C. M., Okogun, J. I., Ekong, D.E.U. and Maxwell, J. R. (1979) Preliminary
organic geochemical studies of samples from the Niger Delta (Nigeria). Analyses of
crude oils for triterpanes. Chemical Geology, 27, 11-29

[22] Moldowan, J.M., Dahl, J., Huizinga, B. and Fago, F., (1994) The molecular fossil re‐
cord of oleanane and its relation to angiosperms. Science 265, 768-771.

[23] Connan, J., Bouroullec, J., Dessort, T. D. and Albrecht, P. (1986) The microbial input
in carbonate anhydrite facies of sabkha environment from Guatemala; A molecular
approach In : Leythaeuser, D. and Rullkotter, J. (Eds.) Advances in Organic Geo‐
chemistry, 1985. Oxford-Pergamon, 20-50.

[24] Mann, A. L., Goodwin, N. S. and Lowes, S. (1987) Geochemical characteristics of la‐
custrine source rocks: A combined palynological - molecular study of Tertiary se‐
quence from offshore China. In Proced. Indonesian Petroleum Association, 16th
Annual Convention, Jakarta, 241-258.

[25] Seifert, W.K. and Moldowan, J. M. (1981) Paleoreconstruction by biological markers.

Geoch. et Cosmoch. Acta, 45, 783-795.

[26] Sharaf, L.M. (2003) Source rock evaluation and geochemistry of condensates and nat‐
ural gases, offshore Nile Delta, Egypt. Journal of Petroleum Geology, V.26(2), pp.
189-209.

[27] Schoell, M., (1984) Stable isotopes in petroleum research. In: Brooks, J.B., Welte, D.
(Eds.), Advances in Petroleum Geochemistry, vol. 1. Academic Press, London, pp.
215–245.
40 Advances in Petrochemicals

[28] Whiticar, M.J., (1994) Correlation of natural gases with their sources. In: Magoon,
L.B., Dow, W.G. (Eds.), The Petroleum System From Source to Trap, vol. 60. Am. Ass.
Pet. Geol. Memoir, pp. 261–283.

[29] Bernard, B., Brooks, J.M. and Sackett, W.M., (1978) Light hydrocarbons in Recent
Texas continental shelf and slope sediments. Journal of Geophysical Research vol. 83,
4053–4061.

[30] Faber, E. and Stahl, W., (1984) Geochemical surface exploration for hydrocarbons in
the North Sea. Am. Ass. Pet. Geol. Bulletin vol.68, pp.363–386.

[31] Schoell, M., (1983) Genetic characterization of natural gases. Am. Ass. Pet. Geol. Bul‐
letin vol.67, 2225–2238.

[32] Whiticar, M.J., Faber, E., Schoell, M., (1986) Biogenic methane formation in marine
and fresh water environments: CO2- reduction vs. acetate fermentation – Isotope evi‐
dence. Geochim. et Cosmochim. Acta 50, 693–709.

[33] Stahl, W.J., (1977) Carbon and nitrogen isotopes in hydrocarbon research and explo‐
ration. Chemical Geology 20, 121–149.

[34] Berner, U., Faber, E., Scheeder, G., Panten, D., (1995) Primary cracking of algal and
land plant kerogens: kinetic models of isotope variations in methane, ethane and pro‐
pane. Chemical Geology 126, 233–245.

[35] Berner, U. and Faber, E., (1996) Empirical carbon isotope/maturity relationships for
gases from algal kerogens and terrigenous organic matter, based on dry, open-sys‐
tem pyrolysis. Oganic Geochemistry 24, 947–955.

[36] Wever, H.E., (2000) Petroleum and source rock characterization based on C7 star plot
results: examples from Egypt. American Association of Petroleum Geologists Bulle‐
tin 84, 1041–1054.

[37] Vandre´, C., Cramer, B., Gerling, P., Winsemann, J., (2004) The geochemistry of natu‐
ral gas and condensates from the western o.shore Nile delta, Egypt. In: Proceedings
of the DGMK Conference, Celle, Germany, pp. 371–380.

[38] Mosconi, A., Rebora, A., Venturino, G., Bocc, P., and Khalil, M. H., 1996. Egypt – Nile
Delta and North Sinai Cenozoic tectonic evolutionary model. EGPC, 13th Petrol. Exp.
Prod. Conf., Cairo, vol. 2, p. 203–223.

[39] Hemdan, K., El Alfy, M., Enani, N., Barrasi, M., and Monir, M., (2002) Structural
Complexity of Pliocene and its Impact on Trapping Mechanism, N. Port Said Conces‐
sion, Egypt. Mediterranean offshore conference. (MOC, 2002).

[40] Claudius, V., Bernhard, C., Gerling, P.and Winsemann, J. (2007). Natural gas forma‐
tion in the western Nile delta (Eastern Mediterranean): Thermogenic versus microbi‐
al. Organic Geochemistry v.38, pp. 523–539.
 Chapter 3

Synthesis of Nanostructured
Materials for Storing Hydrogen as an
Alternative Source to Fossil Fuel Derivatives

Omar Reyes-Martínez and

José Luis Velázquez Ortega

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/61076

Abstract

The decline in global reserves of fossil fuels due to the increasing energy demand has
caused the petrochemical industry to be interested in finding new energy sources. An
alternative that should be considered is the technology based on hydrogen as it is
friendly to the environment and its combustion is greenhouse.

The technology based on hydrogen considers the synthesis of metal-organic materials

that have the ability to store, although this phenomenon (storage) is one of the biggest
problems to overcome. For this reason, options synthesized for storing materials are
provided in this chapter of Book Two. These materials are considered nanostructured
systems with specific features in 2D and 3D. The synthesized materials are tetracyano-
niquelates ( [M (H2O)2 (Ni (CN)4) (H2O)n M = manganese, cobalt, and nickel) and
hexacyano-cobaltates ((M3 [Co (CN) 6] 2xH2O); M: manganese, nickel, cobalt, zinc,
cadmium, and copper), both systems with individual cavities that require study and
characterization. Moreover, in this chapter, a thermogravimetric characterization is
performed in order to establish the activation energy of the mobility of water
molecules contained in the cavities, relevant information to establish the energy
barrier to overcome in the storage of hydrogen.

Keywords: Fossil fuel, hydrogen, nanoporous, thermogravimetry, activation energy

44 Advances in Petrochemicals

1. Introduction

In recent years, micro-porous and nanocomposites have been wide, and there are special
interests in specific areas in order to generate improved technological processes such as
separation, gas adsorption, ion exchange, and heterogeneous catalysis, to mention some of
them [1, 2].
Particularly in the separation and gas adsorption area in microporous and nanosystems,
research has focused on hydrogen’s adsorption and storage as an alternative energetic
alternative resource since this element might become a long-term fossil fuel substitute because
its caloric power is three times higher than gasoline (142 kJ/mol). It is noteworthy that when
the hydrogen is at room temperature in its supercritical state (Tc = 32.7 ° K), storage is difficult,
hence the importance of finding new porous materials having cavities with the ability to store
it safely. Similarly, once stored, it can be used in mobile systems (automotive), avoiding the
production of greenhouse gas emissions [3].
Studies on porous media properties have focused mainly on inorganic materials such as
zeolites or carbon-based materials such as activated carbons, the last one having a high porosity
on one side and an irregular pore, while zeolites have opposite characteristics [4].
In order to generate a material having defined pores and specific physicochemical properties,
the interest is held in the synthesis of new porous materials showing specific conditions from
defined synthesis models, examples of these are as follows: (i) layered systems (2D), tetracya‐
no-niquelates attached to a metal transition [M (H2O)2 (Ni (CN)4) n (H2O)], M = Co, Ni, Mn,
known as Hoffmann-type compounds; and (ii) latticed porous materials, hexacyano-cobaltates
bound to a transition metal [M3 [Co (CN)6] 2 nH2O], M = Co, Ni, Mn, Cd, Cu, Zn, known as
Prussian blue analogue materials.
The importance of lamellar materials known as two-dimensional (2D) lies in the ability to
include molecules in their interlamellar spaces known as guest molecules, with the sole
purpose of generating pores or cavities with specific characteristics according to the same
properties of the included molecule, generating a three-dimensional network, in addition, to
be able to store various molecules such as H2 and CO2 in the pores obtained. The transformation
of a layered structure in a porous structure throughout a molecular spacer insertion was first
introduced into the clay mineral smectite to overcome the limitations of the size of the cavities
in zeolites for the new materials obtained [5].
The proposed 2D systems have water molecules between the sheets, joined by the system for
various attractive forces. There are two types of water molecules included in the material, some
are called coordinated water molecules, which are forming bonds with transition metals
present in the sheets and play the role of guest molecules to form the pillars of the final
structure. Additionally, there are others known as zeolitic water, which are placed in the
cavities or interlamellar region linked by hydrogen bond type interactions.
The water molecules (coordinated and zeolite) are also in the hexacyano-cobaltates, but the
interaction with the system is weaker so the energy required to abandon the system is lower
compared with the 2D systems.
 Synthesis of Nanostructured Materials for Storing Hydrogen as an Alternative Source to Fossil Fuel Derivatives 45
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Another important feature of layered systems is its ability to crystallize into three different
phases known as L0, L1, and K [6, 7, 8]. All the structures contain water molecules between
blades, and each phase has a different number of water molecules. The structural configuration
that adopts the set of water molecules and its interaction with the crystal lattice is the cause of
the three different phases.

Latticed porous materials are crystallized in a cubic cell (Fm-3m) and have between 10 and 13
water molecules (coordinated zeolite) per unit cell. In these structures, the transition metals
(Co, Mn, Cd, Zn, Cu, and Ni) have the center of inversion, and Ni atoms are in a plane of
symmetry [7]. Known latticed porous materials (hexacyano-cobaltates) as Prussian blue
analogue materials are interesting to form windows and pore volumes suitable for the
separation and storage of small molecular forms, as in the case of the hydrogen molecule [9,
10]. In both families, the main objective is to generate materials that provide these properties
and specific characteristics such as pore size, shape of the window, pore volume of adsorption,
etc., as this will dictate whether it is a functional material to be used as molecular sieve to catch
species among its pores.

Once the structures of porous materials are defined, the property characterization of these is
critical because it will determine whether the guest molecules may or may not remain in such
pores. For this reason, special emphasis must be taken on the study of the interactions of the
water molecules (coordinated and zeolitic water molecules) partially hosted on both materials
and kinetic parameters involved in the dehydration process.

In the study of kinetics and their associated parameters, one of them is activation energy
(Ea), which is the most relevant to study without leaving physicochemical aspects such as
thermal stability and structural systems obtained from different aspects. There are several
forms of useful characterization to define the structures and properties of materials under
study. The use of thermal analysis is a fundamental technique, especially supported by
high-resolution modulated thermogravimetric analysis (Hi/ResMTGA) supplemented with
the technique of X-ray diffraction (XRD), which is the immediate basic characterization to
provide relevant information and thus provide the monitoring structural changes during
dehydration processes.

2. Porous systems

At the end of the 1990s, there were basically two types of porous materials: inorganic and
carbon derivatives. In the case of the former, the two most important subclasses of materials
with open structures are aluminosilicates (zeolites) and aluminophosphates (AlPO4s); whose
crystalline lattices offer permanent porosity to be stable before the removal of molecules of
water of hydration. The market of zeolites is of several million tons per year, and it has success
in a wide range of applications, especially in the petrochemical industry and the hydrocarbon
separation, purification of gases and liquids, and the catalytic fragmentation of chain hydro‐
carbons long. Additionally, they have also been applied in ionexchange as detergent additives
46 Advances in Petrochemicals

and the separation of gases and solvents, for example, as "molecular sieves” to the dehydration
of organic solvents.

In the case of activated carbons, they have large specific surface area as well as high porosity;
however, they have a disordered structure. These materials are widely used in the processes
of separation, catalytic converters, capacitors, storage of gas, and biomedical engineering
applications [11].

2.1. Zeolites

Zeolites have been widely studied because of their H2 storage capacity. For equal surface areas,
there is a smaller capacity of absorption in the case of zeolites in comparison with the ones
which are bases on carbon structures.

Zeolites have structures mostly mesoporous, with volumes of relatively small microporous,
which make them the least promising materials based on H2 storage, as referred to in [12].
Their abilities range from 2% to 2.5% based on the weight of the lattice. Zeolites are crystalline
aluminosilicates with a structure consisting of a three-dimensional combination of TO4-
tetrahedra (T =Si, Al) linked together via oxygen atoms. The structural formula of zeolites can
be expressed as [13] Mx/n [(AlO2)x (SiO) and]. wH2O, where M is the exchangeable cation, n is
the cation’s valence, (x, and) are the total number of tetrahedra per unit cell, and w is the number
of water molecules. The structure of zeolites presents channels and cavities of molecular
dimensions, which are water molecules, adsorbates, and compensating cations’ charge
(negative charge created by the presence of AlO4 structure). These channels and cavities give
zeolites a porous structure, which allows these materials to have a very large internal surface
compared to the external.

Some zeolitic materials pass through an intermediary laminating these precursors during their
training, evidenced by their X-ray diffractogram. Zeolitic laminars are attractive candidates
for pillarization processes, which could result in very interesting features such as microporous
sheets and activity type zeolite, together with their properties such as mesoporous adsorbents.

Leonowicz et al. [14] proposed two sets of independent pores for the so-called zeolite MCM-22
type. One of the systems of pores is defined by sinusoidal and bidirectional channels; the other
consists of large supercavities with a 7.1-Å free inner diameter A and an internal height of 18.2
Å. Figure 1 schematically illustrates the structure of MCM-22, where you can see the two
systems of pores.

2.2. Structures of carbon-based materials

Materials with carbon-based structures offer potential to adsorb H2, values of relatively low
density, appropriate chemical stability, and large pore structure, and they can be found in a
wide variety of structural forms. These forms are closely related to the conditions of synthesis,
carbonization, and activation, employed during its preparation [15]. Among the materials
based on carbon are the so-called activated carbons (AC). In this type of material, the existence
of a porous structure is determined by the spatial arrangement of the grapheme, which can be
 Synthesis of Nanostructured Materials for Storing Hydrogen as an Alternative Source to Fossil Fuel Derivatives 47
http://dx.doi.org/10.5772/61076

Figure 1. Diagram of the zeolite MCM-22 structure [1].

stacked to give place to the development of a porous structure relatively little polar. The
adsorption/desorption processes of H2 in such materials are characterized by a relatively rapid
kinetics, and corresponding isotherms are hysteresis, in which results are attractive in systems
that require a high-speed H2 loading and unloading. However, the use of these materials is
limited by highly dependent temperature and pressure adsorption capabilities [16, 17].

In materials based on structures of carbon, whose surface is not chemically modified, the
physical adsorption of H2 is only due to the existence of weak van der Waals adsorbent–
adsorbate interactions. At environmental temperature, the energy corresponding to these
interactions is similar to the energy of the thermal motion of the molecules of the gas, so by
only decreasing the temperature, the adsorbent–adsorbate interaction energy becomes greater
than the thermal movement, which decreases proportionally with the temperature [18, 19].

It has been reported that at low pressures, the amount of adsorbed H2 increases with the
increasing density in carbon nanostructures because the pores favor narrowing H2–
surface interactions. At high pressures, the specific surface area available for the adsorp‐
tion of H2 is the determining factor, and the amount adsorbed increases by decreasing the
material density [20].

2.3. Layered systems

Lamellar materials are solids with two-dimensional structures possessing atoms firmly linked
together in two directions of space forming foil (planes), and they are weakly linked in the
perpendicular direction among them. The region of weak interaction between the sheets is
normally known as interlamellar region or gallery [21]. Many kinds of solid lamellar blades
have electric charge due to substitutions of isomorphic ions of different network load. To reach
the electrical neutrality of the structure, ions of opposite charge, normally solvated by water
or other polar molecules, occupying the interlamellar region, are known as compensation ions.
Layered solids have high surface areas between 100 and 1000 m2/g. In many cases, the
48 Advances in Petrochemicals

interlamellar surface is accessible only to water and other small polar molecules that are
capable of solvated ions of compensation.

The elimination of molecules of solvation by degassing at elevated temperatures results in a

collapse of the interlamellar region, especially if interspersed compensating charge ions are
small in relation to the occupied space; on the other hand, if the compensating charge ions are
relatively large, they can have the role of pillars and prevent the collapse of the interlamellar
regions when the middle of solvation is eliminated, resulting in solids called solid lamellar
pillars. Figure 2 presents a system that shows some characteristics of layered solids.

Figure 2. Representation of a layered solid pillared, wherein pores are defined by the height of the interlamellar space
(d2) and the lateral spacing (d1) between the guest molecules or pillars (P). R denotes the interlamellar region.

Laminar solid pillars can be described as sandwich compounds serving three important
criteria:
1. Interlamellar species must be sufficiently robust to promote the vertical expansion of the
blades (d2) and to prevent their collapse during any thermal process to which they are
subjected.

2. The pillars must be sufficiently separated (d1) to allow access to molecules. Simply
expanding the blades to molecular size, collation of pillars, is not significant in relation to
the properties of adsorption and catalytic behaviour of solid if the interlamellar region is
fully occupied by pillars.

3. The blades must be rigid enough to maintain the separation desired between pillars.
Otherwise, the flexibility of the blades could close gaps between pillar and pillar.
Lamellar surface area presented by solids (between 100 and 1000 m2/g) makes these materials
an object of study important above all in the area of nanoscience and nanotechnology because
they have been shown to generate opportunities in different fields of application, such as
biomedical electronics, applications in the area of storage and energy conversion, and catalysis
[22].

2.3.1. Host molecules (pillarization)

The basic function of the pillarization is to include molecules in the interlamellar region to
obtain a three-dimensional porous system with well-defined and specific characteristics
according to the material or molecules that are embedded as a result. The interaction host
 Synthesis of Nanostructured Materials for Storing Hydrogen as an Alternative Source to Fossil Fuel Derivatives 49
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species with active sites, which are normally present on the surface of the plates, is the driving
force of the mechanism of formation of pillars in a structure laminating. These sites may be
crystallographic positions or groups influenced by positive or negative charges, or sites with
acid, basic, or polar character in general. The density of active sites on the surface on one side
of the blade is expressed by the number of sites per cm2 of surface layer.

The reciprocal value of the density of surface represents the average area per active site. This
value, also called free area, is an important characteristic of a laminated solid. Knowing this,
it is possible in many cases to predict whether the full collation of guest molecule stoichiometry
is viable or not. In nature, the surface density and availability of the active sites is usually the
same on both sides of the layers. However, in some cases, there are asymmetric blades.

The layout of the active sites in each side of the blade and its free area can be determined
precisely when the blade structure is known.

In general, the pillarization process variables are as follows [23]:

1. Properties of the material, such as composition and location of the load on the blade

2. Nature of the agent formed with pillars

3. Ion exchange process

4. Subsequent treatments such as drying, cleaning, etc.

The most important parameters affecting the formation and the properties of the polynuclear
cations as agent formed with pillars are as follows [24]:
a. Metal ion concentration

b. Basicity or degree of hydrolysis

c. Preparation temperature

d. Time and temperature aging

e. Method of preparation
The water molecules in some materials tend to be regarded as pillars of the same due to
interactions that generate with the transition metals present, and the study of these molecules
provides information of the nature of the material.

Pillar materials include clay Al-montmorillonite and the Al-bentonite, which is used in gas-oil
cracking and reactions of phenols hydroxylation reactions, respectively.

2.3.2. Tetracyano-metallates

In recent years, great efforts have been devoted to research directed toward the synthesis and
characterization of multidimensional metal complexes with cyanide bridge groups [25]. The
most common and controlled strategy at the time of preparing this type of system is in
autoassembly specifically designed predecessors. They are normally used as a complex
50 Advances in Petrochemicals

cyanometallate that acts as a ligand and a complex of a metal transition coordination position
for atoms of nitrogen from the groups free of cyanide (see Figure 3).

Figure 3. Assembly blocks of cyanometallate systems: (a) the anionic block [M (CN)6]3-, (b) the cationic block [M´L2]n+.

Tetracyano-metallates and hexacyano-metallates (Prussian blue analogues) are part of the

materials with cyanide bridge group. Anion cyano (CN-) is a functional group with the ability
to be simultaneously coordinated by both atoms at different cations. This makes it an excellent
molecular block to generate different lattices structural at 1, 2, and 3 dimensions. The chemical
bond in the cyanometallate in networks is the linear bridge M-CN-M; M = metal, with a distance
M–M approximately 5 to 6 Å.

When linear polyhedron [Ag (CN)] acts as a binding between two centers of greater coordi‐
nation, the others are connected to 2D or 3D networks [26]. In the union of blocks, the same
metal center generates various structural patterns, showing the variability of crystal structures.
There are other types of binders such as NH3 and H2O, which play an important role in the 3D
structure stabilization and the volume of empty space that is occupied by species guests.

The initial structure of compounds including cyanometallate [Ni (CN) 4]2. The flat square is
the clathrate of Hoffmann’s formula [Ni (NH3) 2Ni (CN) 4], where a 2D network shares a corner
in units of [Ni (CN) 4]2, separated by NH3 binders. The resulting structure is in 2-dimensional
(2D) structure, with the distance between blades occupied by the guest of benzene molecules
that are perpendicular to the blades.

Materials with transition metals have been developed, which provide specific features to the
two-dimensional network for the sole purpose of including pillars to further the creation of
the same form, providing structures with defined pore and known dimensions. Such is the
case of the tetracyano-niquelates. Although they are based on the principle of a structure-type
Hoffmann, including transition metals such as Co, Mn, and Ni, the result is to have water
molecules in the central part or interlamellar, which serve as pillars of the main structure.

The formation of tetracyano-niquelates involves square plane anion [Ni (CN) 4]2, with four
sites attached to metal ions M = Ni, Co, Mn, via the nitrogen atoms of the cyano group. To have
the octahedral geometry, the block has two further binders. For this particular case, those
 Synthesis of Nanostructured Materials for Storing Hydrogen as an Alternative Source to Fossil Fuel Derivatives 51
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additional ligands bind to water molecules to complete the coordination sphere as shown in
Figure 4. The consecutive joining molecular building blocks of this two-dimensional space can
build a two-dimensional structure.

Figure 4. Schematic representation of the assembling process for obtaining K, L1, and L0 phases. The zeolite-like water
molecules are highlighted with open circles in the interlayer region.

2.4. Prussian blue analogues

Historically, the “iron blue” is known as (ferric ferrocyanide) “soluble” Prussian blue and the
blue is known as “insoluble” Turnbull (ferrous ferrocyanide); however, all recent studies
conclude that both are identical. The formation of this pigment can be written as

4-
4 éëFe ùû ac + 3 éëFe ( CN )6 ùû ® Azul de Prusia, Fe 4 éëFe ( CN )6 ùû xH 2 O ( x = 14 - 16 )
3+

( ) ( ac ) 3

Its low solubility evidence is the polymeric nature of the solid product. Due to the 4:3 ratio of
Fe (III) and Fe (II), 25% of the sites of Fe (II) are vacant. The occurrence of more than one
oxidation state of the same element in a particular compound is defined as a mixture of valence.
Due to the partial relocation of electrons from valence, the Prussian blue is a semiconductor.
52 Advances in Petrochemicals

Depending on the properties desired in the product, many routes of preparation are known.
Given its porous nature, it has a certain zeolitic character, which allows you to store small
molecules in their cavities [27].
They have now developed materials under the same principle of formation of Prussian blue
by changing the formation of anionic block metals. The hexacyano-cobaltates (of the family of
the hexacyano-metallates) are an example of these materials considered as Prussian blue
analogues.

2.4.1. Hexacyano-metallates
The hexacyano-metallates of the transition metals are microporous molecular family, whose
structures are based on a three-dimensional arrangement of chains M-C≡N-M. Metal M (inner
metal), linked to the carbon atom, is always forming octahedral molecular blocks [Mn + (CN)
6] as the metal M (external metal) acts as an assembler of the octahedral blocks and possibly
6-n

octahedral or tetrahedral coordination [28, 29].

The first studies of H2 adsorption in this polymer-coordinated family were published in 2005,
simultaneous with the reports of Long et al. [30] and Kepert et al. [31], who studied the formula
of general Prussian blue analogues M3 [Co (CN)6]2, known as hexacyano-cobaltates as the
internal metal cobalt and being able to change the external metal; M= Mn, Fe, Co, Ni, Cu, Zn,
and Cd.
Figure 5 shows the structure of a Prussian blue analogue in the cubic phase due to the
octahedral coordination adopted by the external metal.

Figure 5. Porous framework for the cubic form, by a hexacyano-cobaltates and a transition metal [30].

2.5. Materials synthesis

Interest in synthesizing nanostructured materials has led to the study of families with specific
characteristics. Here two families are addressed: (1) the family of tetracyano-niquelates (II)
[with three different external metals, that is, (Co+2) cobalt, nickel (Ni+2), and manganese (Mn
 Synthesis of Nanostructured Materials for Storing Hydrogen as an Alternative Source to Fossil Fuel Derivatives 53
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+2
)], which is synthesized in L1, K, and L0 phases for three metals, and (2) the hexacyano-
cobaltates (III) [with six different external metals, that is, cobalt (Co+2), nickel (Ni+2), manganese
(Mn+2), copper (Cu+2), (Zn+2) Zinc, and cadmium (Cd+2)]. X-ray diffraction (XRD) should be used
to check the phases and structures of these materials.

Modulated thermogravimetry (MTG) is used for the kinetic analysis of dehydration, and
scanning electronic microscopy (SEM) is used to analyze the morphology of the materials
during the process of dehydration.

2.5.1. Tetracyano-niquelates synthesis (lamellar materials)

Figure 6 shows the procedure for the synthesis of materials [M (H2O) 2 (Ni (CN) 4) (H2O) n: M
= Ni, Co, Mn, n = 1, 2, 4], which are obtained by the method of precipitation.

Figure 6. Materials synthesis M(H2O)2(Ni(CN)4)n(H2O): M = Ni, Co, Mn; n=1,2,4 .

Once the corresponding blends are obtained, the resulting precipitated solid is separated by
centrifugation, and the solid fraction obtained is repeatedly washed with distilled water to
remove the excess ions and then left at room temperature air-dried to constant weight.
54 Advances in Petrochemicals

2.5.2. Hexacyano-cobaltates synthesis (porous materials)

Figure 7 shows the hexacyano-cobaltates synthesis process.

Figure 7. Hexacyano-cobaltates synthesis.

The amount in excess of the metals involved guarantees the formation of a single phase. The
resulting precipitate remains for a week in the mixture. Then it is separated by centrifugation.
The solid fraction is repeatedly washed with distilled water to remove the excess ions, and
finally the material is air-dried to constant weight.

2.6. Characterization techniques

To ensure that the phases that have been obtained during the synthesis are correct, various
techniques are used. This chapter will talk about three of them, which allude to the obtaining
of the phases. One of them is X-ray diffraction (XRD), which is used under two aspects: to get
the diffraction patterns of the synthesized material and to ensure that the crystalline phases of
the structures meet the required specifications, which includes synthesis. On the other hand,
this technique is used to perform a constant monitoring during the dehydration of materials
and thus observe the structural change to drop out of the same water molecules present in the
 Synthesis of Nanostructured Materials for Storing Hydrogen as an Alternative Source to Fossil Fuel Derivatives 55
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system. Coupled with this technique, an SEM was used in order to follow up on the morphol‐
ogy of the material during the synthesis when dehydration was carried out. Finally, a thermal
analysis to corroborate the number of molecules of water, in addition to providing information
about the kinetic parameters, was involved during the dehydration of the study materials.

2.6.1. Systems lamellar characterizations

The family of tetracyano-niquelates (M (H2O) 2 [Ni (CN) 4] ⋅xH2O); M: Mn, Co and Ni, x = 1, 2,
and 4 has been studied recently due to its ability to store molecules such as H2, CO2, and N2. It
is known that they crystallize in three different ways, that is, phase L1, phase K, and phase L0
[7]. The forms adopted due to the water molecules present in the structure and their interaction
with metals assemblers. Figure 8 shows three phases reported.

Figure 8. Framework for L1 (a), K (b), and L0 (c) phases. Coordinated water molecules from neighboring layers re‐
mains linked through aquo-bridges (hydrogen bonding interactions).
56 Advances in Petrochemicals

Thermal analysis is performed in four aspects: (i) analyze how to change kinetic parameters
in a same phase for different metals of assembly, (ii) observe the influence of kinetic parameters
over the same metal assembly on three different stages, (iii) analyze L0 to L1 phase change
during the process of dehydration, and (iv) vary kinetic parameters as the partial pressure of
water in the system is changed. All materials are needed to monitor the process of dehydration
with the help of XRD to observe when there is a change in the structure or collapse once the
material molecules are removed totally or partially.

2.6.1.1. Two-dimensional network of water molecules in the three phases interpretation

In order to understand how water molecules are found in the material and thus to make one
website speedily of the kinetic parameters during the process of dehydration, two-dimensional
networks of water molecules are presented in three different phases (see Figure 9). Note that
the water molecules are organized along two-dimensional planes alternating the position
between coordinated octahedral (defined by the position of the metal) sites and the position
in the existing cavities between polyhedral.

Figure 9. Two-dimensional representation of the network of water molecules in the different lamellar systems for (a)
L1 phase, (b) K phase, and (c) L0 phase. Each red sphere is a water molecule without the hydrogen atoms.

2.6.1.2. Systems thermogravimetry lamellar characterization

Figure 10 shows samples of thermograms of the corresponding phase L1 as well as profiles of
conventional or normal activation energy obtained from synthesized, likewise in gray color.
The samples shown are the activation energy profiles obtained after dehydration of the
 Synthesis of Nanostructured Materials for Storing Hydrogen as an Alternative Source to Fossil Fuel Derivatives 57
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corresponding material in its phase L0. The difference between the profiles of activation energy
is due to local variations of the chemical potential of water or kinetic disabilities in reversible
reactions caused by the removal of part of the water when the temperature is increased in the
same way.

Figure 10. Thermogravimetric and activation energy profiles for K phase with the different transition metals: (a) Nickel
(Ni2+), (b) cobalt (Co2+), and (c) manganese (Mn2+). Blue points are activation energy profiles.

In Figures 11a and 11b, it can be observed that the morphology of the system once it passes
from step L0 to L1 phase is maintained when three molecules of water are removed, showing
only a change in the volume of material during the transition. The system presents forms as
flakes, which is a laminar structure manifestation in these materials that crystallize. The L1
phase synthesized presents particle sizes smaller than that obtained by the transition.

In the characterization by SEM, the only sample that differs from the others is the phase L0
with nickel and external metal because this has very organized small flakes. Figure 12 shows
that this structural arrangement explains why this material has low activation energies for the
L1 phase derived from the corresponding L0.
58 Advances in Petrochemicals

Figure 11. SEM micrographs of (a) as-prepared L0 phase, (b) L1 derived from L0 after heating, and (c) as-prepared L1
phase. The insets show a magnification of a selected area.

Figure 12. SEM micrograph of the as-prepared Ni-L0 phase.

 Synthesis of Nanostructured Materials for Storing Hydrogen as an Alternative Source to Fossil Fuel Derivatives 59
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2.7. Porous molecular materials

The second family studied is similar to the Prussian blue materials. These materials are referred
to as hexacyano-cobaltates (M3 [Co (CN) 6] 2xH2O); M: Mn, Ni, Co, Zn, Cd and Cu (see Figure
13). These materials form an interesting family with windows and pore volumes appropriate
for the separation and storage of small molecules [32]. The synthesized material boasts of water
molecules in pores formed, and these can be reversibly moved through the window without
having some structural rearrangement in the material. The unitary formula specifies that six
water molecules are coordinated to the material, and the remaining space is occupied by water
molecules that are linked weakly by hydrogen bonds mainly.

Figure 13. Lattice porous materials under study. (a) Representation of cavity Zinc cobalticyanide. (b) Porous lattice of
the cubic phase in cadmium cobalticyanide.

The characterization in this family is carried out to evaluate the material according to its ability
to remain at the same level and with the same crystal structure once the water molecules
between the cavities are removed, as well as to obtain the corresponding activation energy
profiles during dehydration as necessary energy values for the rupture of the interaction. Thus,
this provides an idea of the power required for a molecule to be hosted inside the material.

2.7.1. Thermogravimetric molecular porous materials characterization

Materials under study lose the total number of molecules of water (both the coordinates and
the zeolite) between 90°C and 180°C. The temperature dehydrated in a total way is highly
linked with the polarizing power of the outer material, in addition to electrostatic forces with
water molecules. Dehydration temperatures carry the following order: (117.54 °C) > Mn (106.57
°C) > Co (99.26 °C) > Cd (89.82 °C) > Cu> Zn (67.44 ° C). This sequence of dehydration can be
seen clearly in Figure 14, in addition to showing the corresponding graphics of the derivative
for each sample. In the particular case of the material with Zinc as metal coordination, low
temperatures of dehydration due to the tendency of this material to adopt a tetrahedral
coordination by forming a rhombohedral phase, which tends to be anhydrous. In these
materials, for all the samples, the water molecules, both the coordinates and that of the zeolitic
type, leave the system through a virtually continuous and simple process, resulting in
60 Advances in Petrochemicals

dehydration cooperatively between the two types of water resulting in TG profiles without
well-defined inflections, although at the beginning of all samples, a slight disturbance is
recorded by the team (through the measurement of Ea).

Figure 14. Thermogravimetric (TG) curves and the corresponding derivative (DTG) that expresses the progress of de‐
hydration.

Figure 15. TG and DTG profile, modulation of temperature, and time set on a measure imposed on high resolution and
modulated for material Co3 [Co(CN)6]2xH2O.
 Synthesis of Nanostructured Materials for Storing Hydrogen as an Alternative Source to Fossil Fuel Derivatives 61
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As an example of a deeper analysis system, cadmium hexacyano-cobaltates are considered. In

addition to being plotted and based on the weight loss derived from the corresponding weight,
Figure 15 will also include the time of the process and the derivative of the temperature
modulation time. The latter refers to the temperature disturbance along throughout the
dehydration process, and the information provided is the resistance of the phenomenon, that
is, as the modulation is increasing, the resistance of the water molecules evolves in the system.
So, considering a constant disturbance implies that water molecules get out of the system
without offering any more resistance. This agrees with what the Ea charts show.

2.7.2. Hexacyano-cobaltates activation energy

The activation energy profiles for these materials show that the Ea values are very close
together, in a range between 60 and 90 kJ/mol with 60 kJ/mol in the case of Zinc as an external
metal and 90 kJ/mol for nickel. Figure 16 shows the corresponding profiles mentioned. These
two materials are considered because both ends are minimum and maximum in dehydration
temperature.

Figure 16. TG curves and profile of Ea for dewatering M3 [Co(CN)6]2xH2O, con M = Ni2+ y Zn2+.

3. Suggestions

In future research, we intend use a lattice Boltzmann method in order to copy the porous
medium obtained experimentally and to make simulations. Figure 17 shows the simulation
using the lattice Boltzmann method of randomly generated porous media [33].
62 Advances in Petrochemicals

Figure 17. Lattice Boltzmann simulations through porous media.

4. Conclusions

In general, the study of the relative stability of the tetracyano-niquelates and hexacyano-
cobaltates processes of dehydration shows that this depends in the first instance of the
interactions of the water molecule with the outside. A more polarizing power metal is the
stability of the link M-H2O (for identical structures). Lamellar systems presented an energy
barrier that must overcome the water molecules to begin to spread on the system. This barrier
is the activation energy that lies in a range between 60 and 500 kJ/mol, depending on the type
of water that comes out. In systems where the water molecules of subnetworks are homoge‐
neous, water zeolite is indistinguishable from the coordinated water molecules.

To increase the partial pressure of water in laminar systems, there is an increase in the
temperature of dehydration due to the increase in chemical potential of water in the system,
and the immediate consequence is reflected in the increase in activation energy.

Studies by X-ray diffraction report the existence of a transition from L0 phase to L1 phase
during the dehydration process, and during this transition, the phase change morphology of
the material is maintained.

The process of dehydration in the hexacyano-cobaltates, which also presented the two types
of water molecules (zeolite and coordinated), is carried out to lower activation energy values
 Synthesis of Nanostructured Materials for Storing Hydrogen as an Alternative Source to Fossil Fuel Derivatives 63
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(between 60 and 90 kJ/mol) compared to lamellar systems since coordinated molecules are
linked weakly to assemble metal.
For molecular materials during dehydration, there was no structural collapse, even if there are
changes in the material locally, which has a shrinkage of only 4% of the unit cell.
In future research, we aim to use the lattice Boltzmann method for the characterization of
porous medium, which would help with different configurations of porous media.

Author details

Omar Reyes-Martínez and José Luis Velázquez Ortega*

*Address all correspondence to: [email protected]

Facultad de Estudios Superiores Cuautitlán, UNAM, Cuautitlán Izcalli, Edo. de Méx, México

References

[1] Knoblauch, K.: Pressure swing adsorption geared for small volume users. Chem.
Eng. 1978;85( 25):87.
[2] Cheng C.D., Silvestri A.J.: The conversion of methanol and other O-compounds to
hydrocarbons over zeolite catalysts. J. Catal. 1997;47(2);249–259. doi:
10.1016/0021-9517(77)90172-5.
[3] Schlapbach L., Züttel A.: Hydrogen-storage materials for mobile applications. Na‐
ture. 2001;414;353–358, doi:10.1038/35104634.
[4] Kitagawa S., Kitaura R.: Pillared layer compounds based on metal complexes. Syn‐
thesis and properties towards porous materials. Comments Mod. Chem. A. Com‐
ments Inorg. Chem. 2002;23(2);101–126. doi:10.1080/02603590214512.
[5] Mathey Y., Mazieres C.: Les phases cyanures de nickel(II) hydratés. Can. J. Chem.
1974;52(21):3637–3644. doi:10.1139/v74-544.
[6] Barrer R.M., MacLeod D.M.: Activation of montmorillonite by ion exchange and
sorption complexes of tetra-alkyl ammonium montmorillonites. Trans. Faraday Soc.
1995;51:1290–1300. doi:10.1039/TF9555101290.
[7] Lemus-Santana A.A., Rodriguez-Hernandez J., del Castillo L.F., Basterrechea M.,
Reguera E.: Unique coordination of pyrazine in T [Ni(CN)4]⋅2pyz with T = Mn, Zn,
Cd. J. Solid State Chem. 2009;182(4):757–766. doi:10.1016/j.jssc.2008.12.028.
[8] Rodriguez-Hernandez J., Lemus-Santana A.A., Cargas C.N., Reguera E.: Three struc‐
tural modifications in the series of layered solids T(H2O)2 [Ni(CN)4]⋅xH2O with T =
64 Advances in Petrochemicals

Mn, Co, Ni: their nature and crystal structures. C. R. Chim. 2012;15(4):350–355. doi:
10.1016/j.crci.2011.11.004.

[9] Ferlay S., Mallah T., Ouahès R., Veillet P., Verdaguer M.: A room-temperature orga‐
nometallic magnet based on Prussian blue. Nature. 1995:378;701–703. doi:
10.1038/378701a0.

[10] Shin-ichi O., Ken-ichi A., Yusuke S., Kazuhito H.: Humidity-induced magnetization
and magnetic pole inversion in a cyano-bridged metal assembly. Nat. Mater.
2004;3:857–861. doi:10.1038/nmat1260.

[11] Lemus A.A.: Incorporación de pirazina y 4,4´-bipiridina en estructuras laminares de

tetracianoniquelatos: síntesis, estructura, adsorción y separación de gases (Tesis),
México, D.F., UNAM, 2010.

[12] Nijkamp M. G., Raaymakers J. E. M. J., van Dillen A. J., and de Jong K.P.: Hydrogen
storage using physisorption – materials demands.Applied Physics A: Materials sci‐
ence and Processing; 2001; 72(5): 619-623. doi: 10.1007/s003390100847.

[13] Breck D.: Zeolite Molecular Sieves: Structure, Chemistry and Use. New York: J. Wi‐
ley; 1974. ISBN 0471099856, 9780471099857.

[14] Leonowicz M.E., Lawton J.A., Lawton S.L., Rubin M.K.: MCM-22: a molecular sieve
with two independent multidimensional channel systems. Science. 1994;264(5167):
1910–1913. doi:10.1126/science.264.5167.1910.

[15] Thomas K.M.: Hydrogen adsorption and storage on porous materials. J. Catal. To‐
day. 2007:120(3–4);389–398. doi:10.1016/j.cattod.2006.09.015.

[16] Zhao X.B., Xiao B., Fletcher A.J., Thomas K.M.: Hydrogen adsorption on functional‐
ized nanoporous activated carbons. J. Phys. Chem. B.2005:109(18);8880–8888. doi:
10.1021/jp050080z.

[17] Zhao X., Villar R., Fletcher A.J., Thomas K.M.: Kinetic isotope effect for H2 and D2
quantum molecular sieving in adsorption/desorption on porous carbon materials. J.
Phys. Chem. B.:2006;110(20):9947–9955. doi:10.1021/jp060748p.

[18] Panella B., Hirscher M., Roth S.: Hydrogen adsorption in different carbon nanostruc‐
tures. Carbon, 2005:43(10):2209–2214. doi:10.1016/j.carbon.2005.03.037.

[19] Züttel A.,Sudan P., Mauron P., and Wenger P.: Model for the hydrogen adsorption
on carbon nanostructures. Appl. Phys. A. Mater. Sci. Process. 2004;78(7);941–946,
2004. doi:10.1007/s00339-003-2412-1.

[20] Lachance P., Benard P.: Specific surface effects on the storage of hydrogen on carbon
nanostructures. Int. J. Green Energy. 2007;4(4):377–384. doi:
10.1080/15435070701337434.

[21] Pinnavaia T.J.: Nanoporous layered materials. ACS Adv. Chem. Ser. 1995;245:283–
300 doi:10.1021/ba-1995-0245.ix001.
 Synthesis of Nanostructured Materials for Storing Hydrogen as an Alternative Source to Fossil Fuel Derivatives 65
http://dx.doi.org/10.5772/61076

[22] Bizeto M.A., Shiguihara A.L., Constantino V.R.L.: Layered niobate nanosheets: build‐
ing blocks for advanced materials assembly. J. Mater. Chem. 2009;19(17):2512–2525.
doi:10.1039/B821435B.

[23] Vieira P. and Santos C.A.C.: Propriedades catalíticas dos argilominerais (Parte II): Ar‐
gilominerais intercalados e pilarizados. Boletín Técnico de Petrobras. 1988;31(2):143–
157.

[24] Sterte J.: Hydrothermal treatment of hydroxycation precursor solutions. Catal. To‐
day. 1988;2(2):219–231. doi:10.1016/0920-5861(88)85005-3.

[25] Dunbar K.R., Heintz R.A.: Chemistry of transition metal cyanide compounds: mod‐
ern perspectives. Prog. Inorg. Chem. 1997;45:295–296. doi:10.1002/9780470166468.ch4.

[26] Iwamoto T., Nishikiori S.-I., Kitazawa Y.H.: Dalton transactions. J. Chem. Soc.
1997;22:4127–4136. doi:10.1039/A702539D.

[27] Ludi A.: Prussian blue, an inorganic evergreen. J. Chem. Educ. 1981;58:1013. doi:
10.1021/ed058p1013.

[28] Ludi A., Gudel H.U.: Structural chemistry of polynuclear transition metal cyanides. J.
Inorg. Chem. 1973;14:1–21 doi:10.1007/BFb0016869.

[29] Roque J., Reguera E., Balmaseda J., Rodriguez H.J., Reguera L., del castillo L.F.: Po‐
rous hexacyanocobaltates(III): role of the metal on the framework properties. Micro‐
porous Mesoporous Mater. 2007;103:57–71. doi:10.1016/j.micromeso.2007.01.030.

[30] Kaye S.S., Long J.R.: Hydrogen storage in the dehydrated Prussian blue analogues
M3 [Co(CN)6]2 (M = Mn, Fe, Co, Ni, Cu, Zn). J. Am. Chem. Soc. 2005;127:6506–6507.
doi:10.1021/ja051168t.

[31] Chapman K.W., Southon P.D.,Weeks C.L., Kepert C.J.: Reversible hydrogen gas up‐
take in nanoporous Prussian Blue analogues. J. Chem. Commun. 2005;26:3322–3324.
doi:10.1039/B502850G

[32] Boxhoorn G., Moolhuysen J., Coolegem J.G.F., van Santen S.R.: Cyanometallates: an
underestimated class of molecular sieves. J. Chem. Soc., Chem. Commun.
1985;19:1305. doi:10.1039/C39850001305.

[33] Romo S.R., Ortega J.L.V.Simulation of non-Newtonian fluids through porous media.
Chapter 5. In Patel V (ed.),Petrochemicals.Rijeka, Croatia: Intech; 2012:75–100. doi:
10.5772/2069. ISBN 978-953-51-0411-7.
 Chapter 4

Crude Oil Desalting Process

Juan Pereira, Ingrid Velasquez, Ronald Blanco, Meraldo Sanchez,

César Pernalete and Carlos Canelón

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/61274

Abstract
Desalting is a water-washing operation performed initially at the production field and
thereafter at the refinery site for additional crude oil cleanup. Salt and water content
specifications are even more rigid because of their negative effect in downstream
processes due to corrosion, and catalyst deactivation. An optimum formulation
concept is presented to describe emulsion breaking in desalting process. In the
stabilization mechanism is accepted that water droplets are stabilized by the
formation of a mechanically strong and viscoelastic film at the interface composed of
asphaltenes. In the case of water-in-crude-oil emulsions, a balanced optimum
formulation is attained by adding to the lipophilic natural surfactants contained in
the crude oil, demulsifiers which are hydrophilic. The aim is to relate the nature and
concentration of the added demulsifier products to the amphiphilic mixture at the
interface. All formulation parameters, such as solvent, alcohols, kind and concentra‐
tion of demulsifier, amoung others, can be explained for proportional and saturation
regimens.

Keywords: Desalting, asphaltenes, demulsifier, , emulsions, physicochemical for‐

mulation

1. Introduction

Petroleum recovered from reservoir is mixed with a variety of substances such as gases, water,
chloride salts, and dirt, which contain other minerals. Thus, petroleum processing actually
commences shortly after the production of fluids from reservoir, where pretreatment opera‐
68 Advances in Petrochemicals

tions are applied to the crude oil prior to transportation. Any crude oil to be shipped by
pipeline, or by any other form of transportation, must meet strict regulations in regard to water
and salt content.

Desalting is a water-washing operation performed initially at the production field and

thereafter at the refinery site for additional crude oil cleanup, where the salt and water content
specifications are even more rigid because of their negative effect in the downstream processes
due to scale formation, corrosion, and catalyst deactivation. Desalting involves mixing heated
crude oil with washing water, using a mixing valve or static mixers to ensure a proper contact
between the crude oil and the water, and then passing it to a separating vessel, where a proper
separation between the aqueous and organic phases is achieved.

Since emulsions can be formed in this process, there is a risk of water carryover in the organic
phase. In order to overcome this problem chemical demulsifiers are added to promote the
emulsion breaking. When this operation is performed at a refinery, an electric field across the
settling vessel is applied to coalesce the polar salty water droplets, and, therefore, a decreasing
in water and salt content is achieved.

The understanding of the different variables that affect the desalting process, especially the
effect of the amount of chemical demulsifiers used, is imperative in order to optimize operating
costs. According to data published by Vafajoo [1], the demulsifier concentration used for
desalting could reach up to 100 ppm. Considering a demulsifier cost about 1.5 $/lb [2] for a
medium capacity refinery (200 MBPD), the operating cost related to chemical demulsifiers
would be in the order of 2 MM$/year. Thus, any reduction in demulsifier concentration in
crude oil desalting would generate savings in the order of many thousand dollars. In the
current work, a technical description of desalting crude oil and a wide description of stability
emulsion phenomena are carried out. Finally, this work aims mainly at understanding the
demulsifiers role from the viewpoint of physicochemical formulation.

2. Process description

Salts in crude oil are mainly in the form of magnesium, calcium, and sodium chlorides, sodium
chloride being the most abundant. These salts can be found in two forms: dissolved in
emulsified water droplets in the crude oil, as a water-in-oil emulsion, or crystallized and
suspended solids.

The negative effect of these salts in downstream processes can be summarized as follows: salt
deposit formation as scales where water-to-steam phase change takes place and corrosion by
hydrochloric acid formation. Hydrochloric acid is formed by magnesium and calcium
chlorides’ decomposition at high temperatures (about 350 °C) as follows [3]:

CaCl2 + 2H2O → Ca(OH)2 + 2HCl

MgCl2 + 2H2O → Mg(OH)2 + 2HCl

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In addition, other metals in inorganic compounds present in reservoir dirt and sand produce
catalyst poisoning in downstream processes such as hydrotreaters and cat crackers because of
they are chemically adsorbed on the catalyst surface.

The objective of desalting process is to remove chloride salts and other minerals from the crude
oil by water-washing. Depending on the desired salt content in the desalted crude oil, a one-
or two-step process could be applied. For refining purposes, a salt concentration of maximum
1, 5 PTB (pound of salt measured as NaCl per thousand barrels) is desired. By desalting, a
considerable percentage of suspended solids (sand, clay, or soil particles, or even particles
product from corrosion of pipelines and other upstream equipments) are removed. Figure 1
shows a general process flow diagram for one- and two-step desalting process.

Figure 1. Simplified desalting process flow diagrams for different configurations: (a) one-step and (b) two-step.

The process starts by mixing the raw crude oil with an appropriate amount of washing water
also known as dilution water. The washing water as a volume percent of the crude oil processed
could oscillate between 3 and 10%, depending on the API gravity of the crude oil – the heavier
the crude oil, the more the water required [2]. Demulsifiers are added to the crude oil in this
process step.
70 Advances in Petrochemicals

In order to promote the effective mixing between the organic and aqueous phases, and ensure
the proper dilution of the salts and minerals in the aqueous phase, a mixing valve is used. This
is a common globe valvewhich causes a pressure drop and, as a result, a shear stress over the
droplets that promotes an intimate water and oil mixture. The main aspect that needs to be
considered is the pressure drop, whose value it is about 10-50 psi and varies according to the
flux through the valve (automatic differential pressure controllers could be used). In addition
to the mixing valve, upstream premixing device could be used, such as spray nozzles at the
point of water injection or static mixers, between the water injection point and the mixing valve
[4]. High delta pressure in the mixing valve promotes smaller droplets, which is positive
because it improves the contact among the phases; however, very small droplets could yield
a more stable emulsion, which could cause problems in the separating vessel. Therefore, it is
very important to balance both effects in the selection of the operation pressure drop.

Then this mixture goes to the desalter, a horizontal cylindrical tank that provides long enough
residence time to separate the water and oil mixture in two phases. Some water droplets
diameters are so small that they could not be separated by gravity; so, an electrostatic field
between two electrodes installed into the desalter is used to promote coalescence. Due to the
dipolar nature of the water molecule, this electric field promotes an attraction with the other
water molecules in the neighbor droplets promoting coalescence. According to Gary et Al. [2],
either AC or DC fields may be used and potentials from 12, 000 to 35, 000 volts. The attraction
force (F) between the water droplets is given by:

Ks × e 2 × d 6
F= (1)
s4

where ε is voltage gradient, d is droplet diameter, s is the distance between drops centers and
Ks is a constant for the system [4].

Finally, after coalescence, water droplets settle according to the well-known Stock’s law given
by:

k × ( r water - r oil ) × d 2
Settling rate = (2)
m oil

where k is a constant, d is the droplet diameter, ρ is density, and μ is viscosity.

In a one-step configuration, shown in Figure 1(a), 90% of salt removal can be achieved. For
higher salt removal percentages, a two-step configuration, shown in Figure 1(b), should be
required. As far as the last process configuration is concerned two demulsifier injection points
are used, both before the mixing valve in the first and second step. In addition, freshwater is
fed to the second stage, and effluent water from this stage is recycled to the first one. With this
configuration, a 99% salt removal could be achieved.
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3. Crude oil emulsions

Emulsions are present in the main operations of the petroleum industry. The more well-
known emulsions in the petroleum industry are those when the crude oil is the external
phase (W/O). Water-in-oil emulsions are robustly stabilized by natural surfactants from
crude oil, where a “special film” takes place and it is the responsible for emulsion stability.
Film at the oil–water interface is highly viscous and is formed by asphaltenes, resins, waxes,
and small solid particles [5, 6].
A main feature for interfacial film is the irreversible adsorption of asphaltenes at the oil−water
interface in combination with other natural surfactants [7-10].
In the study of water-in-oil emulsions, it is important to know the structure and properties of
the crude oil components, their tendency to associate and accumulate at the interface, as well
as solubility and sensitivity to pressure and temperature changes.

3.1. Formation of water-in-oil emulsions

In secondary oil recovery processes, the oil is contacted with formation water or water injected
to produce the oil drain water. Water is used as a piston to push the oil from the well during
the production process and then remove to the refinery [11]. In the reservoir, the fluid velocity
is very slow (1 ft/day) to produce the emulsion, and emulsion is not formed during the two
phase flow in porous media but later in equipment where oil is processed. Hence, the shear is
responsible of making emulsion by pumping through valves, pipes, elbows, and others [7].
Damage to environment may occurs when petroleum or its products are spilled into the sea
or the river, due to which water–oil emulsions are also formed. These emulsions (called
‘‘chocolate mousse’’) has special properties and characteristics [12-13]. Changes in the
emulsions properties, such as viscosity and stability, are notable due to internal phase
increasing [13].
The formation of water/oil emulsions is generally caused by the presence of resins and
asphaltenes present in the oil, which play the role of natural emulsifiers [9]. These emulsifiers
have a mutual attraction resulting in the formation of an elastic membrane around the droplets,
preventing water droplets from uniting and decanting by gravity. This membrane is thick and
could be easily visible using an optical microscope [14].

3.2. Asphaltenes

Asphaltene is the petroleum most complex fraction which is insoluble in normal alkanes
such as n-pentane, n-hexane, or n-heptane, but soluble in benzene or toluene. Asphal‐
tenes are composed by high molecular weight molecules and the most polar components
in crude oil [15].
Usually, asphaltene structure comprises fused polyaromatic rings substituted by short
aliphatic chains (1-3 carbons atoms) and cycloalkanes. Aromatic rings containing some polar
functional group than content heteroatom such as sulfur, nitrogen and oxygen and some
72 Advances in Petrochemicals

metals like nickel, vanadium and iron, which confer polarity and amphiphilic characteristics
to these macromolecules [16]. Asphaltenes can generate a wide distribution of molecular
structures that can vary greatly from one crude to another [17].

Asphaltenes are composed of several polynuclear aromatic sheets surrounded by hydrocarbon

tails, and form particles whose molar masses are between 500 and 20.000 g. They contain many
functional groups, including some acids and bases [18].

The specific structure of asphaltenes is unknown; however, molecular weight averages

about 750 and there is a planar aromatic structure surrounded by alkane groups, some with
heteroatoms, sulfur (S), nitrogen (N), and oxygen (O) [19]. Deposition of asphaltenes often
causes some changes in the flow behavior of the oil fields through processing facilities, and
difficulties in oil recovery. The problems caused by asphaltenes are closely related to its
stability. Due to pressure variations, oil composition, and temperature, asphaltenes tend to
form aggregates [14].

Experimental evidence from a combination of spectroscopy techniques and elemental analysis

suggest that resins contains several fused five-and-six carbons rings in addition to alkyl chains.

Crude oil can be defined as a dispersed system where asphaltenes are colloids. Asphaltene
molecules are in the center of the structure of the liquid oil, the other components are organized
around the layer of asphaltenes decreasing polarity (resins, saturated and aromatic hydrocar‐
bons). This simple model allows reconciling the compatibility presence within the same fluid
and asphaltenes.

3.3. Mechanism of asphaltene aggregation: Colloidal behavior

Asphaltenes can be considered as a complex polydisperse system of molecules in which

subcomponents with significantly different characteristics can be distinguished as the result
of solubility differences [17, 20].

From the colloidal point of view, it has been stated that asphaltenes in general are a blend of
two main fractions. Acevedo et al. [21] proposed a model for asphaltene colloids in toluene
which consists of two subfractions with different solubilities, called A1 and A2. The subfraction
A1 (90 mg/L in toluene), which is insoluble in aromatic solvents such as toluene, cumene, and
others, is found in greater proportion than a second subfraction A2 (57 g/L in toluene), which
is soluble in these solvents and acts as a promotor in the dispersion of A1. The solubility of the
latter is similar to the total mixture. Asphaltene aggregation phenomena is well understanding
under the vision of colloidal nature of both fractions. [22]. Furthermore, this colloidal model
has been found very useful in accounting for other phenomena such as trapping of compounds,
flocculation, aggregation promoted by A1, asphaltene aggregation at very low concentration,
and metal distribution [17].

In the vapor pressure osmometry (VPO) technique for molecular weight measures, the polarity
of solvent is a critical parameter. Using o-dichlorobenzene, a 1000 g mol-1 value was reported
for A2 solutions at 120 °C. On the other side, A1 afforded higher values (around 2600 g mol-1),
emphasizing the strong aggregation tendency of this fraction [23].
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Asphaltenes can form different types of aggregates depending on the environment: oil, solvent,
interface, and others. Mullins et al. [24] proposed a scheme to explain the aggregation of
asphaltenes in toluene. At low concentration, asphaltene is a group of individual molecules
that evolve into nanoclusters and are associated in particles until reaching a system susceptible
to flocculate. Floccules are unstable aggregates that eventually precipitate. In certain cases,
stable aggregates that give the crude viscoelastic properties are formed.

Due to the presence of polar groups, asphaltenes can behave as surfactants, exhibiting the
phenomena of adsorption and aggregation. However, it is wrong to attribute a critical micelle
concentration (CMC) for asphaltenes and other macromolecules from crude oil. CMC is a
parameter exclusive for surfactants, such as sodium dodecyl sulfate (8.3 * 10-3 M in water).
Parameters such as aggregation number, shape and size of the micelle, electrolyte effect on the
micellization and other additives are well known for surfactants. For petroleum asphaltenes
this knowledge does not exist, mainly because the structure of an asphaltenes molecule is
unknown. Aggregates phenomena best describes asphaltenes behavior. Asphaltene in toluene
begins to form aggregates at 50 ppm concentration [25].

In summary, the use of CMC term for asphaltenes and other natural surfactants contained in
the crude oil should be avoided. The emulsions in crude oil are produced for a mechanism
starting with asphaltenes migrate into the oil–water interface, a process which is regulated by
the diffusion of the soluble asphaltenes [19]. Adsorption of asphaltenes at the interfaces is a
very slow process. The initial diffusion step toward the interface is rapid and it is followed by
a long reorganization and the progressive building of multilayers. Asphaltenes diffuse from
the bulk of crude oil to oil–water interface and are then adsorbed, decreasing the interfacial
tension [26]. Asphaltenes can also form multilayers on solid surfaces such as silica. It has been
found that increasing the concentration of asphaltenes in solution tends to increase its state of
aggregation, which decreases the rate of adsorption on the surface [22].

3.4. Stability of water-in-crude-oil emulsions

In terms of time, the stability of the emulsion has a range from few minutes to years and it varies
by the characteristics of the crude oil and water [27]. The stability mechanism is, of course,
related to the composition of crude oil, such as type and the concentration of natural surfac‐
tants, the physical properties of oil, and the interfacial rheology of the interface around water
droplet, which provides information about elasticity and viscosity and, for instance, the presence
of a film (called skin) for the specific case of petroleum crude oil at this interface [10, 28].

Gao et al. [29] quantitatively studied the formation of interfacial film by the asphaltenes on the
oil–water interface. They propose to measure the appearance of crumpling in the interfacial
film, using imaging drop following compression by extraction volume, by the following
relationship:

Af p Rf 2 Rf 2
CR = = = (3)
Ai p Ri2 Ri2
74 Advances in Petrochemicals

where CR is crumpling ratio; Ai is the projected drop initial area; Af is the projected area of the
drop observed just before crumpling; Ri is the projected drop initial radio; and Rf is the radio
of the drop observed just before crumpling. Figure 2 shows a schema of the contraction of a
drop of oil in water. In Figure 2 (a), crumpling phenomenon does not occur; drop reduces its
volume to be sucked into the syringe. In Figure 2 (b), volume drop is contracted when the drop
crumpling phenomenon occurs in the interfacial film. The scheme shows its building. CR
parameter is related to the irreversible adsorption of asphaltenes at the water–crude interface;
an increasing of CR means an increasing in emulsion stability.

Figure 2. Volume contraction scheme of a drop of oil in water system: (a) absence of crumpling phenomenon and (b)
presence of crumpling phenomenon occurs.

As part of the stabilization mechanism, it is accepted that the water droplets are stabilized by
the formation of a mechanically strong and viscoelastic film at the interface, composed of
asphaltenes [30].

Subsequently, several workers reviewed emulsions and concluded that asphaltene content is
the most important factor in the formation of emulsions [7-10]. Asphaltene fraction is mainly
responsible for the high emulsion stability of water-in-crude-oil; thus, they were found to be
capable of forming rigid, cross-linked, and elastic films [19].
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Asphaltenes stabilize water-in-oil emulsions if they are near or above the point of incipient
flocculation, i.e., solid particles which can be. Other investigators have also suggested that
asphaltene colloids are responsible for stable emulsions. Asphaltenes may be at the interface
as fine solid particles or resin-asphaltene colloids. However, Yarranton et al. [31] reported that,
at low asphaltene concentrations (<0.2 wt %), molecular state of asphaltenes predominant onto
the colloidal form. It is also necessary to consider the effect of resins as they may influence
asphaltene aggregation, adsorption on the interface, and emulsion stability [32].

One of the most used methods for studying emulsion stability is the bottle test. Figure 3 shows
the bottle test sample for evaluating the stability of water-in-oil emulsion. It was observed that
in the tubes on the left side there are stable emulsions, while in the tubes in the center and on
the right side, there is a good separation of the two phases.

Figure 3. Stability bottle test of water-in-crude-oil emulsion (Silva, 2012).

Langmuir technique has been widely used for the characterization of the interfacial film
formed by natural surfactants from crude oil [33-37]. Isotherms provide surface-pressure-area
information on the compressibility of the film formed by the asphaltenes and other natural
surfactants. The interfacial film can be collected with the Langmuir-Blodgett technique.
Extensive morphological characterization of the interfacial film has been performed, including
properties such as contact angle, thickness, and aggregate size, among other. Images obtained
using Atomic Force Microscopy have contributed to the understanding of the mechanisms of
interfacial adsorption, swelling, aggregation of colloidal interactions, and asphaltene [38, 39].

Aromaticity, length of the alkyl side chains, and branch reduction in the aliphatic chains of
resins and asphaltenes are associated with the formation of stable emulsions. Another
important parameter is the pH of the aqueous phase. Asphaltenes and resins are composed of
polar functional groups; these groups can be ionized at alkaline pH. Surface charge density
increases due to ionization of polar groups, generating internal repulsive forces destroying the
mechanical properties preventing droplet coalescence [14].
76 Advances in Petrochemicals

4. Chemical demulsification: physicochemical formulation

When emulsion formation and stabilization take place, demulsifiers (generally a surfactant)
must be used. A surfactant is a specie that, when present at low concentration in a medium,
has the property of adsorbing onto the surfaces or interfaces of the system, altering the surface
or interfacial free energies of those surfaces (or interfaces) [40].
Balsamo et al. [41] showed that effective demulsifiers formed complexes with natural anionic
surfactants present in the oil phase, weakening the irreversible film; this is well correlated with
low emulsion stability. When emulsion breaker was added to the system, a synergistic effect
was observed between natural surfactant and demulsifier with further lowering of the
interfacial tension (IFT).
It is known that an unstable emulsion occurs when amphiphilic formulation at the interface
corresponds to an exact affinity balance of the surfactant mixture for the oil and water phase
[7, 42-44]. From a physicochemical viewpoint, the optimum formulation is achieved when the
standard potentials (µ*) of a surfactant (or mixture) in oil (µ*o ) and water (µ*w ) are equal, i.e.,
when (µ*w ) = (µ*o ). Physicochemical phenomena have been qualitatively related to the emulsion
breaking occurrence. In the case of water/crude emulsions, the balanced optimum formulation
is attained by adding hydrophilic demulsifiers to the lipophilic natural surfactants contained
in the crude oil. From our point of view the aim is relate to the nature and concentration of the
added demulsifier products to the amphiphilic mixture at the interface.
A new methodology has been presented by several authors [7, 42-44]. It is essentially a
formulation scan study carried out by adding a hydrophilic demulsifier at different concen‐
trations, until a minimum emulsion stability is reached. At this optimum formulation point,
the lipophilic natural surfactants (i.e., asphaltenes, resins, naphthenic acids, and other crude
oil amphiphiles at the interface) referred to as asphaltenes (A) are balanced by the added
hydrophilic demulsifiers (D). The hydrophilic−lipophilic contributions of both types in the
interfacial mixture are dependent on their adsorbed concentration and on the strength of their
effects. Consequently, the hydrophilic contribution of the demulsifier may be varied by
changing its hydrophilicity or its concentration [44]. In general, it has been shown that the
more hydrophilic the nature of the demulsifier, the lower is the concentration required to reach
the minimum emulsion stability when they join asphaltenes [44], mixing rule is approximately
linear, i.e., that the demulsifier is not too hydrophilic (because it would go essentially to water)
or not too close to matching hydrophobicity (because it would not compensate the asphaltene
hydrophobic effect). However, there are others factors to be considered such as the viscoelastic
properties of the asphaltene interfacial layer than improve the understanding of demulsifier
action.
Pensini et al. [45] measured the viscoelastic properties of the interface as a function of aging
time as the asphaltenes diffused toward the interface and adsorbed on the water–toluene
interface. With gradual accumulation of asphaltenes on the toluene–water interface, the
interface changes from a viscous to an elastic-dominant microstructure. Focusing on the effect
of demulsifier addition, at 6000 s of interfacial aging are not shown. Once the condition G’
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(elastic component) = G” (viscous component) was reached, the demulsifier was added at 2.3
ppm (optimum dosage from the bottle tests). When the elastic contribution is predominant,
asphaltenes are intimately linked, forming a cohesive interfacial network. To assess the
demulsifier performance, in penetrating and breaking the cohesive network of asphaltenes,
the shear viscoelastic moduli was measured. Upon addition of 2.3 ppm demulsifier in toluene,
both viscous and elastic shear modulus of the interfacial film decreased.
The problem when handling formulation issues in a crude oil system is that only a small part
of the asphaltenes is present at the interface. This implies that the total asphaltenes’ concen‐
tration in the crude oil does not participate with the demulsifier at the interfacial mixture. As
a consequence, the optimum concentration of the demulsifier is not dependent on its mixture
with all the asphaltenes in the system. Only a fraction of asphaltenes is adsorbed, and the rest
forms aggregates, flocculates, or precipitates, an important amount of it being segregated close
to the interface, but not at the interface (see Figure 4). This asphaltene excess is responsible for
the characteristic skin at the water–crude oil interface [7, 9, 10].

Figure 4. Asphaltene excess than there are out of interface. This situation corresponds to Ca> 1, 000 ppm. Solvent can
to penetrate in this layer asphaltene and interact with them for limit its aggregation due solvation effects (Pereira,
2009).

An experimental method has been recently proposed to estimate the asphaltene−demulsifier

adsorbed mixture composition, so that interfacial formulation may be estimated [7]. It consists
in diluting the crude oil so that the asphaltenes’ concentration in the oil phase is reduced. At
some point, asphaltenes’ concentration is low enough so there is no excess of aggregates or
flocculates in the oil phase. In this situation, asphaltenes and demulsifiers species may be
78 Advances in Petrochemicals

considered as two types of surfactants adsorbed at the interface, according to the physico‐
chemical conditions in the bulk phases at equilibrium. It has been found that below a concen‐
tration of asphaltenes 500−1000 ppm, the concentration of demulsifier required to attain
optimum formulation varies proportionally to the concentration of asphaltenes (see Figure 5).
In this so-called proportional regime [7], a quantitative formulation effect at the interface can
be estimated without taking into account physical effects such as viscosity, convection, and
diffusion through bulk oil (these are not formulation issues). This method allows evaluating
the demulsification performance as a function of different formulation variables (demulsifier
hydrophilicity, salinity, and crude oil characteristics) [7, 42-44], which represents a significant
practical progress in designing commercial products.

Figure 5. Demulsifier concentration as a function of the asphaltene concentration to reach optimum formulation (Per‐
eira, 2009).

HLB method (hydrophile–lipophile balance) is often used. In this method, a number (0–40),
indicative of emulsification behavior and related to the balance between the hydrophilic and
lipophilic (hydrophobic) portions of the molecule, has been assigned to many commercial
surfactants [42].

Using HLB concept, the proportional regime can be estimated, as follows, [7, 42-44]:

HLBoptMixt = X A HLBA + X DHLB D (4)

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where XA and XD are the fractions of A and D at the interface (XD = 1 − XA) and HLBOptMixt is a
characteristic value (close to 10 correspond to the affinity) for the system. This can be calculated
from the experimental correlation (bottle test) when the crude, brine, and temperature are
fixed. The effect of any additive can be easily qualified as favorable or not when decreasing
the fraction of demulsifier required (XD) to attain the optimum formulation for the lowest
stability. Since the experiments are much easier and more accurate in the proportional regime,
this is the zone where the tests of the additive effects are mostly carried out. Silva et al. [8] used
this methodology to estimate, in a semiquantitative manner, the effects of organic acid and
amine additives on the formulation of the components at the interface. The results indicate
that water-soluble additives (acetic acid and ethylamine) have no significant effect on the
required demulsifier concentration CD*. Even if they considerably alter the pH aqueous phase,
additives do not reach a value to ionize asphaltenes species. The additives of lipophilic nature
(hexanoic acid and hexylamine) both interact on the other side of the interface (i.e., asphaltenes
in the oil phase). The hexanoic acid is found to marginally increase the emulsion stability,
probably because it could lead to a slightly more hydrophobic co-surfactant effect. In contrast,
the hexylamine, which is likely to interact with the asphaltenes through an acid−base mecha‐
nism, produces the delocalization of charges (ionization), resulting in an increase of hydro‐
philicity, and reducing the hydrophilic demulsifier requirement to attain optimum
formulation.
Commercial demulsifiers are chemical cocktails or complex mixtures of surfactants (active
substance), polymers, polar additives (alcohols, amines, ketones, and others), and solvents.
Alcohols are useful substances to promote changes on the interfacial properties of surfactant–
oil–water systems [46, 47]. Pei et al. [48] reported correlation between the interfacial tension
and solubility in water of alcohols. Interfacial concentration of the surfactant is dependent on
the less water-soluble alcohol additives will provide higher alcohol concentrations at the oil
−water interface. Generally, the formulation of such products is protected by patents. The
mechanisms and modes of action remain undisclosed in open literature. Therefore, the
methodology explained constitutes a useful tool for the petroleum industry.
Solvents are used as carriers of the active molecules, and they play a critical role in the
performance of a commercial demulsifier. Polar aromatic hydrocarbons are soluble in water,
and are frequently used as dissolvent in the formulation of commercial products. Careful
consideration is necessary of the solvent is surfactant dispersions then its addition in crude oil
is most effective. An inadequate choice of solvent may result in a delay in the rate of breaking
of emulsion and therefore other variables of the process physical o chemical are needed in
order to improve crude oil desalter operations. Pereira shows that the solvent role can be
understood using the criteria of proportional regime with solvents mixtures [7]. The position
of optimum concentration of demulsifier (CD*) is influenced by the nature of the solvent.

5. Conclusions

Here it was explained the approach from the optimum formulation concept to assist emulsion
breaking in desalting process. As part of the stabilization mechanism is accepted that the water
80 Advances in Petrochemicals

droplets are stabilized by the formation of a mechanically strong and viscoelastic film at the
interface composed of asphaltenes.

In the case of water-in-crude emulsions, a balanced optimum formulation is attained by adding

demulsifiers which are hydrophilic to the lipophilic natural surfactants contained in the crude
oil. This study aimed to determine an optimal and to relate the nature and concentration of
demulsifier products added to the amphiphilic mixture at the interface. Proportional and
saturation regimens can explaine the impact of formulation parameters, such as solvent,
alcohols, kind and concentration of demulsifier, amoung others as useful tool by the formu‐
lating personal of petroleum industry.

Acknowledgements

Juan Pereira is grateful to the projects 2010-03 CDCH-UC and PEII2012-1184 PEI-FONACIT
for funding.

Author details

Juan Pereira1*, Ingrid Velasquez1, Ronald Blanco1, Meraldo Sanchez2, César Pernalete3 and
Carlos Canelón3

*Address all correspondence to: [email protected]

1 Laboratory of Petroleum, Hydrocarbon and Derivates, University of Carabobo, Valencia,

Venezuela

2 Petróleos de Venezuela S.A. (PDVSA) El Palito Refinery, Carabobo, Venezuela

3 Petróleos de Venezuela S. A. (PDVSA)- Intevep, Gerencia General de Refinación e

Industrialización, Gerencia Departamental de Refinación. Los Teques, Caracas, Venezuela

References

[1] Vafajoo L, Ganjian K, Fattahi M. Influence of key parameters on crude oil desalting:
An experimental and theoretical study. J Petrol Sci Engin. 2012;90-91:107-111. DOI:
10.1016/j.petrol.2012.04.022

[2] Gary J, Handwerck G (eds.). Petroleum Refining: Technology and Economics. 4th edn.
Marcel Dekker, Inc. New York. USA; 2001. p. 49. ISBN: 0-8247-0482-7
 Crude Oil Desalting Process 81
http://dx.doi.org/10.5772/61274

[3] Fahim M, Alsahhaf T, Elkilani A. Crude Distillation. In: Fahim M, Alsahhaf T, Elkila‐
ni A, Fundamentals of Petroleum Refining. 1st edn. Elsevier B.V. Oxford. UK; 2010. p.
77. DOI: 10.1016/B978-0-444-52785-1.00004-8

[4] Arnold K, Stewart M. Choosing a Process. In: Surface Production Operations. Vol‐
ume 1. Design of Oil Handling Systems and Facilities. 1st edn. Elsevier. B.V. Massachu‐
setts. USA; 2007. p.30. DOI: 10.1016/B978-088415821-9/50011-7

[5] Kang W, Xu B, Wang Y, Li Y, Shan X, An F, Liu J. Stability mechanism of w/o crude

oil emulsion stabilized by polymer and surfactant. Colloids Surfaces A: Physicochem
Engin Asp. 2011;384:555-560. DOI:10.1016/j.colsurfa.2011.05.017

[6] Ramalho J, Lechuga FC, Lucas EF, Effect of the structure of commercial poly(ethyl‐
ene oxide-bpropylene oxide) demulsifier bases on the demulsification of water-in-
crude oil emulsions: elucidation of the demulsification mechanism. Quím Nova.
2010;33:1664-1670. DOI: 10.1590/S0100-40422010000800009

[7] Pereira JC, Phenomena of Rupture and Inversion Emulsions: Physicochemical and
Kinetic Aspects [Thesis]. Mérida: University of Los Andes; 2009: 11-12, 33, 11, 25-26,
46-47, 64, 46-47, 61-63, 46-47, 77-81.

[8] Silva I, Borges B, Blanco R, Rondón M, Salager J.L, Pereira JC. Breaking of water-in-
crude oil emulsions. 5. Effect of acid-alkaline additives on the performance of chemi‐
cal demulsifiers. Energy Fuels. 2014;28:3587-3593. DOI: 10.1021/ef5006918

[9] Kilpatrick P. Water-in-crude oil emulsion stabilization: review and unanswered

questions. Energy Fuels. 2012;26:4017-4026. DOI: 10.1021/ef3003262

[10] Kralova I, Sjöblom J, Øye G, Simon S, Grimes B, Paso K. Heavy crude oils/particle
stabilized emulsions. Adv Colloid Interf Sci. 2011;169:106-127. DOI: 10.1016/j.cis.
2011.09.001

[11] Daaou M, Bendedouch D. Water pH and surfactant addition effects on the stability of
an Algerian crude oil emulsion. J Saudi Chem Soc. 2012;16:333-337. DOI: 10.1016/j.jscs.
2011.05.015

[12] Fingas M, Fieldhouse B. Studies of the formation process of water-in-oil emulsions.

Marine Poll Bull. 2003;47:369-396. DOI: 10.1016/S0025-326X(03)00212-1

[13] Fingas M, Fieldhouse B. Studies on water-in-oil products from crude oils and petrole‐
um products. Marine Poll Bull. 2012;64:272-283.DOI: 10.1016/j.marpolbul.2011.11.019

[14] Delgado J. Study of Properties of Asphaltene from Boscan Crude Oil [Thesis]. Méri‐
da: University of Los Andes. 2005: 30-32, 12, 30.

[15] Shirani B, Nikazar M, Naseri A, Mousavi-Dehghani S. Modeling of asphaltene pre‐

cipitation utilizing Association Equation of State. Fuel. 2012;93:59-66. DOI: 10.1016/
j.fuel.2011.07.007
82 Advances in Petrochemicals

[16] Batista J, Lechuga F, Lucas E. Effect of the structure of commercial poly(ethylene ox‐
ide-b-propylene oxide) demulsifier bases on the demulsification of water-in-crude oil
emulsions. Quim Nova. 2010;33:1664-1670. DOI: 10.1590/S0100-40422010000800009

[17] Acevedo S, García L.A, Rodríguez P. Changes of diameter distribution with tempera‐
ture measured for asphaltenes and their fractions A1 and A2. Impact of these meas‐
urements in colloidal and solubility issues of asphaltenes. Energy Fuels.
2012;26:1814-1819.DOI: 10.1021/ef201947h

[18] Dicharry C, Arla D, Sinquin A, Graciaa A, Bouriat P. Stability of water/crude oil

emulsions based on interfacial dilatational rheology. J Colloid Interf Sci. 2006;
297:785-791.DOI: 10.1016/j.jcis.2005.10.069

[19] Fingas M, Fieldhouse B. Studies on crude oil and petroleum product emulsions: wa‐
ter resolution and rheology. Colloids Surfaces A: Physicochem Engin Asp. 2009;333:67–
81.DOI: 10.1016/j.colsurfa.2008.09.029

[20] Pacheco-Sanchez JH, Alvarez-Ramirez F, Martinez-Magadan JM. Morphology of ag‐

gregated asphaltene structural models. Energy Fuels. 2004;18:1676-1686. DOI: 10.1021/
ef049911a

[21] Acevedo S, Castro A, Vasquez E, Marcano F, Ranaudo M.A. Investigation of physical

chemistry properties of asphaltenes using solubility parameters of asphaltenes and
their fractions A1 and A2. Energy Fuels. 2010; 24:5921-5933.DOI: 10.1021/ef1005786

[22] Acevedo S, Ranaudo M.A, García C, Castillo J, Fernández A. Adsorption of asphal‐

tenes at the toluene-silica interface: a kinetic study. Energy Fuels.
2003;17:257-261.DOI: 10.1021/ef020104q

[23] Acevedo S, Caetano M, Ranaudo M, Jaimes B. Simulation of asphaltene aggregation

and related properties using an equilibrium-based mathematical model. Energy Fuels.
2011; 25:3544-3551.DOI: 10.1021/ef200107k

[24] Mullins O, Sheu E, Marshall A (eds.). Asphaltenes, Heavy Oil and Petroleomic. Springer.
2007. p. 668. DOI: 10.1007/0-387-68903-6

[25] Acevedo S, Ranaudo MA, Pereira JC, Castillo J, Fernández A, Pérez P, Caetano M.
Termo-optical studies of asphaltene solutions: Evidence for solvent-solute aggregate
formation. Fuel. 1999;78:997-1003. DOI: 10.1016/S0016-2361(99)00027-7

[26] Jeribi M, Almir-Assad B, Langevin D, Hénaut I, Argillier JF. Adsorption kinetics of

asphaltenes at liquid interfaces. J Colloid Interf Sci. 2002;256:268-272. DOI: 10.1006/jcis.
2002.8660

[27] Roodbari H, Badieia A, Soleimani E, Khaniani Y. Tweens demulsification effects on

heavy crude oil/water emulsion. Arabian J Chem. 2011:1-6. DOI: 10.1016/j.arabjc.
2011.08.009
 Crude Oil Desalting Process 83
http://dx.doi.org/10.5772/61274

[28] Nenningsland A, Gao B, Simon S, Sjöblom J. Comparative study of stabilizing agents

for water-in-oil emulsions. Energy Fuels. 2011;25:5746-5754. DOI: 10.1021/ef2014265

[29] Gao S, Moran K, Xu Z, Masliyah J. Role of naphthenic acids in stabilizing water-in-

diluted model oil emulsions. J Physic Chem B. 2010; 114: 7710-7718. DOI: 10.1021/
jp910855q

[30] Sullivan P, Zaki N, Sjöblom J, Kilpatrick P. The stability of water-in-crude and model
oil emulsions. Canadian J Chem Engin. 2007; 85: 793-807. DOI: 10.1002/cjce.5450850601

[31] Yarranton H, Hussein H, Masliyah JH. Water in-hydrocarbon emulsions stabilized

by asphaltenes at low concentrations. J Colloid Interf Sci. 2000; 228:52-63. DOI:
10.1006/jcis.2000.6938

[32] Gafonova O, Yarranton H. The stabilization of water-in-hydrocarbon emulsions by

asphaltenes and resins. J Colloid Interf Sci. 2001;241:469-478. DOI: 10.1006/jcis.
2001.7731

[33] Silva I. Breaking of Water-in-Crude Oil Emulsions: Effect of Acid-Alkaline Additives

on the Performance of No Ionic Demulsifiers. [Thesis]. Caracas: University Simón Bo‐
lívar. 2012:24.

[34] Zhang L, Breen P, Xu Z, Masliyah JH. Asphaltene films at a toluene/water interface.

Energy Fuels. 2007;21:274-285. DOI: 10.1021/ef0603129

[35] Delgado-Linares J, Pereira JC, Rangel A, Salazar F, Guevara M, Forgiarini A, Bullón J.

Effect of addition of amphiphilic molecules on asphaltene film properties at air-water
interface. Revista de la Facultad de Ingeniería de la UC. 2012;19:16-24. ISSN 1316-6832

[36] Solovyev A, Zhang L, Xu Z, Masliyah LY. Langmuir films of bitumen at oil/water in‐
terfaces. Energy Fuels. 2006;20:1572-1578. DOI: 10.1021/ef050409f

[37] Chandra M, Xu Z, Masliyah JH. Interfacial films adsorbed from bitumen in toluene
solution at a toluene–water interface: a Langmuir and Langmuir–Blodgett film ap‐
proach. Energy Fuels. 2008;22:1784-1791. DOI: 10.1021/ef700786u

[38] Zhang LY, Lawrence S, Xu Z, Masliyah JH. Studies of Athabasca asphaltene Lang‐
muir films at air–water interface. J Colloid Interf Sci. 2003; 264:128-140. DOI: 10.1016/
S0021-9797(03)00355-2

[39] Zhang L.Y, Xu Z, Masliyah JH. Characterization of adsorbed Athabasca asphaltene

films at solvent-water interfaces using a Langmuir interfacial trough. Indust Engin
Chem Res. 2005;44:1160-1174. DOI: 10.1021/ie049913i

[40] Rosen MJ (ed.). Surfactants and Interfacial Phenomena. 3rd edn. Wiley-Interscience,
2004; p. 455. ISBN 0-471-47818-0

[41] Balsamo V, Phan J, Nguyen D. Interfacial films of diluted heavy oil–aqueous systems
at elevated temperatures and pressures: effect of reverse emulsion breakers. Energy
Fuels. 2015;29:2823-2832. DOI: 10.1021/ef502072f
84 Advances in Petrochemicals

[42] Rondón M, Bouriat P, Lachaise J, Salager JL. Breaking of water-in-crude oil emul‐
sions. 1. Physicochemical phenomenology of demulsifier action. Energy Fuels.
2006;20:1600-1604. DOI: 10.1021/ef060017o

[43] Rondón M, Pereira JC, Bouriat P, Graciaa A, Lachaise J, Salager JL. Breaking of wa‐
ter-in-crude-oil emulsions. 2. Influence of asphaltene concentration and diluent na‐
ture on demulsifier action. Energy Fuels. 2008;22:702-707. DOI: 10.1021/ef7003877

[44] Pereira JC, Delgado-Linares J, Scorzza C, Rondón M, Rodríguez S, Salager JL. Break‐
ing of water-in-crude oil emulsions. 4. Estimation of the demulsifier surfactant per‐
formance to destabilize the asphaltenes effect. Energy Fuels. 2011;25:1045-1050. DOI:
10.1021/ef100979y

[45] Pensini E, Harbottle D, Yang F, Tchoukov P, Li Z, Kailey I, Behles J, Masliyah JH, Xu

Z. Demulsification mechanism of asphaltene-stabilized water-in-oil emulsions by a
polymeric ethylene oxide–propylene oxide demulsifier. Energy Fuels.
2014;28:6760-6771. DOI : 10.1021/ef501387k

[46] Baviere M, Schechter R, Wade W. The influence of alcohols on microemulsion com‐

position. J Colloid Interface Sci. 1981;81:266-279. DOI: 10.1016/0021-9797(81)90322-2

[47] Pereira JC. State of the art on the effect of alcohols on the interfacial properties of sur‐
factants. Revista Ingeniería UC. 2012; 19:76-85. ISSN 1316-6832

[48] Pei H, Zhang G., Ge J, Zhang L, Mingchao MA. Effect of the addition of low molecu‐
lar weight alcohols on heavy oil recovery during alkaline flooding. Ind Eng Chem
Res. 2014; 53:1301-1307. DOI: 10.1021/ie4028318
 Chapter 5

Overview about Different Approaches

of Chemical Treatment of NORM and
TE-NORM Produced from Oil Exploitation

N.S. Awwad, M.F. Attallah, E.M. El-Afifi,

H.A. Ibrahium and H.F. Aly

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/61122

Abstract

Crude oil or gas is considered the most important sources of natural radionuclides
from the uranium and thorium series. The radionuclides of primary concern to the oil
and gas industry are Ra226 (U238 decay) and Ra228 (Th232 decay) due to their
radiotoxicity and relatively long half-lives (1620 and 5.75 years, respectively). One of
the decay products of U238 is Rn222, a radioactive noble gas. Radon emanates from
the ground where it can be breathed in. Radon also decays to alpha-emitting progeny
nuclides, so inhaling a single radon atom can lead, ultimately, to up to four alpha
decays in the lungs before reaching stability. Alpha particles are considered as
internally hazardous if a radioactive source emitting its particles is inhaled or
ingested. So, in this chapter we shall make an overview about different approaches of
chemical treatment of NORM and TE-NORM produced from oil exploitation.

Keywords: Chemical Treatment / NORM , TE-NORM/ Oil Exploitation / Scales /

Sludge

1. Introduction

Most of the natural radionuclides in wastes from crude oil exploitation were firstly discovered
in the beginning of the last century. More types of industries have been identified dealing with
86 Advances in Petrochemicals

materials containing enhanced levels of natural radionuclides, which are summarized as TE-
NORM (technologically enhanced naturally occurring radioactive materials). Naturally
occurring radionuclides are present at varying concentrations in the Earth’s crust and can be
concentrated and enhanced by processes associated with the recovery of oil and gas. This
“enhanced’’ NORM, often known as TE-NORM, can be created as a result of industrial
processes and human activity, and in addition, can be the by-product of oil, gas production.
One of the important examples that can contain elevated levels of NORM, and the radioactive
materials may migrate from site to site as the materials and equipment are reused are sludge,
pipe scales, produced water, and drilling mud.
Transportation or decay of radioactive elements produces other radionuclides (daughters)
from the reservoir to the surface with the produced oil and gas carried out under certain
conditions dependent upon pressure, temperature, acidity. NORM with the oil, gas, and water
mixture migrate and accumulate in scale, sludge, and scrapings during the production process.
Moreover, they form a thin film on the interior surfaces of gas-processing vessels and equip‐
ment. The geological formation is considered as important parameters at determining the level
of NORM and it was found that the accumulation can vary from one site to another depending
on it.
There are three types of radiation emitted by NORM, namely:
⋅ Alpha (α) ⋅ Beta (β) ⋅ Gamma (γ)
Alpha particles are considered as internally hazardous if a radioactive source of alpha-emitting
particles is inhaled or ingested. While beta particles have one (negative) charge and interact
more slowly with the material, they are effectively stopped by thin layers of metal, wood, or
plastic and considered hazardous only if a beta-emitter source is ingested or inhaled. Gamma
emitters are associated with alpha, beta decay with high-energy electromagnetic radiation that
interacts lightly with matter. Gamma rays are best shielded by thick layers of lead or other
dense materials and are considered as an external hazard to human bodies. Figure 1 details
the origins of NORM in the recovery process [1].

2. Natural Radionuclides in the Oil Industry

2.1. Radon
One of the decay products of U238 is Rn222, a radioactive noble gas. Radon emanates from
the ground where it can be breathed in. Radon also decays to alpha-emitting progeny nuclides,
so inhaling a single radon atom can lead, ultimately, to up to four alpha decays in the lungs
before reaching stability. Since radon comes from the decay of geologic uranium, radon
concentrations will vary according to local geology. In general, radon dose will be higher in
areas that are underground, poorly ventilated, and in areas with high levels of uranium in the
rocks.
Crude oil or gas is considered the most important sources of natural radionuclides from the
uranium and thorium series. The radionuclides of primary concern to the oil and gas industry
Overview about Different Approaches of Chemical Treatment of NORM and TE-NORM Produced from Oil Exploitation 87
http://dx.doi.org/10.5772/61122

Figure 1. The origins of NORM in the recovery process [1]

are Ra226 (U238 decay) and Ra228 (Th232 decay) due to their radiotoxicity and relatively long
half-lives (1620 and 5.75 years, respectively) as shown in Figures 2 and 3 [1]. Radon radionu‐
clides escaping from the adjacent geological formations are soluble in crude oil, but due to its
half-life (3.825 days) only Rn222 is

present in the pumped oil in varying concentrations from 10 to 800 Bq/kg [1]. Many previous
data on the distribution of the main radon nuclide Rn222 in different gas fields and processing
plants were collected in the United Nations Scientific Committee on the Effects of Atomic
Radiation (UNSCEAR) report [2]. Crude oil is usually pumped to the surface together with
produce water with radon and radium radionuclides while uranium and thorium usually do
not go into solution. Various cations such as barium and strontium, with anions such as sulfate,
chloride, or the bicarbonate solubility of radon in water is lower, and the level of Rn222
concentrations in the petroleum formation water was found in the range of 18.5 Bq/dm3 [3].
Very low concentrations measured for the U and Th and produced waters were obtained under
the reducing conditions. The same result was found with radium nuclides released by alpha
from the surrounding minerals or leaching processes usually recovered by sorption, except
for saline waters with high concentration of chloride anions [4–5]. Typical ranges or average
values of the radium radionuclide concentrations in the formation or produced water from
different oil fields, including the recent data, are listed in Table 1.
88 Advances in Petrochemicals

Figure 2. Uranium238 decay series [1]

The worldwide average concentration of these radionuclides in produced water discharged

to the environment is estimated at 10 Bq/l. These concentrations are approximately three orders
of magnitude higher than the natural concentrations of radium in drinking or sea water.

Scale formation is a complex phenomenon and can be interpreted by the variation of the
solubility of carbonates or sulfates or by pressure and temperature changes, water injection
into the reservoirs, and evaporation in the gas extraction pipes. Radium and radon concen‐
trations in the pipe scale and waste sludge are dependent on three factors: the amount of Ra
present in the subsurface soil, treatment processes applied during oil or gas production, and
formation of water components. Most radium radionuclides are efficiently concentrated from
the water phase during formation of the scale. Therefore, the measured levels of activity
concentrations both in the separated sludge and in the solid scale are much higher than those
 Overview about Different Approaches of Chemical Treatment of NORM and TE-NORM Produced from Oil Exploitation 89
http://dx.doi.org/10.5772/61122

Figure 3. Thorium232 decay series [1]

measured in the produced water from the oil industry. Ra226 and Ra228 activity concentrations
measured in the solid scale and sludge are listed in Table 2.

228
Ra (Bq/dm3) 226
Ra (Bq/dm3) Sample Field

1000–950.000 Scale Algeria [8]

21.000–250.000 Scale Australia [9]
19.100–323.000 Scale Brazil [20]
121.000–3.500.000 Scale Brazil [21]
48.000–300.000
77.900–2.110.000 Scale Brazil [22]
4210–235.000
97–151 Scale Congo [11]
148.000–2.195.000
68.900 Scale Egypt [23]
101.500–1.550.000
7541–143.262 Scale Egypt [12]
24.000
< 2.7–2890 Scale Italy [11]
35.460–368.654
510–51.000 Scale Kazakhstan [24]
200–10.000
114.300–187.750 Scale Malaysia [25]
130.120–206.630
300–32.300 Scale Norway [26]
300–33.500
.08–1.5 Scale Saudi Arabia [27]
30.000
31–1189 Scale Tunisia [11]
4300–658.000 Scale Tunisia [28]
1000–1.000.000 Scale UK [29]
up to 3.700.000 Scale USA [30]
90 Advances in Petrochemicals

228
Ra (Bq/dm3) 226
Ra (Bq/dm3) Sample Field

5.1–14.8 Formation water Algeria [7–8]

23a 17a Produced water Australia [9]

0.05–12 0.01–6 Produced water Brazil [10]

1–59 5.1 a
Produced water Congo [11]

- 5–40 Formation water Egypt [12]

2.8 a
0.2-2 Produced water Italy [11]

0.5–21 0.3–10.4 Formation water Norway [12]

8.8–60.4 3.3a Produced water Norway [13]

- 0.5–16 Produced water Norway [14]

- 9.9-111.2 Produced water Syria [15]

0.7–1.7 1.7 a
Produced water UK [16]

15.1 a
0.1–60 Produced water USA [6]

25–30 0.15–21.6 Produced water USA [17]

12.6a Oilfield brine USA [18]

22–30 Produced water USA [19]

a: Mean activity concentration.

Table 1. Ranges of activity levels in produced water from the oil fields

228
Ra (Bq/dm3) 226
Ra (Bq/dm3) Sample Field

15.400–76.100 Scale USA [31]

25.000 Sludge Australia [9]

Table 2. Ranges of activity levels of 226Ra in different scale and sludge samples

From the data obtained in Table 2, it was found that the concentration levels of radium nuclides
in sludge were much lower than those of the scale. Environmental Protection Agency (EPA)
estimated the average radium nuclide concentration to be around 2800 Bq/kg and 18, 000 Bq/
kg in sludge and scale, respectively [32]. The exposure is caused by external radiation coming
from the 226Ra radionuclide and its progenies: Pb214 and Bi214 as well as by inhalation of α-
emitting radionuclides; Rn222 as well as Po218 and Po214 formed from Rn222 escaping into
the air adjacent to scale deposits, see Table 3.

The main types of scales encountered in oil and gas facilities are sulfate scale such as BaSO4,
which is called barite. Colorless or milky white is the common one, but can have any color,
depending on the impurities trapped in the crystals during barite formation. The high density
of barite is responsible for its value in many applications. It is always chemically inert and
Overview about Different Approaches of Chemical Treatment of NORM and TE-NORM Produced from Oil Exploitation 91
http://dx.doi.org/10.5772/61122

Reported range (µSv/h) Country

Background–100 Algeria [8]

10–300 United Kingdom [8]

50–100 Egypt [23]

0.1–6 Congo, Italy, Tunisia [11]

up to 300 USA [5]

Table 3. Exposure rate levels in the oil industry

insoluble. Due to the high chemical similarity of radium with barium (Ba), strontium (Sr), and
calcium (Ca), radium co-precipitates with Sr, Ba, or Ca scale forming radium sulfate, radium
carbonate, and in some cases radium silicate is produced. As mentioned before, the mixing of
seawater, which is rich in sulfate, with the produced water, which is rich in Cl–1, increases the
scaling tendency. In addition, any change in pressure and temperature or acidity of the
formation water contributes to scale build-up. The build-up of scale on the interior of a pipe
is shown in Figure 4. The activity concentrations of Ra226 and Ra228 in hard scales in Egypt
and some other countries were mentioned in Table 4.

Figure 4. The build-up of scale on the interior of a pipe

Inhibitors may be applied to the piping complexes to prevent scales from slowing the oil
extraction process. If the scales contain TE-NORM, the radiation will remain in solution and
eventually be passed on to the produced waters. The United States generated annually around
100 tons of scale per oil well. Sometimes, in some cases brine is introduced into the produced
water to enhance the recovery of radium; this also increases scale formation.
92 Advances in Petrochemicals

Activity (Bq/g)
Country/region Ref.
226
Ra 228
Ra

Egypt/oil field

Abu Rudeis 68.9 24 [33]

Gabal El Zeit 14.8 4.3 [34]

Badr El Din 31.4 43.3 [34]

Red Sea 195 897.8 [35]

Western desert 59.2 244.5 [35]

Other countries

Australia 20–70 [36]

USA 70.8 [37]

Algeria 1–950 [38]

Tunisia 4.3–658 [39]

UK 1–1000 [40]

Table 4. Activity of 226Ra (U-series), 228Ra (U-series), and 40K in the TE-NORM in Egypt and some countries

2.2. NORM in sludge

Radioactive molecules containing radium which were not incorporated into scale can be found
in sludge, produced sands, and produced waters. Before the treatment investigations, the
activity concentrations of the main three radium isotopes were measured in sludge [41]. It is
found that the average activity level of Ra226, Ra228, and Ra224 for samples taken from Abu
Rudeis region, Government of Sinai–Egypt, were 11950, 1750, and 1900 Bq/kg, respectively.
Due to the accumulated TE-NORM wastes in huge amounts and release of high activity
concentrations to the environment and the workers, treatment approaches are suggested to
reduce the human and environmental hazard potential. Sludge is composed of dissolved solids
which precipitate from produced water as its temperature and pressure change. Sludge
generally consists of oily, loose material often containing silica compounds, but may also
contain large amounts of barium.

2.3. NORM in natural gas

Radon is a radioactive noble gas, present in varying level in natural gas in oil and gas forma‐
tions. In the absence of natural gas, radon easily dissolves in the light hydrocarbon. Radon
usually follows the gas stream when produced with the oil and gas. If the natural gas is
fractionated, higher percentage of radon can concentrate in the propane streams and lower
degree in the ethane streams. Most of the radon decay products are found in ambient aerosols,
airborne particulates, or surfaces. Most radon progeny are short-lived, with the exception of
Po210 and Pb210, which have relatively long half-lives of 138 days and 22.6 years, respectively.
Formation of thin radioactive films on the inner surfaces of gas-processing equipments, such
Overview about Different Approaches of Chemical Treatment of NORM and TE-NORM Produced from Oil Exploitation 93
http://dx.doi.org/10.5772/61122

as scrubbers, compressors, reflux pumps, control valves, and product lines, due to the release
of daughters of radon.

2.4. NORM in produced water

Formation water at oil and gas reservoirs called produced water float to the surface during oil
and gas production. However, gas reservoirs typically produce smaller quantities whereas the
oil reservoirs can contain large volumes of formation water. Water is injected into the reservoir
to maintain pressure and or maximize production in most fields. The produced water stream
can be one of the largest waste products, by volume produced from oil and gas industry. It
was found that the produced water contains a complex mixture of inorganic compounds, such
as dissolved salts, trace metals, suspended particles and organic compounds such as dispersed
and dissolved hydrocarbons, organic acids, and residual chemical additives such as scale and
corrosion inhibitors that are added into the hydrocarbon production process. Technologies of
treatment depending on the application and particular field conditions. Also, it is to consider
include combinations of gravity and / or mechanical separation and chemical treatment, and
may include a multistage system, typically including a parallel plate separator, followed by a
gas flotation cell or hydrocyclone. For disposal of produced water to sea, some criteria should
be considered to reduce the volume of produced water, such as:

Select adequate well management during well completion to minimize water production;

Minimize water production by recompletion of high water-producing wells;

To be economically feasible, use down hole fluid separation techniques, where possible.

For reducing environmental hazards related to residual chemical additives in the produced
water stream, where surface disposal methods are used, production chemicals should be
selected carefully by taking into account their volume, toxicity, and bioaccumulation potential
[42]. The average worldwide activity levels of uranium (U), thorium (Th), and potassium (K)
[43] and the exemption activity levels of NORM as recommended in the IAEA basic safety
standards [44] were given in Tables 5 and 6. The average worldwide levels of the most common
radiological indices [43] were given in Table 7. These indices include radium equivalent (Ra-
eq), total absorbed dose (Dγr), and effective annual dose rate (EDAR).

Radionuclide U Th K

Activity level (Bq/Kg) 50 50 500

Table 5. The average worldwide activity levels of uranium (U), thorium (Th), and potassium (K)

Radionuclide U238 Ra226 Rn222 Th232 Ra228 Ra224

Exemption level (Bq/g) 1 10 10 1 10 10

Table 6. The exemption activity levels of NORM as recommended in the IAEA basic safety standards
94 Advances in Petrochemicals

Radiological indices (Unit) Ra-eq (Bq/Kg) Dγr EADR (mSv/yr) for EADR (mSv/yr)
(nGy/h) worker for Public

Activity level (Bq/Kg) 370 55 20 1

Table 7. The average worldwide levels of the most common radiological indices

3. Resources of NORM and TE-NORM

Earlier, we saw that many natural materials contain radioactivity. Some of these materials are
used in manufacturing: clays and various minerals. In other cases, radioactive elements are
used in manufacturing – not because of the radioactivity, but because of other chemical or
physical properties. For example, thorium is radioactive, and it has a high melting temperature;
for this reason, thorium is used in the manufacture of some welding electrodes, gas lantern
mantles, and jet turbine blades. These products and the wastes from their manufacture will
contain low levels of radioactivity. Many fossil fuels are associated with radioactivity; the
geochemistry of uranium is such that it is often found in petroleum, natural gas, and coal
deposits. The equipment used to extract and process these materials is often contaminated
with NORM materials, especially with radium, which can be present in the scales and sludges
from processing these materials. Although refined petroleum and natural gas products do not
contain large levels of these nuclides, coal can; so, fly ash often contains elevated levels of
radioactivity as well. In fact, when 90% or more of the coal is burned, all of the radioactivity
is left in the remaining 10% that is ash. Thus, fly ash is considerably more radioactive than is
the original coal. Uranium and thorium are fairly common in nature, and many minerals
contain elevated levels of these radioactive elements and their decay series nuclides. In
particular, minerals containing rare earth elements (such as monazite), titanium minerals,
niobium ores, and some precious metal ores can be associated with elevated levels of radio‐
activity. When the minerals are processed, the metal is removed from the ore, and the radio‐
activity concentration in the remaining waste is even higher than in the original ore. In addition
to all of these, anything that contains potassium will be somewhat radioactive because 1/100%
of potassium is naturally radioactive. Potassium is found in many minerals, some forms of
clay, and in many products – consumer and industrial both – so sometimes these items will
also give high levels of radiation. Loads of bananas, kitty litter, and salt substitute all contain
enough radioactive potassium to set off radiation alarms.

3.1. NORM and TE-NORM at the landfill

Many industries produce wastes that might contain natural radionuclides, and most of these
wastes end up at landfills, either hazardous or otherwise. The majority of TE-NORM sources
waste arise from industrial processes. Most of the wastes obtained are produced in very large
amounts with low activity. Improper disposal, recycling, and reuse of TE-NORM have led to
circumstances resulting in contamination and unnecessary public exposures.
Overview about Different Approaches of Chemical Treatment of NORM and TE-NORM Produced from Oil Exploitation 95
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Disposal of TE-NORM in piles or stacks can lead to contamination of groundwater and

airborne releases of radioactive particulates and radon. Improper use and/or disposal of the
TE-NORM used for soil conditioning or fill around homes can lead to accumulation of radon
gas in homes, direct exposure to individuals, and contamination of soil and of the crops
growing in the soil. Reuse of TE-NORM-contaminated materials, such as in concrete aggregate,
ceramic industry, and red stone can lead to increased radiation risks to members of the public
in a variety of ways.
The main radionuclides daughter found in the uranium series in industrial TE-NORM are 238U,
234
U, 230Th, 226Ra, and 222Rn, while the thorium series are 232Th, 228Ra, and 220Rn. In addition, 40K
should be characterized. Radium226 is used as a monitor to show the relative activity and
volume among the TE-NORM sectors. It was found that Radium226 is in equilibrium with its
progeny, but Radium228 is not and their activity appears to be about three times greater than
Radium228.

4. General Technologies for Treatment of TE-NORM Waste

4.1. Use of reagents

A water-bath heater from a gas production facility in North Sea (e.g., the Netherlands) has
been used as a test for equipment in laboratory aimed at the in situ removal of TE-NORM. This
is achieved by circulating an aqueous solution of commercially available scale dissolver
through the contaminated equipment. For this purpose, some scale dissolvers which are
widely used within exploration and production are commonly based on chelating chemistry
and reportedly successfully applied in the dissolution of low specific activity scales [45]. For
instance, application of scale dissolver reagents resulted in the rapid and complete removal of
226
Ra and progeny-containing sulfate scales as well as 210Pb-containing sulfide scales from the
head internals. These studies were performed using scale dissolver consisting of 15% v/v acetic
acid and 1% v/v strongly oxidant, e.g., KMnO4. This reduced the total activity from 20
Bq/cm2 to 6 Bq/cm2, the residual activity may be removed using 0.5 M citric acid. Also, scale
dissolver solution containing 15% v/v acetic acid plus 1% v/v hydrogen peroxide was used to
dissolve TE-NORM contaminated by overall activities of 2000 Bq (226Ra)/g and 600 Bq(2t0Pb)/g.
This was followed by water flush. Generally, the application of a chemical scale dissolver can
remove 95–99% of TE-NORM present in exploration and production facilities. On the other
hand, radioactive scales containing 226Ra and its progeny, such as barium sulfate scales, are
removed chemically using hydrochloric acid, and the dead acid is disposed as waste after
appropriate radiometric checks [46].

4.2. Recycling equipment

The contamination produced from the accumulation of toxic materials mainly include heavy
metals such as mercury and radioactive materials of the natural origin (e.g., 226Ra, 228Ra, 210Pb).
For decontamination purpose, the contaminated equipments were taken into melting plant,
especially built for this process; its annual capacity is 2000 tones of steel and metal scrap
96 Advances in Petrochemicals

contaminated with mercury and TE-NORM. After melting, the radiological measurements
showed that the produced metal did not contain any detectable residual of TE-NORM, and
can be re-used again in steel works. About 98% of TE-NORM were bound to the slag and ~2%
were detected in the filter dust, mainly consisting of the nuclides 210Pb and 210Po. The secondary
waste produced is ∼43% of the total weight of the material supplied, whereas TE-NORM waste
consists of ~95% of slag and ~5% coarse dust [45].
Chemical separation of the radionuclides incorporated in the contaminated equipment
(pipelines, tubes, pumps) is carried out by melting at 1400°C, to further fractionation of
radionuclides in melt, slag, or dust. The analysis of data showed that most of 238U and 232Th
series are transferred from melt (dense main component, contains only 1% of the remainder
radioactivity) into the slag (light minor component, contains only 98% of the total radioactiv‐
ity). All activity of 210Pb was concentrated in the filter dust, because it is evaporated at normal
melting temperature above 1300°C [47]. Equipment should be decontaminated to less than 0.4
Bq/cm2 for alpha emitters or 4 Bq/cm2 for beta and gamma emitter, before any release.

4.3. Solid TE-NORM waste

For TE-NORM-contaminated scale, sludge, and soils with very low levels of radioactivity, a
suitable disposal option is to spread over the ground and mix with non contaminated soils, to
dilute the contaminated soils and reduce the radioactivity level to background levels. This type
of disposal is often the most cost-effective [48]. Subsurface disposal options include under‐
ground injection and down hole encapsulation. This type of disposal is widely acknowledged
as one of the most environmentally sound methods of disposing TE-NORM-contaminated
sludge. The two common forms of subsurface disposal are:

i. Underground injection, established by mixing a TE-NORM-contaminated waste with

cement in a slurry, then injecting the formed mixture into a deep subsurface forma‐
tion.
ii. Down hole encapsulation, entails placing TE-NORM-contaminated scale, sludge,
tubes, and other small pieces of the production equipment (e.g., valves, filters, pumps,
screens) inside the casing of a well, which is to be plugged with cement and then
abandoned.

4.4. Liquid TE-NORM waste

TE-NORM in slurry form (e.g., waste water or solids mixed with water) can be re-injected into
deep formations for disposal [18]. There are three classes for injection:
Class (I): This option is used for any liquid TE-NORM wastes. Over 90% of all produced water
resulting from oil and gas operations is injected through wells into permeable disposal
formations, which lie below underground sources of drinking water (USDW), and surrounded
by impermeable layers. After injection, the well is closed, sealed with cement, and capped,
effectively isolating injected materials from the surface. Injection costs vary based on volume,
depth, formation pressure and permeability, and other factors. The cost of injecting a slurry
could be comparable, or slightly higher.
Overview about Different Approaches of Chemical Treatment of NORM and TE-NORM Produced from Oil Exploitation 97
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Class (II): Well injection, when TE-NORM concentrations prevent disposal in class (I). The used
wells in this class are deeper and are constructed to give great protection against potential
migration of injected fluids to (USDW). Disposal in class (II) well is to some degree more
expensive than class (I) injection. Also, transportation costs would be higher, as limited number
of class (II) disposal wells exist.

Class (III): Deep well injection, these wells consist of injecting liquid wastes contaminated by
TE-NORM fluids into the well at sufficiently high pressure to create a fracture in permeable
shale formations. After the scale/water mixture is displaced into the fracture, then the pressure
is reduced, and the fracture closes.

The scale is trapped between the fracture wells and is incapable of re-entering the well bore.
Deep well injection is generally regarded as an effective method for the disposal of TE-NORM
waste because it does not depend on the mechanical integrity of the well to prevent potential
subsurface contamination.

When the radium ions are present in the produced water, any drops in pressure and temper‐
ature can lead to the solubility products of their sulfates and carbonates being exceeded. This
is the main cause for precipitation of radium as sulfate and carbonate scales on the inner walls
of production tubules, well heads, valves, pumps, separators, water treatment vessels, gas
treatment and oil storage tanks. Particles of clay or sand co-produced from the reservoir may
also act as catalytic surfaces for initiating scale deposition or may adsorb the cations. Daifullah
and Awwad [49] found that oil shale is a good adsorbent for Hg(II) from aqueous solution.
Shales normally contain at least 35% clay minerals, and a significant fraction contains potas‐
sium as an essential constituent. Removal of mercury (II) from wastewater was studied using
camel bone charcoal [50]. Shales can adsorb the series radionuclides [51]. Common anthropo‐
genic sources of mercury include nuclear fuel production as part of the uranium purification
and isotope separation process (235U and 238U). Mercury in the form of Hg(II) also enters aquatic
environments from industrial and nuclear fuel wastes. The feasibility of using oil shale for
removal of Hg(II) has been addressed. Also, it was found when using seawater to enhance oil
recovery, it will increase the sulfate concentration of the produced water and enhance scale
deposition. So, new trends should be used to solve these problems.

5. New Approaches Used in the Treatment of NORM and TE-NORM

Produced from Sludge Waste Obtained from Oil and Gas Production

In oil and gas production, the TE-NORM may be solid waste as scale and/or sludge and
produced water. Our literature shows that TE-NORM contains activity concentrations of Ra226
ranging from undetectable levels to 1000 kBq/kg [52] and the activity level concentrations of
Ra226 in TE-NORM can be much higher than the exemption levels established by IAEA [53].
As mentioned before, the recommended exemption level for uranium-series is: U238 = 1 Bq/g
and Ra226 = 10 Bq/g. For thorium decay, a chain is: Th232 = 1 Bq/g, Ra228 = 10 Bq/g, and Ra224=
10 Bq/g.
98 Advances in Petrochemicals

It is important to focus on the environmental and health impacts from the uncontrolled release
of TE-NORM wastes [54, 34, 23]. Treatment of these wastes is of increasing interest because
accumulation of large amounts with a significant activity may cause health risks to the workers
through exposure, inhalation of radon (Rn222) decayed from radium, and/or ingestion of
waste dust during the periodical maintenance of the equipment used. Treatment of TE-NORM
wastes from many industries still needs more efforts. The traditional methods used before
include subsurface disposal, volume reduction, use of scale and/or sludge inhibitors, recycling,
and leaching using chemical solutions [55–57]. In addition, a simple extraction process is
carried out using saline solutions and chemical solutions [41, 58] to removal of Ra226, Pb210,
Rn220, Th232, Ra228, and Ra224 from TE-NORM wastes produced from oil and gas industry.

Sequential chemical treatment for radium in sludge or scale to reduce its activity concentration
in oil and natural gas production fields is recommended. The proposed treatment method was
carried out on the basis of two approaches using chemical solutions through four successive
steps.

Successive four steps were used to leachate the radium species in the waste of TE-NORM [59].

Before the treatment investigations, the activity concentrations of the main three radium
isotopes were measured. It is found that the average activity level of Ra226, Ra228, and Ra224
were 11950 ± 1700, 1750 ± 200, and 1900 ± 250 Bq/kg, respectively. Due to the high accumulation
of radium species in huge amounts and high activity concentrations causing health hazards
to the environment and the workers, sequential chemicals treatment approaches are suggested
as a new trend to reduce the human and environmental hazard potential.

5.1. Approach of treatment

It is well known that the environmental behavior and toxicity of trace elements and radionu‐
clides depend strongly on their physicochemical forms (i.e., speciation) in the environment
[60]. In this study, the applied treatments involve four steps achieved sequentially for each
approach. Selective extraction of the different radium species present in TE-NORM waste, such
as water-soluble species, exchangeable, carbonates, reducible species, oxidizable organics
becomes allowed.

5.1.1. Approach 1

The treatment of the radium content in TE-NORM using sequential chemical leaching was
based on the individual extraction for each Ra species in the waste, according to the successive
four steps (A.1–4). From the data obtained, it was found that the exchangeable radium species
was removed from the waste. The removal percentages (%) for Ra226, Ra228, and Ra224 are
5.7 ± 2.4, 6.5 ± 1.4, and 3.1± 0.9%, respectively. These values are high if comparable to the
exchangeable Ra species present in and extracted from phosphate ores [61].

In the second step of leaching (A.2), the data obtained show that the removal percentages (%)
are found to be of 9.9 ± 0.4, 7.5 ± 0.9, and 11.8 ± 0.2 % for Ra226, Ra228, and Ra224, respectively.
This leached part is related to the Ra fraction bounded to carbonate species (acidic fraction of
Overview about Different Approaches of Chemical Treatment of NORM and TE-NORM Produced from Oil Exploitation 99
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species Ra). In step number three (A.3), it was found that the removal percentages of Ra226,
Ra228, and Ra224 are 10.9 ± 1.4, 18.3 ± 2.5, and 19.6 ± 0.4%, respectively. This leached part is
related to radium species bounded to metal-oxides such as the Fe-Mn-oxides [62]. The
remaining part of radium species found bounded to organic matter and sulfides was leached
through two substeps (A.4). The final removal percentages by this approach related to Ra226,
Ra228, and Ra224 are 51.5 ± 2.1, 32.5 ± 4.1, and 41.9 ± 5.2%, respectively, as shown in Figure 5.

Step A.1 20% MgCl2 (pH 7, 50 ± 1 oC, 1.5 hrs)

Step A.2
0.04M H2NOH.HCl / 25% CH3COOH (95 ± 2 oC, 6 hrs)

Step A.3
1M CH3COONa/ CH3COOH (pH 5 and
re-adjusted after 2 hrs, 25 ± 1 oC, 5 hrs)

Step A.4
I. 30% H2O2 / 0.0075M HNO3 (pH 2, 85 ± 2 oC, 5 hrs)
II. 3.2M NH4NO3 / 20% HNO3 (25±1 oC, 0.5 hr)

Figure 5 Sequential leaching of the radium content in TE-NORM was based on the
Figure 5. Sequential leachingindividual
of the radiumextraction for eachwas
content in TE-NORM Ra based
species in the
on the wasteextraction for each Ra
individual
species in the waste
According to approach 1, the successive leaching steps released most of the radium species
According
found intothe approach 1, the successive
treated TE-NORM waste.leaching steps
Also, from thereleased most of itthe
data obtained, is radium
observedspecies
that the real
found in the treated TE-NORM waste. Also, from the data obtained, it
removal percentages (%) of Ra226, Ra228, and Ra224 are 78 ± 2.8, 64.8 ± 4.1, and 76.4 is observed that the± 5.2%,
real removal percentages (%) of Ra226, Ra228, and Ra224 are 78 ± 2.8, 64.8 ± 4.1, and 76.4
respectively. There is variation in the leaching % for each Ra-isotope due to the radiochemical factors
± 5.2%, respectively. There is variation in the leaching % for each Ra-isotope due to the
radiochemical factors such
such as the differences as the
in their differences
half-lives. in their
Figure half-lives.
6 shows Figure
the leaching of 6theshows the Ra
different leaching
species in the
of the different
waste. Ra species
It is observed in the
that the waste. It
oxidizable Raisspecies
observed that
is the theRa
main oxidizable
fraction inRa species
this type ofis waste.
the This
main Ra fraction in this type of waste. This may be attributed to the high concentration of
may be attributed to the high concentration of leaching solutions used to remove Ra species within the
leaching solutions used to remove Ra species within the TE-NORM sludge waste. There‐
TE-NORM
fore, the radium sludge waste.
species in Therefore,
the treatedthe radium
waste species
using in the A
approach treated
can bewaste using as:
ordered approach
oxidiza‐A can be
bleordered
> reducible > acidic >> exchangeable.
as: oxidizable reducible > acidic > exchangeable.
100 Advances in Petrochemicals

90

80 R a -2 2 6
70
R a -2 2 8
R a -2 2 4
60
leached %

50

40

30

20

10

E x c h a n g a b le A c id ic R e d u c ib le O x id is a b le O v e r a l ( A .1 - 4 )

R a s p e c ie s
F ig .6 . D is t r ib u t io n o f r a d iu m s p e c ie s in T E N O R M s lu d g e u s in g a p p r o a c h A
Figure 6. Distribution of radium species in T E NORM ludge using approach A

5.1.25.1.2. Approach 2
Approach 2
In approach 2, the TE-NORM waste was treated sequentially using different chemical leaching,
through four leaching
In approach steps.
2, the The de-aerated
TE-NORM and was
waste de-ionized H2Osequentially
treated (pH 6.7, 25 ± 1°C,
using4 h), 1M
different chemic
CH3COONH4 (pH 6.8, 25 ± 1°C, 4 h) as water-soluble and exchangeable solutions for removal
, through four are
of Ra species leaching
used. Thesteps. The de-aerated
results showed andpercentages
that the leached de-ionized
(%) ofH 2O (pH
radium 6.7, 25
isotopes ± 1C,
are 10.6 ± 1.5, 9.7 ± 1.2, and 11.2 ± 0.8 % for Ra226, Ra228, and Ra224, respectively (step B.1).
CH3COONH4 (pH 6.8, 25 ± 1 C, 4 h) as water-soluble and exchangeable solutions for rem
In the second leaching process (B.2), the acidic radium species such as carbonates, and in
species are used.
addition, Theand
some iron results showed
manganese thatarethe
oxides leached
removed. Thepercentages (%) of (%)
leaching percentages radium
of isotopes
radium species are 12.8 ± 2.8, 15.2 ± 0.5, and 16.5 ± 1.2% for Ra226, Ra228, and Ra224, respec‐
1.5, tively.
9.7 ± The
1.2,remaining
and 11.2waste
± 0.8 % for Ra226, Ra228, and Ra224, respectively (step B.1).
was leached through two successive substeps. The solutions used
are selective to the reducible radium species in the waste, such as manganese oxides, amor‐
phous iron oxide, and moderately reducible phase (step B.3). The obtained removal percen‐
In the second leaching process (B.2), the acidic radium species such as carbonates, and
tages (%) of Ra226, Ra228, and Ra224 are 14.2 ± 1.2, 17.4 ± 3.1, and 19.0 ± 1.5%, respectively.
Finally, the remaining waste was treated using oxidizing reagent solution, as a selective
, some iron agent
chemical and manganese oxides are
to leach the oxidizable removed.
radium species The
in theleaching
waste (steppercentages (%) of radium
B.4). The leached
percentages (%) of the oxidizable Ra species are 53.3 ± 1.2, 48.4 ± 1.9, and 45.0 ± 2.3% for Ra226,
12.8Ra228,
± 2.8,and15.2
Ra224, respectively,
± 0.5, and 16.5 as shown in Figure
± 1.2% 7.
for Ra226, Ra228, and Ra224, respectively. The
From the data obtained from two leaching sequence mentioned above, it was found that using
selective
waste chemical through
was leached solutions istwo
more efficient when
successive dealing with
substeps. Thethe different radium
solutions species
used are selective to th
present in the TE-NORM waste. Also, the data showed that the overall removal percentages
(%) ofspecies
radium all radium
inspecies are 90.9 ±such
the waste, 3.5, 86.7
as± 4.1, and 89.7± 6.2%
manganese for Ra226,
oxides, Ra228, andiron
amorphous Ra224,oxide, and
respectively. These values indicate that the amounts leached of the three radium isotopes by
this approach are nearly the same. Figure 8 represents distribution of the actual removed (%)
reducible phase (step B.3). The obtained removal percentages (%) of Ra226, Ra228, and

14.2 ± 1.2, 17.4 ± 3.1, and 19.0 ± 1.5 %, respectively. Finally, the remaining waste was tre

oxidizing reagent solution, as a selective chemical agent to leach the oxidizable radium spe
Overview about Different Approaches of Chemical Treatment of NORM and TE-NORM Produced from Oil Exploitation 101
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Step B.1
I. deaerated & deionized H2O (pH 6.7, 25 ± 1 oC, 4 hrs )
II. 1M CH3COONH4 (pH 6.8, 25 ± 1 oC, 4 hrs)

Step B.2
1M CH3COOH (50 ± 1 oC, 4 hrs)

Step B.3 I. 0.1M H2NOH.HCl / 0.01M CH3COOH (pH 1.4, 25 ± 1 oC, 4 hrs)
II. Sodium citrate solution (pH 1.4, 25 ± 1 oC, 4 hrs)

Step B.4 I. 30% H2O2 (pH, 2, 75 ± 1 oC, 4 hrs)

II. 1M CH3COOH / 1M HNO3 (75 ± 1 oC, 4 hrs)

Figure 7. Sequential leaching of the radium content in TE-NORM was based on the individual extraction for each Ra
species in the waste
Figure 7 Sequential leaching of the radium content in TE-NORM was based on the
individual extraction for each Ra species in the waste
toward different types of the radium species found in the treated TE-NORM waste. It is found
that the high removal % of Ra226 is obtained for the radium oxidizable species. This is due to
the high ability of the leaching solutions used in step (B.4) to remove the radium species from
sludge waste. This conclusion confirms that the same behavior is obtained when using
approach A. Therefore, the oxidizable Ra species is the main Ra fraction in waste. So, the net
conclusion, the sequence of the different radium species present in the treated waste by
leaching (%) can be ordered as: oxidizable > reducible > acidic > exchangeable as shown in
From the data obtained from two leaching sequence mentioned above, it was found that using
Figure 8.
selective chemical solutions is more efficient when dealing with the different radium species present in
The overall removal (%) of the radium species using the both approaches (A and B) are
illustrated in Figurewaste.
the TE-NORM 9. It is showed
Also, that
the data the overall
showed that theremoval percentages
overall removal of Ra226
percentages (%) and
of allRa224
radium
are nearly the same when the waste is leached using approaches A and B. It is found that values
of thespecies
overallareremoval
90.9 ± 3.5,% 86.7 ± 4.1,and
of Ra226 and Ra224
89.7± 6.2% for Ra226,
leached using Ra228, andof
solutions Ra224, respectively.
approach A are 78%These
and 76%,
valuesrespectively.
indicate that theOnamounts
the other hand,
leached it was
of the three found
radium that the by
isotopes overall removal
this approach are%nearly
usingthe
solutions of approach B is increased to ~90 % for Ra226 and Ra224. While the overall leached
% of Ra228 is low8comparable
same. Figure to Ra226 and
represents distribution Ra224
of the actualatremoved
the same (%)leaching
toward conditions,
different typesthe
ofobtained
the radium
overall removal percentages of Ra228 are ~65% and 87.5% using solutions of the approaches
species found in the treated TE-NORM waste. It is found that the high removal % of Ra226 is
A and B, respectively (Figure 9). The variation in the overall removal % between the leached
Ra species from
obtained for the
the TE-NORM sludgespecies.
radium oxidizable waste This
under is the
due same
to theleaching conditions
high ability is difficult
of the leaching to
solutions
be explained. Finally, treatment of the sludge waste using solutions of approach B is more
used in step (B.4) to remove the radium species from sludge waste. This conclusion confirms that the
efficient compared to approach A, toward the overall removal percentages of Ra species.

18
 100

102 Advances in Petrochemicals

R a -2 2 6
80
R a -2 2 8
R a -2 2 4
100
leached %
60
R a -2 2 6
80
R a -2 2 8
40 R a -2 2 4
leached %

60

20
40

0 20
e x c h a n g a b le A c id ic re d u c ib le o x id is a b le O v e ra l (B .1 - 4 )

0
e x c h a n g a b le A c id ic
R a so xpid isea c
re d u c ib le b le
ie s O v e ra l (B .1 - 4 )
Fig.
F ig 8.
.7 . D is tr ib u tio n o f r a d iu m s p e c ie s in T E N O R M s lu d g e u s in g a p p r o a c h B
R a s p e c ie s
Fig.
F ig 8.
.7 . D is tr ib u tio n o f r a d iu m s p e c ie s in T E N O R M s lu d g e u s in g a p p r o a c h B

Figure 8. Distribution of radium species in TENORM s ludge u sin g approach B

approach A
approach A
100100 approach
approach B B

90 90
80
80
70
overall removal %

70
overall removal %

60
60 50

50 40
30
40
20
30
10
20 0
Ra-226 Ra-228 Ra-224
10 Radium species
0
Fig.Fig.8.
9. OverallRa-226
removal percentages (%) of radium species
Ra-228 leached
Ra-224
from TENORM waste sludge
Radiumusing approaches A and B
species

Fig.Fig.8.
Figure 9. Overall 9. Overall
removal removal
percentages percentages
(%) of radium species leached(%)
from of radium
TENORM species
waste leached
sludge using approaches A
and B from TENORM waste sludge using approaches A and B
The sequential chemical treatment could be the key point for environmental-friendly leaching for
The sequential chemical treatment could be the key point for environmental-friendly leaching
for TE-NORM
TE-NORM waste the
waste to select to select the suitable
suitable chemicalschemicals for the treatment
for the treatment processes
processes [33]. [33].
Thealternative
The other other alternative
processprocess for treatment
for treatment of these
of these wastes
wastes is leaching
is leaching or solubilization
or solubilization of of
thethe
different
Theradionuclides.
sequential
differentchemical
This treatment
radionuclides.
is based This could
is based
on partial be the
on partial
dissolution of key point
dissolution of the for environmental-friendly
radionuclides
the radionuclides acids or by leach
using strong
using strong
acids or by conversion of hardly or insoluble radionuclides forms to easily soluble salts. Within
TE-NORM waste
conversion
these of tohardly
merits,select
or the suitable
insoluble
investigations were chemicals
radionuclides
carried for to
forms
out to the
assess treatment
easily
the directsoluble processes
leachingsalts. [33].
Within these
of radionuclides by merits,
HCl or HNO or by treating the waste with carbonate solutions followed
investigations
The other alternativewere 3carried
process out
for totreatment
assess the of
direct leaching
these of
wastes radionuclides
is leaching orbyHCl
by leaching
or HNOthe3 or by
solubilization of the d
treating the waste with carbonate solutions followed by leaching the formed carbonates with dilute
adionuclides. This is based on partial dissolution of the radionuclides using strong acids
acid solution. The different conditions for the maximum removal of the radionuclides Pb210, Ra226,
onversion of hardly
and Ra228 from theorsludge
insoluble
and theradionuclides
scale wastes are forms to easily
given. From soluble
this table, salts.
it is clear thatWithin
leaching these
nvestigations
with nitricwere carried out
acid produced bettertoleaching
assessefficiency
the directfor leaching
the removalofofradionuclides by Ra228
Pb210, Ra226, and HCl or
andHNO
Overview about Different Approaches of Chemical Treatment of NORM and TE-NORM Produced from Oil Exploitation 103
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formed carbonates with dilute acid solution. The different conditions for the maximum
removal of the radionuclides Pb210, Ra226, and Ra228 from the sludge and the scale wastes
are given. From this table, it is clear that leaching with nitric acid produced better leaching
efficiency for the removal of Pb210, Ra226, and Ra228 and then the use of hydrochloric acid.
This is relating mainly to the oxidizing action of nitric acid. It is also clear that treatment with
carbonate before leaching adds some benefits to the removal efficiency. This can be related to
the possible conversion of the sulfate salts to the carbonate, which is easily leachable by dilute
acids.

Leaching the carbonate treated sludge and scale wastes by high acid concentration can produce
better removal for the different radionuclides, Table 8, yet use of strong acid is not recom‐
mended for its hazardous action. Therefore, and out of the different leaching systems studied,
it can be recommended that the treatment of both the sludge and the scale wastes by 10%
Na2CO3 followed by leaching with 1 M HNO3 solution is recommended. This treatment will
remove more than 70% of Pb210, Ra226, and Ra228 from scale waste and more than 55% of the
same radionuclides from the sludge waste. It is also noted that the % removal of Ra226 is
different than that of Ra228. This suggests that Ra226 is concentrated in different species of
these wastes [63].

Method Removal, %

Pb210 Ra226 Ra228

Sludge Scale Sludge Scale Sludge Scale

HCl (7.5M) 36±2.1 56±2.8 29±1.5 19±1 22±1.2 34±1.7

10%Na2CO3/0.5M HCl 63±3.1 77±3.8 52±2.8 50±2.5 39±2 56±2.8

10%(NH4)2CO3/0.5MHCl 21±1.1 63±3.1 23±1.1 32±1.8 44±2.2 37±1.8

25%(NH4)2CO3/0.5MHCl 55±2.6 50±2.5 56±2.8 8.5±0.4 66±3.3 44±2.1

10%Na2CO3/1M HCl 66±3.5 76±3.7 54±2.6 53±2.6 47±2.7 85±4.3

(NH4)2CO3/1M HCl 56±2.6 67±3.4 58±2.7 48±2.4 68±4.1 63±3.2

HNO3 (7.5M) 37±2.2 53±2.5 35±2 16±0.8 21±1 37±1.8

10%Na2CO3/1M HNO3 67±3.5 72±3.7 76±4.3 74±3.7 55±2.6 83±4.2

(NH4)2CO3/1M HNO3 65±4 71±3.6 55±2.9 42±2.1 47±2.3 48±2.4

Table 8. Comparison of maximum % removal of environmental interest radionuclides by different methods

Now, interesting study was done by our team using the solvent extraction technique for
treatment of TE-NORM at scales on the interior of a pipe used in exploration of gas and oil
industry, and several parameters were studied, such as the effect of contact time, organic
extractants concentration, organic liquid/solid ratio, temperature, effect of different aliphatic
and organic diluents. From the data available up till now, it can be concluded that kerosene
as a diluent has a good efficiency on the E % of the radionuclides with the different organic
104 Advances in Petrochemicals

extractants used. The extraction percent order with different types of organic extractants for
226
Ra, separation of 228Ra, 238U, 210Pb, and 40K at kerosene was found in the following order:
TOPO ≈ TBP > TBPO > DEHPA > TPPO > TPAsO for 226Ra
TBP > TOPO > DEHPA > TBPO > TPPO > TPAsO for 228Ra
TBP > DEHPA > TPPO > TBPO > TOPO > TPAsO for 238U
TOPO > TBPO > TBP > DEHPA > TPAsO > TPPO for 210Pb
TBP > DEHPA > TOPO > TBPO > TPAsO > TPPO for 40K
Also, our team examined and evaluated two surfactants as extracting agent for the removal of
radium species from TE-NORM sludge produced from petroleum industry. In this investiga‐
tion, cationic and nonionic surfactants were used as extracting agents for the removal of radium
radionuclides from the sludge waste. Two surfactants namely cetyltrimethylammonium
bromide (CTAB) and Triton X-100 (TX100) were investigated as the extracting agents. Different
parameters affecting the removal of both 226Ra and 228Ra by the two surfactants as well as their
admixture were studied by the batch technique [64]. The influence of contact time on disso‐
lution/desorption of radium radionuclides (226Ra, 228Ra) from TE-NORM sludge waste using
TX100 and CTAB surfactants was investigated. Transport and mass transfers of radium
isotopes from the sludge might be a key process responsible for reducing radium from the
sludge. To achieve maximum radium species removal, a specific period of time is required.
The obtained results are represented in Table 9. It is obvious that the removal efficiency of
radium isotopes is increased as the shaking time was increased and reach maximum after 60
minutes. The highest removal efficiency for 226Ra was obtained using CTAB surfactant, and
using TX100 surfactant for 228Ra. However, further increase in the time of experiment leads to
decrease of the removal efficiency [64].

Time, min TX100 solution CTAB solution

226
Ra (R, %) 228
Ra (R, %) Ra (R, %)
226 228
Ra (R, %)

15 16.0 ± 1.3 17.0 ± 1.4 20.4 ± 1.8 15.0 ± 1.3

30 22.0 ± 1.5 20.5 ± 1.8 22.7 ± 2.0 18.2 ± 1.6

60 25.0 ± 1.7 27.0 ± 2.1 26.0 ± 2.0 22.0 ± 1.3

120 15.7 ± 1.3 24.0 ± 2.2 23.7 ± 2.1 23.7 ± 2.0

240 8.2 ± 0.8 18.5 ± 1.6 4.2 ± 0.4 16.7 ± 1.5

Table 9. Effect of contact time on the removal efficiency (R, %) of 226Ra and 228Ra using 1% (w/v) surfactants solutions

Effect of surfactant concentration on the extraction of radium isotopes is regarded as an

important parameter affecting the removal of radium isotopes from TE-NORM sludge waste.
The removal efficiency of radium species for both surfactant solutions increased with increas‐
ing surfactant concentration up to 1%. At higher surfactants concentration, a slight decrease
was observed in Table 10. The optimum concentrations are found to be 1% for both surfactants
Overview about Different Approaches of Chemical Treatment of NORM and TE-NORM Produced from Oil Exploitation 105
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solutions. The effective removal of radium species from TE-NORM sludge can be explained
by the increased solubility of radium species in the surfactant micelles. Generally, the change
in the concentration of surfactant leads to change in its physical properties such as micelles
formation and its solubilization effect for radium species or any contaminant (organic or
inorganic species) present in TE-NORM sludge waste [65]. Therefore, the optimum surfactants
concentrations are 1% for this treatment to avoid introduction of excess surfactants into sludge
and avoid decrease in the radium removal %.

TX100 solution CTAB solution

Concentration%
226
Ra (R, %) 228
Ra (R, %) 226
Ra (R, %) 228
Ra (R, %)

0.25 13.5 ± 1.4 15.0 ± 1.3 12.5 ± 0.9 14.4 ± 1.3

0.5 17.1 ± 1.1 19.1 ± 1.5 22.7 ± 1.7 20.0 ± 2.0

1.0 25.0 ± 1.7 27.0 ± 2.2 26.0 ± 2.0 22.0 ± 1.3

2.0 11.9 ± 1.1 20.5 ± 1.9 24.9 ± 1.7 23.0 ± 2.2

4.0 9.8 ± 0.9 19.0 ± 1.5 16.9 ± 1.4 14.8 ± 1.3

8.0 9.0 ± 0.8 13.3 ± 1.2 6.8 ± 0.6 8.8 ± 0.9

Table 10. Effect of surfactants concentrations on the removal efficiency (R, %) of 226Ra and 228Ra

The effect of temperature on the surfactants is not straightforward [66]. So that, temperature
of surfactant solutions used for removal of radium species is an important parameter in
surfactant-aided sludge washing process, and the experiments have been investigated with
concentration of 1% TX100 and CTAB at 25–60°C. The results in Table 11 showed that the
removal of Ra-isotopes are increased with increasing temperature and the removal of Ra
species reach a maximum at 60°C using both surfactants solutions. The increase of Ra species
removal efficiency is due to the properties of surfactants, where an increase in temperature
generally results in an increase in the extent of solubility. The cloud point phenomenon occurs
when a surfactant above its CMC causes the separation of the original solution into two phases
when heated at a characteristic temperature called cloud point temperature. At this tempera‐
ture, surfactant is no longer soluble in water and solution becomes hazy and cloudy. Above
the cloud point, micelles formed from surfactant molecules act as an organic solvent in liquid–
liquid extraction and the analytes are partitioned between the micelles and the aqueous phases
[67]. It has been mentioned that the cloud point extraction procedure not only effectively
solubilizes and concentrates pollutants but also appears to offer a means to further the
concentrated surfactant-enhanced wash solutions that have been used in soil treatment
processes [68]. About 25% of the radium species were initially removed from the TE-NORM
sludge by solubilization in surfactants solution. About 55–60% removal was achieved upon
the temperature raise to 60°C as shown in Table 11.

Synergism in surfactants may be defined as any situation where mixtures of surfactants have
superior properties when compared to the properties of any of the single surfactant alone [69].
106 Advances in Petrochemicals

TX100 solution CTAB solution

Temperature °C
226
Ra (R, %) 228
Ra (R, %) Ra (R, %)
226
Ra (R, %)
228

25 25.0 ± 1.7 27.0 ± 2.2 26.0 ± 1.9 22.0 ± 1.3

35 30.0 ± 1.9 39.5 ± 2.2 28.6 ± 2.2 35.9 ± 2.8

45 53.0 ± 1.7 45.3 ± 2.0 43.5 ± 2.7 46.2 ± 3.4

60 58.6 ± 2.1 54.3 ± 3.3 49.8 ± 3.8 50.7 ± 4.2

Table 11. Effect of temperature on the removal efficiency (R, %) of 226Ra and 228Ra using surfactants solutions

There is usually a synergy effect for the CMC of surfactant mixtures (mixture of nonionic and
ionic surfactant) [69]. Mixture of TX100 and CTAB surfactants showed synergistic interactions,
which can be manifested as enhanced surface properties, spreading, and many other phe‐
nomena, as shown in Figure 5. The synergistic behavior of mixed surfactant systems can be
exploited to reduce the total amount of surfactant used in a particular application resulting in
the reduction of cost [70]. It was observed that the removal values of radium isotopes of mixed
systems of both surfactants are higher than their corresponding values without mixing, which
indicate synergistic interaction in mixed CTAB-TX100 as a chemical extraction system.
Removal of 84% and 80% for 226Ra and 228Ra, respectively, are obtained using synergistic effect
of 1% aqueous solution containing 1:1 of the two surfactants investigated. In other words,
mixed micelle formation in aqueous solution can be greater than that of the individual
surfactant, and explained by non-ideal solution theory [70]. Also, it was observed that
combined extraction of cationic and nonionic surfactants was effective in removal of both
226
Ra and 228Ra. Experiments indicated that removal efficiency was optimized (80–84%) when
a mixture of 1% CTAB and 1% TX100 was employed at the ratio 1:1. The theoretical justification
for this surfactants solution is based upon two hypotheses, first that surfactant micelles may
sequester radium radionuclides which are sorbed to the TE-NORM sludge waste, and second
that the surfactant micelles may increase the concentration of radium radionuclides in the
aqueous phase. The developed chemical treatment process would enable to design an
appropriate TE-NORM sludge washing strategy.

Glossary

Brief explanations of few terms are mentioned in the state-of–the-art in this short glossary.

NORM: Naturally occurring radioactive material.

TE-NORM: Technologically enhanced naturally occurring radioactive materials.

by-product: Any product from an (industrial) process that is not the intended primary product,
but inevitable given the process implemented.
Overview about Different Approaches of Chemical Treatment of NORM and TE-NORM Produced from Oil Exploitation 107
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Product: The intended output from an (industrial) process.

REE: Rare earth elements (or lanthanides), comprising 16 chemical elements, including those
with atomic numbers 57 (lanthanum) through 71 (lutetium), as well as yttrium (atomic number
39).

Waste: Any material that is:

(a) The unwanted/substandard output from an (industrial) process that cannot be utilized
under given circumstances (technological/economic perspective);

(b) Declared as unwanted and/or unusable (regulatory perspective).

Scale: Solid deposit of low-solubility sulfates or carbonates on the inside of components of gas
and oil production installations.

Sludge: Mixture of organic and mineral solids in water and liquid hydrocarbons separated
from oil or gas at production facilities.

Radioactive material: Material designated in national law or by a regulatory body as being

subject to regulatory control because of its radioactivity.

Half-life: For a radionuclide, the time required for the activity to decrease, by a radioactive
decay process, by half. i.e., lose 50% of its activity.

Secular equilibrium: is a steady-state condition in which the rate of formation of the radio‐
active daughter products is just equal to the rate of decay; that is, the activity of radioactive
parent and daughter are the same.

Separator: A pressure vessel used for separating well fluids produced from oil and gas wells
into gaseous and liquid components.

Industrial process: This term is used very broadly in the present report to denote any human
activity involving the application of technology, for example, the mining, processing, and
drinking water treatment industries.

EPA: Environmental Protection Agency

UNSCEAR: United Nations Scientific Committee on the Effects of Atomic Radiation

TBP: Tri butyl phosphate

DEHPA: Bis (2-ethylhexyl phosphoric acid)

TOPO: Tri octyl phosphine oxide

TBPO: Tri Butyl phosphine oxide

TPAsO: Tri phenyl arsine oxide

TPPO: Tri phenyl phosphine oxide

108 Advances in Petrochemicals

Author details

N.S. Awwad1,3*, M.F. Attallah3, E.M. El-Afifi3, H.A. Ibrahium2 and H.F. Aly3

*Address all correspondence to: [email protected]

1 Chemistry Department, Faculty of Science, King Khalid University, Abha, KSA

2 Biology Department, Faculty of Science for Girls, King Khalid University, Abha, KSA

3 Hot Laboratories and Waste Management Center, Atomic Energy Authority, Cairo, Egypt

References

[1] OGP Report No. 412, Guidelines for the management of Naturally Occurring Radio‐
active Material (NORM) in the oil & gas industry, September 2008, www.ogp.org.uk.
©Copyright 2008, OGP.

[2] UNSCEAR (1977) United ionising radiations: sources and biological effects of atomic
radiation. Report to the General Assembly. Vienna, New York.

[3] Al-Masri MS, Shwiekani R. Radon distribution in natural gas processing facilities
and workplace air environment. J Environ Radioact 2008;99:574–580.

[4] Dickson BL. Radium in groundwater. In: The Environmental Behavior of Radium.
Reports Series, Vol. 310, No 1. IAEA, Vienna, 1990, pp.335–372.5.

[5] Jonkers G, Hartog FA, Knappen AAI, Lance PFJ. Characterization of NORM in the
oil and gas production (E&P) industry. In: Proc NORM I, Amsterdam, 1997, pp.23–
47.

[6] Snavely ES. Radionuclides in produced water. Report to the American Petroleum In‐
stitute. Publication no 5404. API, Washington, DC, 1989, pp.1–86.

[7] White GJ. Naturally occurring radioactive materials (NORM) in oil and gas industry,
equipment and wastes: a literature review. Report DOE/ID/01570-T158.Bartlesville,
1992.

[8] Hamlat MS, Djeffal S, Kadi H. Assessment of radiation exposures from naturally oc‐
curring radioactive materials in the oil and gas industry. Appl Radiat Isot
2001;55:141–146.

[9] Guidelines for naturally occurring radioactive materials Australian Petroleum Pro‐
duction & Exploration Associated Ltd. Report ABN 44000292773, March 2002, Can‐
berra.
Overview about Different Approaches of Chemical Treatment of NORM and TE-NORM Produced from Oil Exploitation 109
http://dx.doi.org/10.5772/61122

[10] Vegueria JSF, Godoy JM, Miekeley N. Environmental impact studies of barium and
radium discharges by produced waters from the “Bacia deCampos” oil field offshore
platforms, Brazil. J Environ Radioact 2001;62:23–38.

[11] Testa C, Desideri C, Meli MA. Radiation protection and radioactive scales in oil and
gas production. Health Phys 1994;71:34–38.

[12] Shawky S, Amer H, Nada AA, Abd El-Maksoud TM, Ibrahiem NM. Characteristics
of NORM in the oil industry from Eastern and Western deserts of Egypt. Appl Radiat
Isot 2001;55:135–139.

[13] Norwegian Radiation Protection Authority Natural radioactivity in produced water

from the Norwegian oil and gas industry in 2003. Report no 2. NRPA, Ǿsteras, 2005.

[14] Eriksen DO, Sidhu R, Strälberg E. Radionuclides in produced water from Norwegian
oil and gas installations-concentrations and bioavailability. Czechoslovak J Phys
2006;56:D43–D48.

[15] Al-Masri MS. Spatial and monthly variations of radium isotopes in produced water
during oil production. Appl Radiat Isot 2006;64:615–623.

[16] United Kingdom Off-Shore Operations Association UK North Sea oil and gas indus‐
try; environmental inputs, impacts and issues. A report prepared by Environmental
and Resource Technology Ltd, London, 1992.

[17] Stephenson MT, Supernow IR. Offshore Operators Committee 44 Platform study ra‐
dionuclide analysis results. Offshore Operation Committee Report, New Orleans,
Louisiana, 1990.

[18] Swan C, Matthews J, Ericksen R, Kuszmaul J Evaluation of radionuclides of uranium,

thorium, and radium associated with produced water fluids, precipitates and sludge
from oil, gas and oilfield brine injections wells in Mississippi. US DOE Report; 2004,
DE-FG26-02NT 15227.

[19] Zieliński RA, Budahn JR. Mode of occurrence and environmental mobility of oil-field
radioactive material at US Geological Survey research site B. Appl Geochem
2007;22:2125–37.

[20] Godoy MJ, da Cruz RP. 226Ra and 228Ra in scale and sludge samples and their cor‐
relation with the chemical composition. J Environ Radioact 2003;70:199–206.

[21] Gazineu MHP, de Araujo AA, Brandao YB, Hazin CA, Godoy JM. Radioactivity con‐
centration in liquid and solid phases of scale and sludge generated in the petroleum
industry. J Environ Radioact 2005;81:47–54.

[22] Gazineu MHP, Hazin CA. Radium and potassium-40 in solid wastes from the oil in‐
dustry. Appl Radiat Isot 2008;60:90–94.

[23] El Afifi EM, Awwad NS. Characterization of the TENORM waste associated with oil
and natural gas production in Abu Rudeis. Egypt. J Environ Radioact 2005;82:7–19.
110 Advances in Petrochemicals

[24] Kadyrzhanov KK, Tuleushev AZ, Marabaev ZN. Radioactive components of scales at
the inner surface of pipes in oil fields of Kazakhstan. J Radioanal Nucl Chem
2005;264:413–6.

[25] Omar M, Ali HM, Abu MP. Distribution of radium in oil and gas industry wastes
from Malaysia. Appl.Radiat Isot 2004;60:779–782.

[26] Lysebo J, Birovliev A, Strand T. NORM in oil production – occupational doses and
environmental aspects. In: Proc of the 11th Congress of the Nordic Radiation Protec‐
tion Society, 26–30 August 1996, Reykjavik, p.137.

[27] Al-Saleh FS, Al-Harshan GA. Measurements of radiation level in petroleum products
and wastes in Ryad City refinery. J Environ Radioact 2008;99:1026–1031.

[28] Heaton B, Lambley JG. TENORM in the oil and gas industry. Appl Radiat Isot
1995;46:577–581.

[29] Exploration and Production Forum. Low specific activity scale origin treatment and
disposal. Report no 6.6/127. London, 1987;pp.25–38.

[30] Scot ML. Naturally occurring radioactive materials in non-nuclear industry. In: Proc
of the 2nd Int. Symp. on the Treatment of Naturally Occurring Radioactive Materials
NORM II, 10–13 November 1998, Klefeld, Germany, pp.163–167.

[31] White GJ, Rod SA. Radon emanation from NORM-contaminated pipe scale and soil
at petroleum industry sites. J Environ Radioact 2001;54:401–413.

[32] Oil and gas production wastes. http://www.epa.gov/rpdweb00/ tenorm/

oilandgas.html.

[33] El Afifi EM, Awwad NS, Hilal MA. Sequential chemical treatment of radium species
in TENORM waste sludge produced from oil and natural gas production, J Hazard
Mater 2009;161:907–912.

[34] El Afifi EM. Radiochemical studies related to environmental radioactivities. Ph.D.

thesis (Chemistry), Faculty of Science, Ain Shams University, Cairo, Egypt, 2001, p.
98.

[35] Shawky S, Amer H, Nada AA, Abdel Maksoud TM, Ibrahim NM. Characteristics of
NORM in the oil industry from eastern and western deserts of Egypt. Appl Radiat
Isot 2001;55:135–9.

[36] Holland B. Experience with operations involving NORM in the UK and some other
regions. Australian Nuclear Science and Technology Organization, Lucas heights,
Sydney, March 16–20, 1998.

[37] White GJ, Rood AS. Radon emanation from NORM contaminated pipe scale and soil
at petroleum industry sites. J Environ Radioact 2001;54:401–413.
Overview about Different Approaches of Chemical Treatment of NORM and TE-NORM Produced from Oil Exploitation 111
http://dx.doi.org/10.5772/61122

[38] Hamlat MS, Gjeffal S, Kadi H. Assessment of radiation exposures from naturally oc‐
curring radioactive materials in the oil and gas industry. Appl Radiat Isot
2001;55:141–146.

[39] Heaton B, Lambley J. TENORM in the oil, gas and mineral mining industry. Appl
Radiat Isot 1995;46:577–581.

[40] Exploration & Production Forum. Low specific activity scale origin treatment and
disposal. Report no. 6.6/127, Old Burlington Street, London WlX 1LB, 1987, pp.25–28.

[41] Hilal MA, Awwad NS, El Afifi EM, Aly HF. TE-NORM in oil-separator tanks, assess‐
ment and treatment investigations. Arab J Nuc Sci Applic 2005;39(2):109–124.

[42] Environmental, Health, and Safety Guidelines Offshore Oil and Gas Development,
APRIL 30, 2007.

[43] UNSCEAR United Nations Committee on the Effect of Atomic Radiation: Sources
and NCRP. Exposure of the population in the United Sates and Canada from natural
background radiation. NCRP report no.94. National Council on Radiation Protection
and Measurement, Bethesda, Maryland, 1994.

[44] IAEA. International Atomic Energy Agency. Report of analysis on Determination of

thorium and uranium naturally occurring radioisotopes in IAEA reference materials.
IAEA laboratories (Chemistry Unit-01-10), Seibersdorf Austria, pp.1–5.

[45] Eylander JGR, Lancee PFJ, Hartog F, Knaepen WAL, Frigo DM. Proc 2nd Int Symp
Treatment NORM, p.83, Krefeld, Germany, Nov. 10–13, 1998.

[46] Quada U, Kluth T. Proc 2nd Int Symp Treatment NORM, p.95, Krefeld, Germany,
Nov. 10–13, 1998.

[47] Stage G. Proc 2nd Int Symp Treatment NORM, p.95, Krefeld, Germany, Nov. 10–13,
1998.

[48] Smith GE, Fitzgibbon T, Karp S. Proc Exploration Production Environ Conf p.231,
Houston, Texas, USA, March 27–29, 1995.

[49] Daifullah AAM, Awwad NS. Proc 5th Int Sci Conf 25–27 March, pp.57–69, 2003.

[50] Hassan SSM, Awwad NS, Aboterika AHA. Removal of mercury(II) from wastewater
using camel bone charcoal, J Hazard Mater 2008;154:992–997.

[51] Phillip E, Carter H. Health Physics Society, Albuquerque, NM, 24 January, 1999.

[52] Exploration and Production Forum. Low specific activity scale origin treatment and
disposal. Report no. 6.6/127, Old Burlington Street, London, WI1X 1LB, UK, 1987, pp.
25–28.

[53] IAEA, International Atomic Energy Agency, International basic safety standards for
the protection against ionizing radiation and for the safety of radiation sources.
GOV / 2715 / Vienna, 1994.
112 Advances in Petrochemicals

[54] Rood AS, Kendrick DT. Measurement of Rn222 flux, Rn222 emanation and Ra-226
concentration from injection well pipe scale, NORM/NARM: Regulation and risk as‐
sessment, Proceedings of the 29th midyear topical meeting of the Health Physics So‐
ciety, Scottsdale, Arizona, USA, January 7–10, 1996, pp.139–144.

[55] Smith GE, Fitzgibbon T, Karp S. Economic impact of potential NORM regulation,
SPE/EPA exploration and production environmental conference, Houston, Texas,
USA, March 27–29, 1995, pp.181–194.

[56] Eylander JGR, Lancee PFJ, Hartog FA, Knaepen WAI, Frigo DM. Further develop‐
ments in the in-situ removal of TENORM from exploration and production facilities.
Proc 2nd Int Symp Treatment NORM, Krefeld, Germany, November 10–13, 1998, pp.
83–89.

[57] Shehata FA, El Afifi EM, Aly HF. Fractionation and leaching of naturally occurring
radioactive waste produced from oil production, Pro Conf Radioactive Waste Man‐
agement Environ Remediation Nagoya, Japan, September 26–30, 1999, CD-ROM.

[58] El Afifi EM, El-Reefy SA, Aly HF. Treatment of solid waste containing Ra-226. Arab J
Nucl Sci Appl 2006;39:35–47.

[59] Benes P. Speciation procedures. In: The environmental behavior of radium, Technical
reports series No. 310, Vol. 1, Part 3, Ch. 10, International Atomic Energy Agency
(IAEA), Vienna, 1990, pp.273–299.

[60] Florence TM, Batley GE. Chemical speciation in natural waters. CRC, Crit Rev Anal
Chem 1980;9:219–296.

[61] Sam AK, Ahmed MMO, El Khangi FA, El Nigumi YO, Holm E. Radiological and
chemical assessment of Uro and Kurun rock phosphates. J Environ Radioact
1999;42:65–75.

[62] Tessier A, Campbell PGC, Bisson M. Sequential extraction procedure for the specia‐
tion of particulate trace metals. Anal Chem 1979;51:844–851.

[63] Attallah MF, El Afifi EM, Awwad NS, Aly HF. Comparative study on the radioactivi‐
ty of TE-NORM in different components of oil separator tanks Radiochimica Acta
2102;101: 57– 65.

[64] Attallah MF, Hamed MH, El Afifi EM, Aly HF. Removal of Ra-226 and Ra-228 from
TENORM sludge waste using surfactants solutions. Accepted for publication in Jour‐
nal of Environmental Radioactivity, 2014.

[65] Crook EH, Fordyce DB, Trebbi GF. Molecular weight distribution of nonionic surfac‐
tants. I. Surface and interfacial tension of normal distribution and homogeneous p, t-
octylphenoxyethoxyethanols (OPE'S). J Phys Chem 1963;67:1987.

[66] Singh HN, Swarup S, Saleem SM. Effect of electrolytes on the micellization of ionic
surfactants in n-alkanol-water mixtures. J Colloid Inter Sci 1979;68:128.
Overview about Different Approaches of Chemical Treatment of NORM and TE-NORM Produced from Oil Exploitation 113
http://dx.doi.org/10.5772/61122

[67] Schick MJ. Nonionic Surfactants: Physical Chemistry, CRC Press; 2nd edition, 1987.

[68] Abdul AS, Gibson TL. Laboratory studies of surfactant enhanced washing of poly‐
chlorinated biphenyl from sandy material. Environ Sci Technol 1991;25:665.

[69] Holmberg K, Jönsson B, Kronberg B, Lindman B. Surfactants and Polymers in Aque‐

ous solution, 2nd Ed., Wiley, Chichester, 2003.

[70] Stalikas C.D. Micelle mediated extraction as a tool for separation and preconcentra‐
tion in metal analysis, Trends Anal Chem 2002;21:343.
 Chapter 6

Simulation and Optimization of Multi-period Steam

Cracking Process

Lei Zhang, Hangzhou Wang, Tong Qiu and Bingzhen Chen

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/60558

Abstract
Hydrocarbon steam cracking is the most important process for producing industrial
chemicals such as olefin and aromatics. Steam cracking modelling and optimization is
an effective way for increasing production and saving energy. In this chapter, multi-
scale modelling and elementary reaction networks are established and used in the
modelling and optimization of steam cracking. However, the large scale of the
optimization model makes it difficult to obtain a solution. Thus, a surrogate coke
thickness model for long-term steam cracking is proposed in this chapter to remove
the connection between different periods of steam cracking process. By so doing, a
parallel simulation can be used to accelerate optimization. An industrial case study
showed optimization time to be significantly reduced from 17.78 hours to 2.08 hours
using multi-period optimization with parallel simulation and the surrogate coke
thickness model. It has been shown that a 0.62% increase in ethylene yield can be
obtained via operating condition optimization, which demonstrates the effectiveness
of the multi-scale steam cracking model and multi-period optimization with parallel
simulation.

Keywords: Steam cracking, multi-scale modelling, elementary reaction network,

parallel simulation, surrogate model

1. Introduction

Hydrocarbon steam cracking is the most important process for producing industrial chemicals
such as olefin and aromatics. Mathematical models for steam cracking simulation have been
118 Advances in Petrochemicals

studied for several decades and various models have been developed such as SPYRO [1] and
COILSIM [2]. Meanwhile, the steam cracking model can be applied to the steam furnace design
and optimization [3]. As various feedstock and furnaces are used in steam cracking, a more
accurate and robust model is needed.

A mathematical model is a collection of relations among variables representing certain

properties of a system, using equations and inequalities. By solving a model, one can predict
the values of some properties of the system, given the values of some other properties, or
predict the distributions of the values of some properties in particular domains, given certain
boundary conditions. To meet the scientific and engineering demands in terms of revealing
the characteristics of a system in-depth, a mathematical model may involve relations of
properties at different scales of the system [4], referred to as a multi-scale model. The multi-
scale model often consists of nonlinear equations and differential equations, and is not easy to
solve. The information communication between scales is the key factor in multi-scale models
[5]. In recent years, multi-scale modelling has been applied in all fields of chemical engineering
such as thermodynamics, reaction engineering, polymer materials and CFD (computational
fluid dynamics), among others. Multi-scale modelling is used in steam cracking models to
reveal the nature of steam cracking and to establish a more accurate and robust model.

The kernel part of the steam cracking model is the reaction network. Researchers have
developed various reaction models to describe the steam cracking process. There are three
different types of reaction models: empirical models, molecular models and elementary
reaction models. Empirical models use a large database of experimental results to regress a
number of empirical correlations for the yields of the main products as a function of a number
of easily measurable process variables [6]. Empirical reaction models need a large number of
experiment data to render a regression. Once the feedstock or the furnaces change, the reaction
model has to be re-established to obtain accurate simulation results. On the basis of empirical
reaction models, molecular reaction models have been developed and frequently used [7-9],
e.g., the Kumar reaction model [10]; 22 molecular reactions are involved in Kumar’s reaction
model: one primary reaction and 21 secondary reactions. The primary reaction is shown as eq.
(1). The selective coefficients of the primary reaction (a1~a10) have been regressed from
experimental data. If the feedstock or operating conditions change, the selective coefficients
of the primary reaction should be regressed again.

naphtha ® a1H 2 + a2 CH 4 + a3C 2 H 4 + a4 C 2 H6 + a5C 3H6 +

(1)
+ a6 C 3H8 + a7 C 4 H10 + a8 C 4 H8 + a9 C 4 H6 + a10 C 4's

Nowadays, elementary reaction models have been widely used to develop a more reliable and
robust mathematical model. Since the pioneering work of Rice [11-13] there has been a general
consensus about the elementary reaction mechanism. As the mathematical difficulties
encountered for solving the detailed kinetic models can be overcome by the development of
stiff solvers [14], detailed elementary reaction networks are widely used to accurately describe
chemical processes in a wide range of process conditions and feedstock. Sundaram et al. [15]
 Simulation and Optimization of Multi-period Steam Cracking Process 119
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established a radical reaction model for the pyrolysis of simple paraffins, olefins and their
mixtures. Scharfe et al. [16] established a radical reaction model for n-hexane pyrolysis. Joo et
al. [17] established a radical reaction model for industrial naphtha cracking furnaces.

However, it has remained problematic to generate thousands of elementary reactions and to

determine the reaction rate constants of these reactions until an automatic reaction network
generation technique was studied. Today, computers are used not only to solve the simulation
numerically, but also to generate the elementary reaction network, construct the model and
calculate the kinetic parameters [2]. Many research groups have developed computer tools for
automatically generating these mechanisms [18-23] such as RMG [24] and CRACKSIM [25].
The elementary reaction model is expected to be used in furnace design and operating
condition optimization. However, the huge number of reactions in the elementary reaction
network usually requires significant CPU time during simulation. Thus, the steam cracking
simulation model has to be reduced before it can be used in operating condition optimization,
in order to make real-time optimization (RTO) realistic.

There are multiple methods for creating model reduction. In terms of chemistry, quasi-steady-
state approximation (QSSA) [26], reaction rate analysis [27] and reaction path analysis [28],
among others, can be used to reduce a reaction model. In terms of mathematics, principle
component analysis [29] and sensitivity analysis [30] can also be used. On the other hand, data
driven methods can also be used in model reduction, for example, the black box model, a neural
network [31] and PCA based ROMs [32]. Several assumptions can also be applied to help retain
the mechanism at a manageable size. The most important assumption is the μ radical hypoth‐
esis, which assumes that bimolecular reactions can be neglected for radicals with more than
five carbon atoms [33]. The latter are also referred to as μ radicals. Thus, the QSSA method can
be applied to remove μ radicals from the reaction network.

A multi-scale model for the steam cracking process is established in this chapter. The multi-
period steam cracking process is also studied in the context of the established multi-scale
model. Coking is an unavoidable factor during the multi-period steam cracking process.
Coking increases pressure drops in the reaction tube, decreases the coefficient of heat transfer
between the furnace and tube, and most importantly, increases the outer-wall temperature of
the tubes. If one of the tubes in the furnace reaches the maximum allowance temperature of
the tube material, the furnace must be shut down to execute a decoking process, otherwise the
tube will be destroyed. The operation conditions are generally maintained constant during the
long-term steam cracking process. Thus, dynamic operating conditions need to be optimized
using a detailed steam cracking model in order to achieve a higher profit. Abel et al. [34] used
the SQP method to solve a real-time optimization problem in the olefins production process.
Tarafder et al. [35] proposed a multi-objective optimization problem in the operation and
design of a styrene manufacturing process. Li et al. [36] applied an artificial neural network
(ANN) hybrid model in the operation optimization of a naphtha industrial cracking furnace.
Gao et al. [3] used a new parallel hybrid algorithm combining NSGA-II with SQP on multi-
objective optimization for the periodic operation of the naphtha pyrolysis process. However,
due to the complexity of the elementary reaction model, the researchers did not use this
reaction model in the optimization problem. In this chapter, an elementary reaction model is
120 Advances in Petrochemicals

applied to the operating condition optimization problem to obtain a more reliable optimization
result. Based on this, a surrogate coke thickness model is proposed to make multi-period
optimization with parallel simulation possible.

The general idea of this chapter is outlined in Figure 1. The first step in the conceptual
development of a detailed molecule-based model for a complex feedstock is to determine an
accurate molecular representation of the feedstock. Then, a multi-scale steam cracking model
is established following the feedstock prediction. Finally, operating condition optimization of
multi-period steam cracking is carried out using the established multi-scale model.

Figure 1. Diagram of simulation and optimization of the steam cracking process methodology

This chapter is structured as follows. Section 2 offers a detailed discussion of the establishment
of the multi-scale steam cracking model; a case study for naphtha steam cracking simulation
is presented. Section 3 provides the operating condition optimization model; surrogate coke
thickness model and parallel simulation are used to accelerate the computing of the optimi‐
zation model. A case study of operating condition optimization is presented and the results
are presented and discussed. Finally, section 4 offers conclusions from this study.

2. Steam cracking model

2.1. Multi-scale model for steam cracking

A multi-scale model is proposed in this chapter to reveal the nature of the steam cracking
process and to generate a reliable and robust model for accurately predicting the yields of
 Simulation and Optimization of Multi-period Steam Cracking Process 121
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Figure 2. Comparison of experimental and calculated feedstock component mole fractions [39].

products. The multi-scale model is built up from the molecular level, to the reaction level to
the process level. The establishment of the multi-scale model is discussed in detail in the
following sections.

a. Feedstock composition prediction

Conventional analytical techniques are generally incapable of directly measuring the identities
of all the molecules in complex feedstock, especially for the high carbon number range;
however, this applies only to indirect characteristics [37]. Here, the Shannon entropy method
[38] and probability density function were used to predict detailed feedstock composition,
based on the analytical data. A detailed model for feedstock composition prediction can be
found in [39]. The objective function of this NLP (non-linear programming) problem is shown
in eq. (2), where S(x) is Shannon entropy and xi is the mole fraction of component i.

n
max S( x) = -åxi ln xi (2)
i =1

Figure 2 shows the predicted feedstock composition using Shannon entropy, compared with
the experimental data. The predicted results show the effectiveness of the Shannon entropy
theory in obtaining the missing information for models of the steam cracking process.
122 Advances in Petrochemicals

b. Process-level model

A process-level model consists of mass balance equations, momentum balance equation and
energy balance equation (eqs. (3-5)) [40, 41]. For the simulation of smooth tubular reactor types,
the use of a one-dimensional reactor plug-flow model is generally recognized as providing a
sufficient degree of accuracy, as all radical profiles are wiped out due to the high turbulence
corresponding to Reynolds numbers of over 250 000. The plug-flow reactor model implicitly
assumes that there is no mixing in the axial direction, but rather, perfect mixing in the
transverse direction [2].

dN m S
= ån r = f N (T , P , N m )
i ,m i (3)
dL V i

dP f × E( L) × G 2
=- = f P (T , P , N m ) (4)
dL 5.07 ´ r × Di ´ 10 4

dN m
kp Do (Tw - T ) - å DH 0fm ×
dT dL
= m
= fT (T , P , N m ) (5)
dL åc
m
pm
Nm

In eq. (3), Nm is the concentration of species m and L is the length of the reactor tube. S is the
flow area, V is the volume flow rate, μim is the stoichiometric coefficient of reaction i and ri is
the reaction rate of reaction i. In eq. (4), P is the pressure of the mass flow, f is the Fanning
friction factor, E(L)=Le/L, Le is the equivalent length of the reactor tube, G is the mass flow rate,
Di is the internal diameter of the tube and ρ is the density of the gas mixture. In eq. (5), T is the
temperature of the mass flow, Do is the outer diameter of the tube, k is the overall heat transfer
coefficient, Tw is the outer wall temperature of the tube, ΔHfm0 is the standard heat of formation
of species m and cpm is the specific heat of species m.

It should be noted that the measuring point of the COT (coil-outlet temperature) of an
industrial furnace is usually on the outer wall of the tube. Thus, the measured COT has a
temperature difference from the outlet temperature of the gas mixture. Eq. (6) has been derived
from heat balance equations in order to adjust to the temperature difference; the results show
that there exists a 15-20K temperature difference, which agrees well with what has previously
been reported.

æ r ö
ln o
lisolation ( COT - Tisolation _ o ) ç ÷
DCOT = ç ln ri +
ri
+
1 ÷ (6)
ro + disolation ç ri - dcoke ltube a mixture (ri - dcoke ) ÷
ln ç ÷
ro è ø
 Simulation and Optimization of Multi-period Steam Cracking Process 123
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In eq. (6), λisolation is the heat transfer coefficient of the isolation layer. Tisolation_o is the outer wall
temperature of the isolation layer, ro is the external diameter of the tube, ri is the interior
diameter of the tube, disolation is the thickness of isolation layer, dcoke is the thickness of coke and
αmixture is the heat transfer coefficient of the gas mixture in the tube.
c. Reaction-level model
The reaction model is the most important part of the steam cracking model. Many researchers
have conducted in-depth studies on the elementary reaction model. An elementary reaction
model can contain thousands of reactions and hundreds of species. The reaction model can be
extremely hard to solve due to its stiffness. An accurate and robust elementary reaction model
is developed in this chapter, and a Gear algorithm is used to solve the stiff ODEs. Generally,
a detailed reaction network is generated by allowing the feedstock components to react
according to different reaction families. The reaction families can be summarized as follows:
(1) initiation reaction and termination reaction: R1—R2 ↔ R1∙+R2∙; (2) hydrogen abstraction
reaction: R1—H+R2 ↔ R1∙+R2—H; (3) radical addition and β-scission reaction: R1∙+R2=R3 ↔
R1—R2—R3∙.

Figure 3. Sub-models in the generation of hydrocarbon steam cracking reaction networks.

The hydrocarbon steam cracking elementary reaction network can be separated into several
sub-models. based on the composition of feedstock as shown in Figure 3. The sub-models are
generated separately, based on the reaction families described above.

An elementary reaction model for light hydrocarbon can be found in much of the literature
and databases, and it is more accurate than the automatic generated elementary reaction
model. Thus, the elementary model for steam cracking is separated into two parts: a light
hydrocarbon and heavy hydrocarbon reaction model (carbon number greater than five). The
light hydrocarbon reaction model is generated using RMG [24]. RMG considers each species
as unique and comprising a set of molecular structural isomers. When a reaction network is
generated using RMG, it need not consider all the isomers in the real steam cracking process;
instead, only a set of representative species are considered during the generation of a reaction
network. The heavy reaction model is combined using different reaction models of pure
compound feedstock and each reaction model is generated from the reaction families. The
reaction coefficients can be obtained from the summary of experimental data (Table 1) in the
124 Advances in Petrochemicals

work of Dente et al. [26]. The heavy hydrocarbon reaction model was generated using our own
code.

The automatic generated reaction network may contain a large number of unimportant
reactions and species. These reactions can increase the complexity of the model and make the
model hard to solve. Thus, reaction model reduction is needed following the automatic model
generation. The QSSA method is introduced first to remove the μ radicals in the reaction
network [33]. As eq. (6) shows, the reaction rate of μ radicals can be treated as zero, based on
the assumption.

Initiation reactions: unimolecular decomposition of C-C bonds

CH3-Csec Csec-Csec Csec-Cter Csec-Cquat

5×1016exp(-83,500/RT) 5×1016exp(-81,000/RT) 5×1016exp(-80,000/RT) 5×1016exp(-78,000/RT)

H-abstraction reactions of alkyl radicals

Primary H-atom Secondary H-atom Tertiary H-atom

Primary radical 10 exp(-13,500/RT)

8
10 exp(-11,200/RT)
8
108exp(-9,000/RT)

Secondary radical 108exp(-14,500/RT) 108exp(-12,200/RT) 108exp(-10,000/RT)

Tertiary radical 108exp(-15,000/RT) 108exp(-12,700/RT) 108exp(-10,500/RT)

Isomerization reactions (Transfer of a primary H-atom)

1-4 H-transfer 1-5 H-transfer 1-6 H-transfer

Primary radical 10 exp(-20,600/RT)

11
1.58×10 exp(-14,500/RT)
10
3.16×109exp(-19,500/RT)

Secondary radical 1011exp(-21,600/RT) 1.58×1010exp(-15,500/RT) 3.16×109exp(-20,500/RT)

Tertiary radical 1011exp(-22,100/RT) 1.58×1010exp(-16,000/RT) 3.16×109exp(-21,000/RT)

Alkyl radical decomposition reactions (to form primary radicals)

Primary radical Secondary radical Tertiary radical

1014exp(-30,000/RT) 1014exp(-31,000/RT) 1014exp(-31,500/RT)

Corrections of decomposition rates to form

Methyl radical Secondary radical Tertiary radical Alkyl radical

exp(-2,500/RT) exp(1,500/RT) exp(2,500/RT) 0.316×exp(8,000/RT)

Table 1. Reference kinetic parameters of pyrolysis reactions [26].

d ëéc ûù
= rformation - rconsumption » 0 (7)
dt

Thus, eq. (8) can be derived from eq. (7):

 Simulation and Optimization of Multi-period Steam Cracking Process 125
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Figure 4. Flowchart of automatic generation and reduction of reaction network.

rj + å ki , j Ri - åk j ,i
+ kdi Rj = 0 (8)
i¹ j i¹ j
126 Advances in Petrochemicals

In eq. (8), rj is the rate of direct formation of j-radical, ki,j is the rate constant for the isomerization
reaction (Ri → Rj) and kdj is the total rate constant for the decomposition reactions of Rj; μ
radicals are reduced using eq. (8). The number of species included in the model is decreased.

Reaction rate analysis is used to reduce the unimportant reactions in the reaction network. The
average reaction rate in the reaction network reflects the importance of the reaction in the
network. Thus, we can rank the reactions based on the average reaction rate and reduce the
reactions where the reaction rate is less than Rmin [44].

The flowchart of the automatic generation and reduction of the reaction network is shown in
Figure 4.

d. Molecular-level model

The physical properties of some species (radical, non-common substances, etc.) involved in
the model are difficult to obtain from databases. The physical properties of these species can
be calculated using the group contribution method [42]. RMG also supplies a thermochemistry
estimates utility using the group contribution method and was used in our model to auto‐
matically calculate the physical properties of these species.

Reaction A n E Reaction A n E
(kcal/mol) (kcal/mol)
CH3J+CH3J ↔ C2H6 8.26E+17 -1.4 1 BUT-2+C2H5J ↔ C4H7J 3.36E+12 0 12.39
+C2H6
CH3J+C2H5J ↔ C3H8 1.37E+13 0 0 BUT-1+HJ ↔ C4H7J+H2 1.40E+04 2.36 1.11
C2H5J+C2H5J ↔ n-C4H10 1.15E+13 0 0 BUT-2+HJ ↔ C4H7J+H2 2.60E+06 2.38 2.8
C2H5J+HJ ↔ C2H6 1.00E+14 0 0 BUT-1+C3H7J ↔ C4H7J 1.94E+02 2.96 6.79
+C3H8
C2H4+HJ ↔ C2H5J 1.55E+14 0 2.8 BUT-2+C3H7J ↔ C4H7J 1.72E+12 0 12.29
+C3H8
C2H6+HJ ↔ C2H5J+H2 2.27E+08 1.75 7.51 BUT-1+C3H7J ↔ C4H7J 3.12E-04 4.31 3.39
+C3H8
HJ+HJ ↔ H2 1.09E+11 0 1.5 BUT-2+C3H7J ↔ C4H7J 3.36E+12 0 12.39
+C3H8
C3H7J+HJ ↔ C3H8 2.00E+13 0 0 BUT-1+C2H3J ↔ C4H7J 5.11E+00 3.59 5.06
+C2H4
CH3J+C3H7J ↔ i-C4H10 6.64E+14 -0.57 0 BUT-2+C2H3J ↔ C4H7J 4.64E+13 0 7.5
+C2H4
C3H8+C2H5J ↔ C3H7J+C2H6 3.08E+03 2.66 10.1 BUT-1+C4H7J ↔ C4H7J 3.12E-04 4.31 3.39
+BUT-1
C3H8+HJ ↔ C3H7J+H2 1.60E+08 1.69 4.78 BUT-2+C4H7J ↔ C4H7J 3.36E+12 0 12.39
+BUT-1
C3H6+HJ ↔ C3H7J 2.01E+13 0 2.1 C4H7J ↔ C4H7J 2.82E+08 1.28 27.89
 Simulation and Optimization of Multi-period Steam Cracking Process 127
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Reaction A n E Reaction A n E
(kcal/mol) (kcal/mol)
C3H7J+HJ ↔ C3H8 1.00E+14 0 0 C4H7J+BUT-1 ↔ 3.12E-04 4.31 3.39
BUT-2+C4H7J
CH3J+C3H7J ↔ n-C4H10 3.37E+13 0 0 C2H3J+C2H3J ↔ C4H6 7.23E+13 0 0
C2H4+CH3J ↔ C3H7J 1.94E+13 0 9 C4H6+HJ ↔ C4H7J 5.70E+13 0 4.3
C3H8+C2H5J ↔ C3H7J+C2H6 3.95E+03 2.71 12.91 C4H6+HJ ↔ C4H7J 7.42E+13 0 1
C3H8+HJ ↔ C3H7J+H2 3.77E+08 1.75 7.51 C3H5J+HJ ↔ C3H6 5.00E+13 0 0
C3H6+HJ ↔ C3H7J 1.18E+13 0 3.8 C3H5J+CH3J ↔ BUT-1 1.00E+13 0 0
C3H7J+C3H8 ↔ C3H8+C3H7J 3.08E+03 2.66 10.1 C3H6+CH3J ↔ C3H5J+CH4 2.41E+02 2.92 7.16
C3H7J ↔ C3H7J 1.94E+10 0.89 35.78 C3H6+C2H5J ↔ C3H5J 1.01E-04 4.75 4.13
+C2H6
C2H6+CH3J ↔ C2H5J+CH4 1.67E+06 1.9 11.04 C3H6+HJ ↔ C3H5J+H2 1.30E+06 2.38 2.8
C3H8+CH3J ↔ C3H7J+CH4 1.67E+06 1.9 11.04 C3H6+C3H7J ↔ C3H5J 8.61E+11 0 12.29
+C3H8
C3H8+CH3 ↔ C3H7J+CH4 2.90E+06 1.77 8.53 C3H6+C3H7J ↔ C3H5J 1.01E-04 4.75 4.13
+C3H8
HJ+CH3J ↔ CH4 1.93E+14 0 0.27 C3H6+C2H3J ↔ C3H5J 2.32E+13 0 7.5
+C2H4
HJ+CH4 ↔ H2+CH3J 1.22E+08 1.87 10.59 C3H6+C4H7 ↔ C3H5J 1.01E-04 4.75 4.13
+BUT-1
C2H3J+HJ ↔ C2H4 5.36E+14 0 0.98 C3H5J+BUT-1 ↔ 3.12E-04 4.31 3.39
C3H6+C4H7J
C2H3J+CH3J ↔ C3H6 7.23E+13 0 0 C3H5J+BUT-2 ↔ 3.47E+13 0 21.39
C3H6+C4H7J
C2H3J+C2H5J ↔ BUT-1 1.00E+13 0 0 C4H7J+C2H3J ↔ C6H10 1.00E+13 0 0
C2H3J+CH4 ↔ C2H4+CH3J 5.36E+14 0 13.69 C3H5J+C3H5J ↔ C6H10 1.00E+13 0 0
C2H3J+C2H6 ↔ C2H4+C2H5J 5.30E+04 2.44 5.5 C4H6+CH3J ↔ C5H9J 1.46E+13 0 5.7
C2H3J+H2 ↔ C2H4+HJ 8.98E+12 0 10.3 C2H4+C3H5J ↔ C5H9J 1.43E+12 0 14.39
C2H3J+C3H8 ↔ C2H4+C3H7J 1.02E+03 3.1 8.82 C5H9 ↔ C5H9J 3.32E+08 1.1 29.39
C2H3J+C3H8 ↔ C2H4+C3H7J 9.30E+04 2.44 5.5 C4H9J+H ↔ n-C4H10 1.00E+14 0 0
C4H7J+HJ ↔ BUT-1 1.00E+14 0 0 n-C4H10+CH3 ↔ C4H9J 1.67E+06 1.9 11.04
+CH4
BUT-1+CH3J ↔ C4H7J+CH4 8.34E+05 1.9 11.04 C4H9J+C2H6 ↔ n- 1.93E-05 5.28 7.78
C4H10+C2H5J
C4H7J+C2H6 ↔ BUT-1+C2H5J 1.93E-05 5.28 7.78 C2H4+C2H5J ↔ C4H9J 3.98E+03 2.44 5.37
BUT-1+HJ ↔ C4H7J+H2 1.88E+08 1.75 7.51 n-C4H10+HJ ↔ C4H9J+H2 3.77E+08 1.75 7.51
C4H7J+C3H8 ↔ BUT-1+C3H7J 3.08E+03 2.66 10.1 BUT-1+HJ ↔ C4H9J 1.18E+13 0 3.8
C4H7J+C3H8 ↔ BUT-1+C3H7J 3.95E+03 2.71 12.91 C4H9J+C3H8 ↔ n- 3.08E+03 2.66 10.1
C4H10+C3H7J
BUT-1+C2H3J ↔ C4H7J+C2H4 4.65E+04 2.44 5.5 C4H9J+C3H8 ↔ n- 3.95E+03 2.71 12.91
C4H10+C3H7J
128 Advances in Petrochemicals

Reaction A n E Reaction A n E
(kcal/mol) (kcal/mol)
C2H4+C2H3J ↔ C4H7J 4.18E+10 0 5.2 n-C4H10+C2H3 ↔ C4H9J 9.30E+04 2.44 5.5
+C2H4
C4H7J+HJ ↔ BUT-1 5.00E+13 0 0 n-C4H10+C4H7J ↔ C4H9J 3.95E+03 2.71 12.9
+BUT-1
C4H7J+HJ ↔ BUT-2 5.00E+13 0 0 C4H9J+BUT-1 ↔ n- 3.12E-04 4.31 3.39
C4H10+C4H7J
BUT-1+CH3J ↔ C4H7J+CH4 5.46E+13 0 10.39 C4H9J+BUT-2 ↔ n- 3.36E+12 0 12.39
C4H10+C4H7J
BUT-2+CH3J ↔ C4H7J+CH4 4.82E+02 2.92 7.16 C4H9J+C3H6 ↔ n- 1.01E-04 4.75 4.13
C4H10+C3H5J
BUT-1+C2H5J ↔ C4H7J+C2H6 3.12E-04 4.31 3.39

Table 2. Elementary reaction network for light hydrocarbon steam cracking.

2.2. Case study: Naphtha steam cracking model simulation

A light hydrocarbon reaction model was generated using RMG, which contained 91 reactions
and 26 species (Table 2). A naphtha steam cracking reaction network was generated based on
the light hydrocarbon network. The naphtha reaction network contained 2424 reactions and
125 species.

Thirteen sets of industrial data (Table 3) were used here to verify the established multi-scale
steam cracking model. The industrial data were taken from a steam cracking furnace designed
by KBR (Kellogg Brown & Root). The data were collected twice a day and each set of data was
the average value of these two parallel experiments as a means for preventing any errors. The
multi-scale steam cracking simulation took roughly 70s CPU time. The simulation results and
the industrial data of the mass fraction of the main products are shown in Figure 5, where the
x-axis represents the industrial data and y-axis represents the simulation results. All points in
Figure 5 are around the 1:1 diagonal line, which shows that the error of most results were small.
Thus, the established multi-scale model was defined as accurate and robust; it satisfies
industrial needs and can be applied further in our study of operating conditions optimization.

3. Multi-period steam cracking optimization

3.1. Multi-period optimization model for steam cracking

Coking is an unavoidable factor in the long-term steam cracking process. During the steam
cracking process, coke forms on the inner walls of the tube. With coke formation, the internal
diameter of the tube decreases, pressure drops increase and outer wall temperature increases.
It is generally accepted that coke forms from unsaturated hydrocarbons and aromatics [43];
on this basis, an empirical model for coke formation rate is proposed, as shown in eq. (9).
 Simulation and Optimization of Multi-period Steam Cracking Process 129
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9
æ E ö
rc = åAi exp ç - i ÷ ci (9)
i =1 è RT ø

In eq. (9): 1=C2H2; 2=C2H4; 3=C3H6; 4=1-C4H8; 5=C4H6; 6=C6H6; 7=C7H8; 8=xylene; 9=C2H3-C6H5.

Steam cracking is a dynamic process, as coke grows inside the tube. However, coke formation

is slow enough that we can divide the entire cracking period into a series of virtual steady state

periods. Thus, the established multi-scale model can be used in each steady state period, with

coke thickness updated between periods.

No. 1 2 3 4 5 6 7 8 9 10 11 12 13

Feed
D15 0.7091 0.7106 0.7109 0.7099 0.7122 0.694 0.7099 0.6981 0.7109 0.6796 0.7121 0.7115 0.7109
M 94.1 94.76 94.68 94.29 94.31 94.43 94.6 93.67 94.74 95.26 95.26 95.41 94.83
T °C 99.3 101.7 101.6 103.38 101.7 99.6 96.4 99 100.9 101.2 103.3 98.2 97
K 12.45 12.45 12.45 12.48 12.41 12.71 11.17 12.64 12.44 13.02 12.44 12.4 12.39
Operating conditions
F t/h 6.3686 5.413 5.4166 6.0792 5.1948 5.2302 4.9632 4.9812 5.3286 5.397 5.3726 5.431 5.5722
W/O t/t 0.5 0.53 0.53 0.5 0.53 0.53 0.54 0.53 0.52 0.54 0.53 0.52 0.53
CIT °C 639.6 639.4 639.5 633.4 640.9 639.8 642.5 641.4 636.5 634.8 638.8 640.8 639.1
COT °C 871.6 867.6 867.2 872.6 865.6 869.2 865.8 861.6 865.4 863.4 868.4 865.8 867
CIP Mpa 0.366 0.314 0.312 0.345 0.641 0.303 0.292 0.289 0.302 0.312 0.311 0.313 0.326
COP Mpa 0.044 0.043 0.042 0.039 0.043 0.048 0.044 0.04 0.044 0.044 0.043 0.042 0.045
Yields of major products
H2 wt% 1.07 0.99 1.09 1.10 0.99 1.07 0.87 1.01 0.93 1.15 1.19 1.06 1.15
CH4 wt% 16.55 15.62 16.73 16.83 15.39 16.73 13.90 15.76 15.15 18.09 18.80 16.98 17.64
C2H4 wt% 30.65 28.62 29.59 30.03 28.57 30.52 29.23 28.45 30.91 30.64 30.82 30.55 29.56
C2H6 wt% 3.79 3.44 3.54 3.56 3.34 3.64 3.49 3.69 3.61 3.63 3.65 3.68 3.60
C3H6 wt% 16.13 17.38 16.51 16.09 14.88 14.95 15.72 16.95 17.22 15.89 16.50 17.08 16.72
C3H8 wt% 0.90 1.74 0.87 0.82 0.83 0.69 0.99 0.88 1.53 0.96 1.05 1.21 1.17
C4H6 wt% 6.02 6.13 6.09 6.03 5.74 5.76 5.51 6.06 5.63 5.62 5.80 5.57 5.48
N-C4H8 wt% 1.41 1.59 1.70 1.54 1.40 1.31 1.46 2.07 1.38 1.37 1.43 1.58 1.57
I-C4H8 wt% 2.66 2.83 2.98 2.70 2.38 2.32 2.57 3.18 2.79 2.67 2.88 3.09 3.09
others wt% 20.82 21.66 20.9 21.3 26.48 23.01 26.26 21.95 20.85 19.98 17.88 19.2 20.02

Table 3. Industrial data for feedstock, operating conditions and yields of major products.
130 Advances in Petrochemicals

Operation condition optimization is carried out based on the multi-period process model. Coil
outlet temperature (COT) is selected as the variable to be optimized. Thus, the COT of all time
periods of the multi-period model is discretized as [COT1, COT2,..., COTn].

The optimization model is summarized below.

1 M N
N åå
max wt y oj ,t (10)
j =1 i =1

Subject to:

dym ,t St
= ån r
i , m i ,t
"m Î {1,2,L , M} "t Î {1,2,L , N} (11)
dL Vt i

dPt f × E ( L ) × Gt2
=- "t Î {1,2 ,L , N} (12)
dL 5.07 ´ rt × Di ,t ´ 10 4

dym ,t
dTt
( )
ktp Do Tw ,t - Tt - å DH 0fm ,t ×
dL
= m
"t Î {1,2,L , N} (13)
dL å cpm ,t ym ,t
m

rc ,t
Di ,t + 1 = Di ,t - 2 Dd c ,t = Di ,t - 2 × "t Î {1,2,L , N - 1} (14)
r c ,t

9
æ E ö
rc ,t = åAi exp ç - i ÷ ci ,t "t Î {1,2,L , N} (15)
i =1 è RT ø

max Tw ,t £ TM "t Î {1,2,L , N} (16)

t

COTt + 1 - COTt £ d "t Î {1,2,L , N - 1} (17)

LB £ COTt £ UB "t Î {1,2,L , N} (18)

In objective function (10), M is the number of considered species, N is the period number, ωt
(t=1, 2,..., M) are weighted fractions based on the price of each species and yoj,t is the mass
fraction of selected species j in products of period t. Eqs. (11-13) describes mass balance,
momentum balance and energy balance equations in period t (t=1, 2,..., N). In eq. (14), the
internal diameter of period t+1 Di,t+1 equals the internal diameter of the previous period Di,t
 Simulation and Optimization of Multi-period Steam Cracking Process 131
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minus the coke layer thickness. In eq. (16), peak outer-wall temperature should not exceed the
maximum temperature of the tube material. Eq. (17) shows that the adjacent COT difference
is restricted to a certain region to keep the operation stable. Eq. (18) shows the upper and lower
boundaries of optimization variables.

Figure 5. Simulation results compared with industrial data.

The optimization procedure is shown in Figure 6.

3.2. Surrogate coke thickness model

The most time-consuming part of the optimization is the simulation of the multi-period model.
As Figure 6 shows, the only connection between adjacent periods is the coke thickness. Coke
thickness is related to the feedstock component, furnace running time and operating condi‐
tions. As it has been assumed that the feedstock component is fixed between periods and only
COT changes in operating conditions, as eq. (19) shows, then dt is the coke thickness in period t.

dt = f ( feed,period number, COT1 , COT2 ,L , COTt ) (19)

The accumulated coke thickness within a certain period δdt is assumed to only be related to
the furnace running time and COTt (t=1, 2,..., N-1), shown as eqs. (20) and (21).

d dt = dt + 1 - dt = f ( t , COTt ) = a ´ COTt2 + b ´ t 2 + c ´ COTt + d ´ COTt + e ´ t + f

(20)
"t Î {1,2,L , N - 1}
132 Advances in Petrochemicals

i i
dt = å d dt = å ft ( t , COTt ) (21)
t =1 t =1

Figure 6. Optimization procedure with multi-period steam cracking simulation.

Thus, δdt in period t can be regressed using the polynomial function shown as eq. (20). Here,
the coke thickness data is generated using the original multi-period simulation model and
based on this, a surrogate coke thickness model is obtained through regression. The coke
thickness using the surrogate model and original multi-period simulation model are shown
in Figure 7. Dots in Figure 7 are coke thickness from the original multi-period simulation model
and the surface is from surrogate model.

The coke thickness from the surrogate model fits well with the original model; thus, the
decoupled multi-period cracking model, combined with the surrogate coke thickness model
was used in the multi-period simulation. The initial coke distribution along the serial operation
periods was carried out using the surrogate model. Thus, the multi-period simulation problem
was decoupled into N sub-problems and simulated, respectively, in parallel, as shown in
Figure 8.
 Simulation and Optimization of Multi-period Steam Cracking Process 133
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3.3. Optimization with parallel simulation

Figure 8 shows optimization with a parallel simulation procedure using the surrogate coke
thickness model.

Figure 7. Coke thickness from the surrogate model and original multi-period model.

In Figure 8, a surrogate coke thickness model is regressed from the results of the original multi-
period model and the surrogate coke thickness model generates the coke thickness distribution
for each period prior to the simulation. Once the surrogate model is regressed, the process for
each period can be simulated in parallel. The simulation results are sent to the optimization
model. If the criteria are satisfied, the optimization stops; if not, the optimization model
generates a new set of COT and returns it to the simulation model.
There are several common types of parallel computing methods: phase parallel, divide and
conquer parallel, pipeline parallel, master-slave parallel and work pool parallel methods. In
this instance, the work pool parallel job partitioning method was used in the optimization.
Simulation for one period can be treated as one job in the parallel simulation. All the jobs are
stored in the work pool; processors fetch jobs from the work pool as long as the work pool is
not empty. A detailed scheme for parallel simulation is shown in Figure 9.
In Figure 9, NP is the resources that can be used in a parallel simulation (NP=computer
number×processor number for each computer) and NJ is the period number in the multi-period
simulation. If NP≥NJ, that means all jobs can be calculated in one iteration. Otherwise, NP jobs
134 Advances in Petrochemicals

Figure 8. Optimization using a parallel simulation procedure.

Figure 9. Detailed scheme for parallel simulation.

 Simulation and Optimization of Multi-period Steam Cracking Process 135
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must be fetched from the work pool and be postponed until all processors are idle before the
next iteration. Simulation will continue until the work pool is empty.

Another benefit of using parallel simulation is a warm start. To accelerate the steam cracking
simulation, iteration information is stored after the first simulation, which is called a warm
start. If the iteration information is recorded, it can be used as an initial value in the next
simulation for reducing CPU time. A comparison between a warm start for serial and parallel
simulation is shown in Figure 10.

Figure 10. Comparison between a warm start for serial and parallel simulation, based on the multi-period steam crack‐
ing model.

Iteration information for the most recent period is stored in serial simulation. The iteration
information for each period is not entirely the same. Inconsistency of iteration information
makes the simulation slow. In a parallel simulation, however, iteration information for each
period can be stored. This delivers a faster simulation for each period.

3.4. Case study: Naphtha steam cracking model optimization

An industrial multi-period steam cracking instance was used as a case study. Input data is
shown in Table 4. The detailed feedstock composition was calculated using the Shannon
entropy method [39]. An elementary reaction model and optimization with parallel simulation
was used in this case study. The computer used in this optimization had eight cores of i7-2600
CPU and 4GB memory.

The optimization results show a 0.62% ethylene increase compared to the invariant operat‐
ing condition that was implemented in the practice. The comparison of the serial optimiza‐
tion results and optimization with parallel simulation results are shown in Figure 11 and
Figure 12. It can be seen that the tendency of serial and parallel optimization results were
the same. There was a high outlet temperature and high conversion of the major products in
136 Advances in Petrochemicals

the beginning and intermediate periods, and the outlet temperature of final periods were
rather low for reducing the coke formation and for avoiding a high outer-wall temperature.

Feed
Molecular weight 95.26
H/C 2.11
P I N A
PINA 0.3096 0.3223 0.2856 0.0825
IBP 10% 30% 50% 70% 90% EBP
ASTM (°C) 41.2 58.2 80.1 99.0 119.6 148.9 175.9
Operating condition
Feed rate (t/h) 5.4
Water/Oil (t/t) 0.54
Coil inlet temperature (°C) 636.5
Coil inlet pressure (Mpa) 0.31
Coil outlet pressure (Mpa) 0.04
Optimization variables
Objective function 1
(
max 10 0.52∑ yCo H
10

t=1
2 4,t
10
+ 0.48∑ yCo H
t=1
3 6,t
)
Furnace runtime (day) 50
NP 8
TM (°C) 1000.0
δ (°C) 5.0
LB (°C) 855.0
UB (°C) 872.0

Table 4. Supporting information for the steam cracking optimization model.

The error of parallel simulation compared to serial simulation is shown in Table 5.

The CPU time of serial optimization was 17.78hr, while the CPU time of parallel optimization
was 2.08hr. There was a 8.55 x speedup compared with serial optimization, because parallel
calculation and a warm start strategy were used. Thus, the operating conditions could be
dynamically optimized to track the changing market conditions.

The error in optimization with the parallel simulation model was caused by the surrogate coke
thickness model. In eq. (22),

d dt = dt + 1 - dt = f ( t , COTt ) "t Î {1, 2,L , N - 1} (22)

 Simulation and Optimization of Multi-period Steam Cracking Process 137
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Figure 11. COT optimization results for serial and parallel simulation.

Figure 12. C2H4 and C3H6 optimization results for serial and parallel calculation.
138 Advances in Petrochemicals

The feedstock composition and operating conditions, except COT, were fixed. However,

d dt = dt + 1 - dt = f ( t , COT1 , COT2 ,L , COTt ) "t Î {1,2,L , N - 1} (23)

Accumulate coke thickness in each period was related to the operating conditions of all
previous periods. Eq. (23) is simplified as eq. (22) to make the model easier to regress and the
error caused by the simplification is acceptable according to the error shown in Table 5.

COT C2H4 C3H6

Parallel Serial (wt Parallel (wt Serial (wt Parallel (wt

Period Serial (°C) Error (%) Error (%) Error (%)
(°C) %) %) %) %)

1 872.00 872.00 0.00 32.13 32.13 0.01 16.54 16.54 0.00

2 872.00 872.00 0.00 32.22 32.24 0.05 16.55 16.55 0.00

3 872.00 872.00 0.00 32.31 32.36 0.14 16.57 16.57 0.01

4 872.00 872.00 0.00 32.42 32.48 0.21 16.59 16.59 0.02

5 872.00 872.00 0.00 32.56 32.65 0.27 16.58 16.56 0.14

6 872.00 872.00 0.00 32.70 32.84 0.44 16.55 16.49 0.34

7 870.58 871.38 0.09 32.84 33.02 0.54 16.46 16.40 0.34

8 865.58 866.38 0.09 32.89 33.07 0.54 16.31 16.22 0.52

9 860.58 861.38 0.09 32.98 33.09 0.35 16.11 16.04 0.39

10 855.58 856.38 0.09 33.11 33.09 0.04 15.87 15.88 0.07

Average
- - 0.04 - - 0.26 - - 0.18
error

Table 5. Summarized optimization results for serial and parallel calculation.

4. Conclusion

A multi-scale steam cracking model was established in this chapter. An elementary reaction
network was generated to obtain a more accurate and robust model. The results showed that
the established multi-scale model agrees well with the industrial data. A surrogate coke
thickness model is thus proposed to make multi-period optimization with parallel simulation
possible. A case study showed that multi-period optimization with parallel computing
possesses an 8.55 x speedup compared to optimization with serial simulation. Parallel
computing makes real-time optimization (RTO) possible in multi-period optimization. The
average error of optimization using a parallel simulation model was 0.04% compared to
optimization using a serial model. The error was deemed acceptable for the optimization of
large-scale industrial steam cracking processes.
 Simulation and Optimization of Multi-period Steam Cracking Process 139
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Optimization using the parallel computing method can also be used in other aspects of
chemical processes. Due to the complexity of chemical processes, it is always difficult to
conduct a simulation or optimization using a multi-scale model. The connections of different
levels in a multi-scale model or different equipment in chemical process can be decoupled and
transferred to a multiple sub-system model, which can be simulated in parallel. This method
can bring powerful computing performance into play in chemical engineering.

Acknowledgements

The authors gratefully acknowledge the financial support of the National Basic Research
Programme (No. 2012CB720500) and the NSFC (No. 21306100).

Author details

Lei Zhang, Hangzhou Wang, Tong Qiu and Bingzhen Chen*

*Address all correspondence to: [email protected]

Department of Chemical Engineering, Tsinghua University, Beijing, China

References

[1] Van Goethem, Marco et al. Equation-based SPYRO model and solver for the simula‐
tion of the steam cracking process. Computers & Chemical Engineering. 2001; 25(4):
905-911.

[2] Van Geem, K. Single event microkinetic model for steam cracking of hydrocarbons.
Ph.D. thesis. Ghent University; 2006.

[3] Gao, X., Chen, B., He, X., Qiu, T., Li, J., Wang, C., Zhang, L. Multi-objective optimiza‐
tion for the periodic operation of the naphtha pyrolysis process using a new parallel
hybrid algorithm combining NSGA-II with SQP. Computers & Chemical Engineer‐
ing. 2008; 32(11): 2801-2811.

[4] Yang, A., Marquardt, W. An ontological conceptualization of multiscale models.

Computers & Chemical Engineering. 2009; 33(4): 822-837.

[5] Lucia, A. Multi-scale methods and complex processes: A survey and look ahead.
Computers & chemical engineering. 2010; 34(9): 1467-1475.
140 Advances in Petrochemicals

[6] Davis, H. G., Farrell, T. J. Relative and absolute rates of decomposition of light paraf‐
fins under practical operating conditions. Industrial & Engineering Chemistry Proc‐
ess Design and Development. 1973; 12(2): 171-181.

[7] Sundaram, K. M., Froment, G. F. Modeling of thermal cracking kinetics-I: Thermal

cracking of ethane, propane and their mixtures. Chemical Engineering Science. 1977;
32(6): 601-608.

[8] Sundaram, K. M., Froment, G. F. Modeling of thermal cracking kinetics-II: Cracking

of iso-butane, of n-butane and of mixtures ethane-propane-n-butane. Chemical Engi‐
neering Science. 1977; 32(6): 609-617.

[9] Hirato, M., Yoshioka, S. Simulation of pyrolysis of naphtha, kerosene, and gas oil
with a tubular reactor. International Chemical Engineering. 1973; 13(2): 347-355.

[10] Kumar, P., Kunzru, D. Modeling of naphtha pyrolysis. Industrial & Engineering
Chemistry Process Design and Development. 1985; 24(3): 774-782.

[11] Rice, F. O. The thermal decomposition of organic compounds from the standpoint of
free radicals. I. Saturated hydrocarbons. Journal of the American Chemical Society.
1931; 53(5): 1959-1972.

[12] Rice, F. O., Herzfeld, K. F. The thermal decomposition of organic compounds from
the standpoint of free radicals. VI. The mechanism of some chain reactions. Journal of
the American Chemical Society. 1934; 56(2): 284-289.

[13] Kossiakoff, A., Rice, F. O. Thermal Decomposition of Hydrocarbons, Resonance Sta‐

bilization and Isomerization of Free Radicals. Journal of the American Chemical Soci‐
ety. 1943; 65(4): 590-595.

[14] Gear, C. W. The automatic integration of ordinary differential equations. Communi‐

cations of the ACM. 1971; 14(3): 176-179.

[15] Sundaram, K. M., Froment, G. F. Modeling of thermal cracking kinetics. 3. Radical

mechanisms for the pyrolysis of simple paraffins, olefins, and their mixtures. Indus‐
trial & Engineering Chemistry Fundamentals. 1978; 17(3): 174-182.

[16] Scharfe, M., Ederer, H. J., Stabel, U., Ebert, K. H. Modeling of n-hexane pyrolysis: ex‐
perimental investigations in a flow reactor at normal pressure. German chemical en‐
gineering. 1985; 8(2): 119-129.

[17] Joo, E., Park, S., Lee, M. Pyrolysis reaction mechanism for industrial naphtha crack‐
ing furnaces. Industrial & engineering chemistry research. 2001; 40(11): 2409-2415.

[18] Battin-Leclerc, F. Development of kinetic models for the formation and degradation
of unsaturated hydrocarbons at high temperature. Physical Chemistry Chemical
Physics. 2002; 4(11): 2072-2078.
 Simulation and Optimization of Multi-period Steam Cracking Process 141
http://dx.doi.org/10.5772/60558

[19] Warth, V., Battin-Leclerc, F., Fournet, R., Glaude, P. A., Côme, G. M., Scacchi, G.
Computer based generation of reaction mechanisms for gas-phase oxidation. Com‐
puters & chemistry. 2000; 24(5): 541-560.

[20] Broadbelt, L. J., Stark, S. M., Klein, M. T. Computer generated pyrolysis modeling:
on-the-fly generation of species, reactions, and rates. Industrial & Engineering Chem‐
istry Research. 1994; 33(4): 790-799.

[21] Quann, R. J., Jaffe, S. B. Structure-oriented lumping: describing the chemistry of com‐
plex hydrocarbon mixtures. Industrial & engineering chemistry research. 1992;
31(11): 2483-2497.

[22] Di Maio, F. P., Lignola, P. G. KING, a kinetic network generator. Chemical engineer‐
ing science. 1992; 47(9): 2713-2718.

[23] Hillewaert, L. P., Dierickx, J. L., Froment, G. F. Computer generation of reaction

schemes and rate equations for thermal cracking. AIChE Journal. 1988; 34(1): 17-24.

[24] Song, J., Raman, S., Yu, J., Wijaya, C. D., Stephanopoulos, G., Green, W. H. RMG: the
Next Generation of Automatic Chemical Reaction Mechanism Generator. proceed‐
ings. 2003. In AIChE Annual Meeting.

[25] Clymans, P. J., Froment, G. F. Computer-generation of reaction paths and rate equa‐
tions in the thermal cracking of normal and branched paraffins. Computers & chemi‐
cal engineering. 1984; 8(2): 137-142.

[26] Ranzi, E., Dente, M., Goldaniga, A., Bozzano, G., Faravelli, T. Lumping procedures in
detailed kinetic modeling of gasification, pyrolysis, partial oxidation and combustion
of hydrocarbon mixtures. Progress in Energy and Combustion Science. 2001; 27(1):
99-139.

[27] Turanyi, T., Berces, T., Vajda, S. Reaction rate analysis of complex kinetic systems. In‐
ternational Journal of Chemical Kinetics. 1989; 21(2): 83-99.

[28] Ravikeerthi, T., Thyagarajan, R., Kaisare, N. S., Aghalayam, P. Microkinetic model
for NO–CO reaction: Model reduction. International Journal of Chemical Kinetics.
2012; 44(9): 577-585.

[29] Vajda, S., Valko, P., Turanyi, T. Principal component analysis of kinetic models. In‐
ternational Journal of Chemical Kinetics. 1985; 17(1): 55-81.

[30] Turanyi, T. Applications of sensitivity analysis to combustion chemistry. Reliability

Engineering & System Safety. 1997; 57(1): 41-48.

[31] Bellamine, F. H., Elkamel, A. Model order reduction using neural network principal
component analysis and generalized dimensional analysis. Engineering Computa‐
tions. 2008; 25(5): 443-463.
142 Advances in Petrochemicals

[32] Lang, Y. D., Malacina, A., Biegler, L. T., Munteanu, S., Madsen, J. I., Zitney, S. E. Re‐
duced Order Model Based on Principal Component Analysis for Process Simulation
and Optimization. Energy & Fuels. 2009; 23(3): 1695-1706.

[33] Ranzi, E., Dente, M., Pierucci, S., Biardi, G. Initial product distributions from pyroly‐
sis of normal and branched paraffins. Industrial & Engineering Chemistry Funda‐
mentals. 1983; 22(1): 132-139.

[34] Abel, O., Birk, J. Real Time Optimization of Chemical Processes with Application to
Olefins Production. AUTOMATISIERUNGSTECHNIK. 2002; 50(12): 586-596.

[35] Tarafder, A., Rangaiah, G. P., Ray, A. K. Multiobjective optimization of an industrial

styrene monomer manufacturing process. Chemical Engineering Science. 2005; 60(2):
347-363.

[36] Li, C., Zhu, Q., Geng, Z. Multi-objective particle swarm optimization hybrid algo‐
rithm: An application on industrial cracking furnace. Industrial & engineering chem‐
istry research. 2007; 46(11): 3602-3609.

[37] Klein, M. T., Hou, G., Bertolacini, R., Broadbelt, L. J., Kumar, A. Molecular modeling
in heavy hydrocarbon conversions. CRC Press; 2010.

[38] Shannon, C. E. A mathematical theory of communication. ACM SIGMOBILE Mobile

Computing and Communications Review. 2011; 5(1): 3-55.

[39] Zhang, L., Chen, B. Applications of Shannon's entropy theory to naphtha pyrolysis
simulation. Chemical Engineering & Technology. 2012; 35(2): 281-286.

[40] Jae Lee, W., Froment, G. F. Ethylbenzene dehydrogenation into styrene: kinetic mod‐
eling and reactor simulation. Industrial & Engineering Chemistry Research. 2008;
47(23): 9183-9194.

[41] Xu Q., Chen, B., He, X. A fast simulation algorithm for industrial cracking furnaces.
Hydrocarbon processing. 2002; 81: 65-68.

[42] Constantinou, L., Gani, R. New group contribution method for estimating properties
of pure compounds. AIChE Journal. 1994; 40(10): 1697-1710.

[43] Kumar, P., Kunzru, D. Coke formation during naphtha pyrolysis in a tubular reactor.
The Canadian Journal of Chemical Engineering. 1987; 65(2): 280-285.

[44] Zhang, L. Radical Reaction Model Based Simulation and Optimization Method for
Steam Cracking Process. Ph.D. thesis. Tsinghua University; 2014.