UNIVERSITI TUNKU ABDUL RAHMAN

FACULTY OF ENGINEERING AND GREEN TECHNOLOGY

BACHELOR OF ENGINEERING (HONS) PETROCHEMICAL ENGINEERING

UGPA4104 CAPSTONE PROJECT

TITLE: PRODUCTION OF 1, 3-BUTADIENE

Student(s) detail(s):

NAME STUDENT ID YEAR/SEMESTER

HAMZA SUDQI HAMAD 1607688 Y5S2
MOHAMMAD
SURTHI BATHUMALAI 1600726 Y4S2

YAP CHEN KONG 1607415 Y5S2

YONG JIA WEI 1700454 Y4S1

Supervisor : DR. TAN KOK TAT

Moderator : DR. ONG

: IR. DR. LOW CHONG YU

Submission Date :
 TABLE OF CONTENTS

TABLE OF CONTENTS

LIST OF FIGURES

LIST OF TABLES

CHAPTER

1 Literature Review and Project Conception 1

1.1 Process Background 1

1.1.1 Introduction 1

1.1.2 History of Butadiene and Its Production 2

1.1.3 Application of Butadiene 3

1.1.4 Transport, Storage and Safe Handling of Butadiene 5

1.1.5 Health Hazard 6

1.1.6 Environmental Impacts 10

1.2 Physical and Chemical Property 13

1.2.1. Physical and Chemical Properties of Butadiene 13

1.2.2 Physical and Chemical Properties of Butane 16

1.3 Market Survey 18

1.3.1 Market Size and Forecast 18

1.3.2 Supply and Demand 22

1.3.3 Targeted Customers 24

1.4 Site Study 24

1.4.1 Availability of Raw Material 25

1.4.2. Availability of Land and Climate 26

i
 1.4.3 Transportation and Other Facilities 28

1.3.4. Availability of Infrastructure, Labor and Utilities 29

1.4.5 Environmental Impact and Effluent Disposal 32

1.5 Process Selection 33

1.5.1 Alternative Processes 33

1.5.2 Economic Potential 43

1.5.3 Comparison between Alternative Processes 46

CHAPTER

2 Process Synthesis Of Process Flow Diagram(PFD) 49

2.1 Process Database

2.1.1 Material Safety Data Sheet 49

2.1.1.1.n-Butane 49

2.1.1.2.1,3-butadiene 53

2.1.1.3 Hydrogen 57

2.1.1.4 n-Butene 61

2.2 Process Synthesis Approaches and Heuristics 64

2.3 Preliminary Screening Process 66

2.3.1. Literature Review Based on Licensors 66

2.3.2 Catalyst Selection 67

2.3.3 Reactor Selection 72

2.3.4 Heat Exchanger selection 75

2.3.5 Separation Process 77

2.3.5.1 Distillation Column selection 77

2.3.6 Solvent selection 78

2.4 Development Of Base Case Flowsheet And Plant Layout 80

ii
2.4.1 Block Flow Diagram 82

2.4.2 Process Flow Diagram 84

2.4.3 Plant Layout 85

iii
 LIST OF FIGURES

FIGURE TITLE PAGE

1.1 trans 1,3-Butadiene (Molecular structure) 1

1.2 trans 1,3-Butadiene (3D structure) 1

1.3 Application of Butadiene 2019 4

1.4 Anthropological Sources of 1,3-Butadiene 11

1.5 Global Butadiene Demand, by Region - 2018 19

1.6 Global Butadiene Demand, by Application - 2020 21

1.7 Global Butadiene Supply and Demand, 2000- 2045 23

1.8 Travel Distance from Gas Processing Plants Kertih to Polymer 25

Park Kertih

1.9 1,3-Butadiene Production Plant Location 26

1.10 Average Monthly Rainfall at Kertih, Terenganu 27

1.11 Annual Average High and Low Temperature at Kertih, Terenganu 27

1.12 Medical Welfare Centres around Kertih District 29

1.13 Flow Diagram of Steam Cracking Process 34

1.14 Flow diagram of Lummus Catadiene Process 36

1.15 Flow Diagram TPC/UOP OXO-D Process 38

1.16 Flow Diagram of Ostromislensky Process 40

1.17 Flow Diagram of Production of 1,3-Butadiene from Propylene 42

2.1 Block Flow Diagram (Equipment units) 80

2.2 Block Flow Diagram 81

2.3 Process Flow Diagram 82

2.4 Plant Site Layout 85

iv
LIST OF TABLES

TABLE TITLE PAGE

1.1 Application of Butadiene 4

1.2 Health Hazard caused by 1, 3-Butadiene 7

1.3 Type of Exposure Monitoring 9

1.4 Monitoring Frequency of Periodic Monitoring 10

1.5 Recommendations and Regulations for 1,3-Butadiene 12

1.6 Computed Properties of Butadiene 13

1.7 Physical and Chemical Properties of Butadiene 14

1.8 Physical and Chemical Properties of Butane 16

1.9 Industrial Electricity Tariff by Tenaga National Malaysia 30

1.10 Industrial Water Rate Supply by Syarikat Air Terengganu (SATU) 31

1.11 The Type of Waste and Charging Rate 32

1.12 Typical Yield of Steam Cracking 33

1.13 Chemical Reaction for Production of 1,3-Butadiene from n-Butane 35

1.14 Chemical Reaction for Production of 1,3-Butadiene from Butene 37

1.15 Chemical Reaction for Production of 1,3-Butadiene from Ethanol 39

1.16 Chemical Reaction for Production of 1,3-Butadiene from 41

Propylene

1.17 Unit Price of Chemicals 43

1.18 Economic Potential of Production of 1,3-Butadiene from n-Butane 43

1.19 Economic Potential of Production of 1,3-Butadiene from Butene 44

1.20 Economic Potential of Production of 1,3-Butadiene from Ethanol 44

1.21 Economic Potential of Production of 1,3-Butadiene from 45

v
 Propylene

1.22 Comparison between Alternative Processes 46

1.23 Summary of Advantages and Disadvantages for each Alternative 47

Process

2.1 Physical and Chemical Properties of n-Butane 50

2.2 Safety and Hazard Properties of n-Butane 52

2.3 Physical and Chemical Properties of 1,3-butadiene 54

2.4 Safety and Hazard Properties of 1,3-butadiene 56

2.5 Physical and Chemical Properties of Hydrogen 58

2.6 Safety and Hazard Properties of Hydrogen 60

2.7 Physical and Chemical Properties of n-Butene 61

2,8 Safety and Hazard Properties of n-Butene 63

2.9 Type of support material 69

2.10 Advantages and Disadvantages of Packed Bed and Fluidized Bed 72

. Reactor

2.11 Modification of shell and tube heat exchanger part 75

2.12 Advantages and Limitations of shell and tube heat exchanger 76

2.13 Critical Steps for Distillation Column design 77

2.14 Type of Solvent and Effect 79

2.15 Equipment's name in Block Unit 83

vi
 CHAPTER 1

Literature Review and Project Conception

1.1 Process Background

1.1.1 Introduction

Butadiene is an organic compound that contains two carbon-carbon double bonds, and is
classified as an alkene in terms of functional groups (Butadiene: Uses, Polymerization & Production,
n.d.). An aliphatic compound is any compound with a minimum of one carbon-carbon double bond.
Butadiene can occupy either a cis or trans conformers and at room temperature, 96% of butadiene
exists as the trans conformer, which is 2.3 kcal/mole more stable than the cis structure. This structure
is most stable as the orbital overlap between double bonds is maximized; hence allow the maximum
conjugation, meanwhile steric effects are minimized. Conventionally, the trans structure is
considered to have a C2-C3 dihedral angle of 180°. In contrast, the cis structure, in which the dihedral
angle is 0°, with the pair of double bonds facing the same direction, is approximately 16.5 kJ/mol
(3.9 kcal/mol) higher in energy due to steric hindrance. 1, 3-Butadiene contains two double bonds
that are conjugated. 4 sp2 hybridised C atoms were "built", each contributing a p atomic orbital
containing 1 electron.

Figure 1.1: trans 1,3-Butadiene Figure 1.2: trans 1,3-Butadiene

(Molecular structure) (3D structure)
 Butadiene is a synthetic colourless gas and non-corrosive gas. It condenses to a liquid at
minus 4.5 degrees centigrade and has a mild aromatic odor. It is practically insoluble in water and
soluble in organic solvent such as ethanol, ether, acetone and benzene (Hazardous Substances Data
Bank (HSDB) : 181, 2021). It is used primarily as a monomer to manufacture many different types
of polymers and copolymers and as a chemical intermediate in the production of industrial chemicals.
However, the major use of butadiene is in the production of tires. SBR is also used in adhesives,
sealants, coatings and in rubber articles like shoe soles. Besides, polymerized butadiene
(polybutadiene) can be used as an intermediate in the production of acrylonitrile-butadiene-styrene
(ABS). ABS is widely used in items such as telephones, computer casings and other appliances.
Styrene-butadiene latex that used in carpet backings and adhesives; nitrile rubber, used in hoses, fuel
lines, gasket seals, gloves and footwear; and styrene-butadiene block copolymers which are used in
many end-uses ranging from asphalt modifiers (road and roofing construction applications), to
adhesives, footwear and toys, all are the polymers that made from butadiene. Chemical intermediates
made from butadiene include adiponitrile and chloroprene which are used, respectively, in the
manufacture of nylon and neoprene.

1.1.2 History of Butadiene and Its Production

1,3-Butadiene (H2C=CHCH=CH2) is also known as butadiene, alpha,beta-butadiene, buta-

1,3-diene, bivinyl, divinyl, erythrene, vinylethylene, biethylene, and pyrrolylene. It is a chemical
compound that is produced through the processing of petroleum and is mainly used in the production
of synthetic rubber, but is also found in smaller amounts in plastics and fuel. An oragnic compound
occurs naturally in petroleum and it is extracted at refineries. The first discovery of butadiene in
petroleum in 1886 was by an English chemist Henry E. Armstrong and his colleague A. K. Miller
through pyrolysis process. The practical application (as to be too soft to replace natural rubber in
many applications) implemented by a Russian chemist Sergei Lebedev in 1910 when he approached
to conduct butadiene polymerization. Even then, Lebedev's invention, called polybutadiene, was
primarily a laboratory curiosity. There was relatively little demand for rubber products that could not
be met by the vast supplies of natural rubber from Southeast Asia.

In the literature, the most common method of producing butadiene was the ethanol-to-
butadiene(ETB) reaction and have two processes were historically industrialized by this reaction.
The one-step process (or Lebedev process) refers to the direct gas-phase conversion of ethanol to

2
butadiene over active materials (Pomalaza, Capron, Ordomsky and Dumeignil, 2016). The two-step
process (or Ostromislensky process) in which ethanol is oxidized to acetaldehyde and then reacts
with additional ethanol over a tantala-promoted silica catalyst to yield butadiene. Before and during
World War II, this process was used in the United States and the Soviet Union. Since then it has not
been used widely as it is less economical than the hydrocarbon extraction route, but it is still used in
some parts of the world, such as China and India.

Because the two processes have been recognized to undergo the same reaction pathway, both
can be studied conjointly. Butadiene synthesis through the one-step process usually results in the
production of acetaldehyde as a byproduct of the reaction, which has to be recycled in the system in
the case of implementation in an industrial process. Thus, even in the one step process it is necessary
to test feeds containing acetaldehyde in order to assess the behavior of the catalytic system in
acetaldehyde-containing mixtures, however, in lower amounts compared to the two-step process.

Currently, the most widely used technique for production of butadiene is extraction from the
unsaturated hydrocarbon mixture produced from steam cracking of saturated hydrocarbons (butane)
and n-butane dehydrogenation, meanwhile Lebedev process and Ostromislensky process no longer
used on economic grounds. These processes are practiced primarily in the United States, Western
Europe, and Japan. At present, more than 95% of the world’s total butadiene is produced from either
naphtha cracking or n-butane dehydrogenation.

1.1.3 Application of Butadiene

Most butadiene is polymerized to produce synthetic rubber. However, polybutadiene itself is

a very soft, almost liquid material of commercial interest. Therefore, butadiene is used to prepare
copolymers with styrene and/or acrylonitrile, such as acrylonitrile butadiene styrene (ABS), nitrile-
butadiene (NBR) and styrene-butadiene (SBR) are tough and/or elastic. SBR is the material most
commonly used for the production of automobile tires. Moreover, rubbers and latexes made from
butadiene are used to make the following materials and product:

3
 Table 1.1: Application of Butadiene

Raw material Intermediate Product End Product

ABS Resin pipe, conduit, auto parts,

appliance and equipment parts

SBR and PBR tires, hoses, belts , seals, gaskets

Styrene-butadiene latex carpet and paper coatings

Neoprene gloves, wetsuits, waders and

foams
Butadiene
Nitrile rubber hoses, gloves, gaskets and seals.

Adiponitrile Nylon-6, 6, which is used to

produce carpets, textiles and
plastic parts

Other Footwear, adhesive and chemical

intermediate

4
 Figure 1.3: Application of Butadiene 2019 (Butadiene Market | Growth, Trends, and Forecast
(2020 - 2025), 2019)

1.1.4 Transport, Storage and Safe Handling of Butadiene

Although 1,3-butadiene is non-corrosive, but it is highly flammable as it is a unsaturated

hydrocarbon, with two double bonds (diene) which very reactive. As a gas, it's always ready to burn
if it has the proper air mixture and ignition source. Accumulations of butadiene gas within
the flammable range will ignite explosively (L. FIRE, 1987). Hence, butadiene will be liquefied in
order to be transported and stored. Liquefied butadiene will be shipped by pipelines, ships, barges,
rail tank cars, tank trucks and bulk liquid containers. The transported butadiene is required to be
inhibited and the current industry- wide recognized inhibitor is tertiary butyl catechol (TBC). Also,
to minimize the formation of peroxides in butadiene during shipping and handling, the oxygen level
in the vapor space of loaded equipment is not to exceed 1000 ppm. Vessels are specially equipped in
order to carry liquefied gases and typically operate in dedicated service, with limited tonnage
available on a spot basis. For small quantities, pressurized containers may be used. Vessels and
marine facilities shipping butadiene in bulk are regulated by the U.S. Coast Guard. Shipping of
butadiene in containers is regulated by the Department of Transportation (DOT) (BUTADIENE
PRODUCT STEWARDSHIP GUIDANCE MANUAL, 2019).

1,3 butadiene is stored and kept in a standing, spherical storage tank for liquefied petroleum
gas. The pressure in the tank must maintain at a defined value for example, as it may undergo rapid
and uncontrolled polymerization that results in an explosion and in case increase the pressure of
safety valves. In order to maintain low vapour pressures (prevent vaporization), the stored liquefied
product normally is cooled (about 0-6°C) by auto-refrigeration or an external refrigeration unit. To
prevent heating under the influence of solar radiation, the tank is insulated. Insulation used for filling
between the walls space must be a non-combustible material that resists absorption of liquid
hydrocarbon. The area between the two walls contains hydrocarbon vapour or nitrogen which
depends on the design of the storage vessel. If nitrogen is provided between the two walls, the
minimum pressure should be kept above atmospheric pressure to reduce the possibility of a leak.

In order to provide the conditions for safe storage, segregation from oxidant gases and other
oxidants being stored must be done. Condition for butadiene storage should highly anti-corrosion.
Next, stored butadiene should be periodically checked for general conditions and leakage and
container valve guards or caps should be in place. Store containers in location free from fire risk and
away from sources of heat and ignition for example, keep away from combustible material as

5
butadiene has been classified as flammable gas by both Occupational Safety and Health
Administration (OSHA) and Department of Transportation (DOT) (BUTADIENE PRODUCT
STEWARDSHIP GUIDANCE MANUAL, 2019). Besides, all electrical equipment in the storage
areas should be compatible with the risk of a potentially explosive atmosphere. Moreover, the safety
hazards, industrial health risks and exposure limits for butadiene must be often updated or modified
through studies and regulatory changes. And only experienced and properly instructed persons
should handle gases under pressure. Use only properly specified equipment which is suitable for this
product, its supply pressure and temperature.

1.1.5 Health Hazard

Butadiene in liquid or vapour phase in high concentrations can also potentially result in safety
and health risks to workers through immediate or long-term exposure. Additionally, butadiene has
been recognized as a human carcinogen by international agencies like the International Agency for
Research on Cancer (IARC). And butadiene is also classified as a mutagen. In the work environment,
the Occupational Exposure Limit (OEL) for butadiene globally ranges from 1 to 2 ppm, an 8-hour
Time Weighted Average (TWA)(Millar, 1984). Besides, a 5 ppm of short-term Exposure Level
(STEL) of has been set by Occupational Safety and Health Administration (OSHA) and a few other
countries (Regulation Update – 1, 3-Butadiene, 1997).

At the same time, the health effects caused by exposure to 1, 3-butadiene is identified into
two categories which are acute and chronic. While acute exposures can further be split into low and
high doses. Acute low exposures (1,000 ppm or greater) may cause irritation to the eyes, throat, nose,
and lungs. Frostbite may also occur with skin exposure. Acute high exposures (8-hour exposures to
8,000 ppm) may cause damage to the central nervous system or cause symptoms such as distorted
blurred vision, vertigo, general tiredness, decreased blood pressure, headache, nausea, decreased
pulse rate, and fainting. Acute toxicity of 1, 3-butadiene is due to its narcotic effects, metabolize of 1,
3-Butadiene into two DNA reactive metabolites: butadiene monoepoxide and butadiene
diepoxide (ATSDR - Public Health Statement: 1,3-Butadiene, n.d.).

6
 Table 1.2: Health Hazard caused by 1, 3-Butadiene

Health Hazard Effect

Central nervous system In humans, inhalation of very high

concentrations of 1,3-butadiene can result in
CNS effects including lethargy, headache,
drowsiness, fatigue, vertigo, ataxia,
unconsciousness, coma, and respiratory
depression and death. Humans exposed to 2,000
ppm in air for 7 hours reported hallucinations
and distortions in perception. In experimental
animal studies, concentrations of 150,000 to
200,000 ppm have produced mild anaesthesia.
At concentrations of 200,000 to 250,000 ppm,
respiratory depression leading to death has been
reported within 35 minutes. As air levels
approach those high enough to seriously
threaten CNS function, however, the far greater
danger is from explosion.

Respiratory Acute inhalation of 2,000 to 8,000 ppm 1,3-

butadiene can cause irritation of the upper
respiratory tract. Coughing and bronchospasm
can occur, especially in susceptible individuals,
such as persons with asthma.

Dermal Skin contact with liquid 1,3-butadiene may lead

mild to moderate irritation and frostbite.
Mixtures of 1,3-butadiene and clay minerals
have been reported to cause dermatitis.

7
Ocular Exposure to 2,000 to 8,000 ppm 1,3-butadiene
gas able causing eye irritation, chemical
conjunctivitis, and corneal irritation.

Cardiovascular Bradycardia and hypotension secondary to CNS

depression is possible with exposure to very
high concentrations (150,000-250,000 ppm) of
1,3-butadiene.

Gastrointestinal Nausea and dryness of the mouth will occur.

Chronic effects caused by exposure to 1, 3-butadiene are disputable. Cardiovascular diseases

and cancer have shown an increase from the studied several human epidemiological. The factors
causing these excess cancers have not been determined due to the confounding factors such as
smoking, and simultaneous exposure to benzene and styrene, hence true causal relationship cannot
be established. A strong causal relationship between 1,3-butadiene exposure and cancer have been
shown by the experiments that involved chronic exposures to mice and rats. Only at doses toxic to
the mother butadiene will causing birth defects in laboratory animals; however, butadiene has been
shown to be toxic to the foetus in laboratory animals at doses that are not toxic to the mothers.
Moreover, butadiene also shown to cause injury to reproductive organs in mice, although no
reproductive effects was observed in rats following exposure to high levels of butadiene. Based on
human and animal studies, the EPA has classified 1,3-butadiene as a known human carcinogen. The
American Conference of Governmental Industrial Hygienists (ACGIH) has given 1,3-butadiene a
rating of A2, suspected human carcinogen (Oehha.ca.gov. 1992).

Due to the health hazard of butadiene, therefore the Exposure Standards and Guides have
been set by some of agencies and parties such as OSHA. The following table has shown the
regulation of exposure limit of butadiene.

8
 Table 1.3: Type of Exposure Monitoring (ATSDR - Public Health Statement: 1,3-Butadiene,
n.d.).

Exposure Monitoring

General Used to determine the employee exposure shall be

made from breathing zone samples that are
representative of the 8-hour TWA and 15-minute
short-term exposures of each employee.

1. 8-hr TWA exposure evaluation: Representative 8-

hour TWA employee exposure shall be determined on
the basis of one or more samples representing full-
shift exposure for each shift and for each job
classification in each work area.

2. STEL exposure evaluation: Representative 15-

minute short-term employee exposure shall be
determined on the basis of one or more samples
representing 15-minute exposures associated with
operations that are most likely to produce exposures
above the STEL for each shift and each job
classification in each work area.

Initial Monitoring Used to determine accurately the airborne

concentrations of butadiene to which employees may
be exposed.

Periodic Monitoring Used to determine the frequency of periodic

monitoring through the results of the initial
monitoring. Table gives five exposure scenarios and
their required monitoring frequencies, as required by
the final standard for occupational exposure to
butadiene.

9
 Table 1.4: Monitoring Frequency of Periodic Monitoring (Oehha.ca.gov, 1992)

Action level 8 hrs TWA STEL Required monitoring frequency

Limit Not Limit Not Limit Not 8 hrs TWA or STEL not required.
Exceeded Exceeded Exceeded

Limit Exceeded Limit Not Limit Not STEL not required, 8 hrs TWA required
Exceeded Exceeded
monitoring annually

Limit Exceeded Limit Limit Not STEL not required, 8 hrs TWA required
Exceeded Exceeded
monitoring quarterly

Limit Exceeded Limit Limit 8 hrs TWA required monitoring quarterly

Exceeded Exceeded

Limit Exceeded Limit Not Limit STEL required monitoring quarterly,

Exceeded Exceeded
8 hrs TWA required monitoring annually

1.1.6 Environmental Impacts

1,3-butadiene is classified as a Hazardous Air Pollutant (HAP) by Environmental Protection

Agency (EPA) as it is highly mobile in the environment, and not naturally removed or detoxified at a
rate that would significantly reduce public exposure (PROPOSED IDENTIFICATION OF 1,3-
BUTADIENE AS A TOXIC AIR CONTAMINANT, 2001). The largest source of butadiene is the
mobile sources on road. Approximately of 96% (anthropological sources) of the emissions of 1,3-
butadiene was due to the incomplete combustion of petroleum-derived fuels by mobile sources
accounts. Additionally, emission of 1,3-butadien is far greater amounts by vehicles that are not
equipped with catalytic converter compared to vehicles with catalytic converter (after 1994),
however, there are still many vehicles that manufactured before 1994 traveling on the road in
globally except Singapore. The next largest source is the stationary area sources. Stationary area
sources of emission of 1,3-butadiene including the n the exhaust of boilers, heaters, internal
combustion engines, and turbines during activities such as agriculture, manufacturing, residential

10
fuel combustion, and oil and gas production. By comparision,1,3-butadiene that released by
industrial to water and soil are relatively low. Next, emission of 1,3-butadiene during stationary
engine fuel combustion, petroleum refining, the production of certain fungicides, and styrene-
butadiene copolymer production for the manufacture of tires, hoses, paint latex, carpet backing, and
other rubber products are considered as stationary point sources. Furthermore, forest fires are
considered to be a natural source of 1,3-butadiene in the air. About 770 000 tonnes per year of total
global emissions of butadiene were estimated from the forest fires (PROPOSED IDENTIFICATION
OF 1,3-BUTADIENE AS A TOXIC AIR CONTAMINANT, 2001).

Figure 1.4: Anthropological Sources of 1,3-Butadiene (BUTADIENE PRODUCT

STEWARDSHIP GUIDANCE MANUAL, 2019)

As a volatile organic compound, 1,3-Butadiene that is spilled onto water or soil will likely
rapidly volatilize into the air based on its physical and chemical properties and is not expected to be
persistent in the air. The primary reaction for butadiene in air is with photo-chemically produced
hydroxyl radicals, the estimated half-life is on the order of a few hours (usually less than two hours)
(BUTADIENE PRODUCT STEWARDSHIP GUIDANCE MANUAL, 2019). Other reactions with
butadiene that are expected to occur in the atmosphere are with ozone and nitrate radicals. The
estimated atmospheric half-life of 1,3-butadiene with ozone is few hours to few days. However, it is
usually found in ambient air at low levels in urban and suburban areas.

11
 Due to its impact to the environment, some of the regulation were set by many countries such
as Canada to restrict the release of butadiene in order the environment and public health. Table below
was shown some guideline.

Table 1.5: Recommendations and Regulations for 1,3-Butadiene (ATSDR - Public Health
Statement: 1,3-Butadiene, n.d.)

Levels in breathing air set by EPA Concentration in breathing air of 0.9 ppb for
1,3-butadiene.

Regulation for contaminated sites set by Canada Soil standards for the protection of human
health:

Agricultural and low density residential sites: 2

μg/g
Urban park and high density residential sites: 4
μg/g
Commercial and industrial sites: 9.5 μg/g

Sets vapour standards for the protection of

human health:
Agricultural, urban park, residential use
standard: 2 μg/m3
Commercial use standard: 2 μg/m3
Industrial use standard: 3 μg/m3
Parkade use standard: 2.5 μg/m3

12
1.2 Physical and Chemical Property

1.2.1 Physical and Chemical Properties of Butadiene

Butadiene is two aliphatic organic compounds with formula C4H6. The 1,3-butadiene has the
simplest member of the series of conjugated dienes, which contain the structure C=C―C=C, the C
being carbon and this allow a wide variety of chemical reactions peculiar to this system makes
butadiene important in chemical synthesis. Butadiene molecules combine with each other or with
other reactive molecules, as acrylonitrile or styrene, to form elastic, rubber like materials under the
influence of catalysts. In uncatalyzed reactions with reactive unsaturated compounds, such as maleic
anhydride, butadiene undergoes the Diels-Alder reaction, forming cyclohexene derivatives.
Butadiene is attacked by the numerous substances that react with ordinary olefins, but the reactions
often involve both double bonds (for example, addition of chlorine yields both 3,4-dichloro-1-butene
and 1,4-dichloro-2-butene). At atmospheric conditions, 1,3-butadiene exists as a colourless gas, but it
is liquefied either by cooling to -4.4° C (24.1° F) or by compressing to 2.8 atmospheres at 25° C (77°
F) (Hazardous Substances Data Bank (HSDB): 181, 2021).

Table 1.6: Computed Properties of Butadiene

Property Name Property Value

Molecular Weight 54.09 g/mol

XLogP3 2

Hydrogen Bond Donor Count 0

Hydrogen Bond Acceptor Count 0

Rotatable Bond Count 1

Exact Mass 54.04695 g/mol

13
Monoisotopic Mass 54.04695 g/mol

Topological Polar Surface Area 0 Ų

Heavy Atom Count 4

Formal Charge 0

Complexity 21

Isotope Atom Count 0

Defined Atom Stereocenter Count 0

Undefined Atom Stereocenter Count 0

Defined Bond Stereocenter Count 0

Undefined Bond Stereocenter Count 0

Covalently-Bonded Unit Count 1

Compound Is Canonicalized Yes

Table 1.7: Physical and Chemical Properties of Butadiene

Property Name Properties

Critical Temperature & Pressure Critical temperature: 161.8 °C; Critical pressure: 42.6
atm

Colour/Form Colourless gas

Odor Mild aromatic or gasoline-like odor

14
Boiling Point -4.4 °C or 24.1 °F at 760 mm Hg

Melting Point -109 °C or -164°F

Flash Point -76 °C or -105°F

Lower Explosive Limit (LEL) 2%

Upper Explosive Limit (UEL) 11.5 %

Auto-ignition Temperature: 420 °C or 788 ° F

Vapour Pressure 1840 mm Hg at 70 ° F ; 760 mm Hg at 23.9° F

Vapor Density (Relative to Air) 1.87

Specific Gravity 0.621 at 68 ° F

Solubility Insoluble in water; soluble in ethanol, ether, benzene;

very soluble in acetone

Ionization Potential 9.07 eV

Density 0.65 (Liquid at 24°F); 1.88(relative gas density)

Atmospheric OH Rate Constant 6.66e-11 cm3/molecule*sec

Viscosity Gas at 101.325 kPa at 20 °C: 0.00754 cP; Liquid at -

40 °C: 0.33 cP

Corrosivity Non-corrosive

Heat of Combustion -2541.5 kJ/mol (gas)

Heat of Vaporization 20.86 kJ/mol 25 °C; 22.47 kJ/mol at -4.41 °C

Surface Tension 13.4 dynes/cm at 20 °C

Odor Threshold 0.35 mg/cu m (odor low) 2.86 mg/cu m (odor high)

Refractive Index 1.4292 at 25 °C

15
1.2 Physical and Chemical Property

1.2.2 Physical and Chemical Properties of Butane

Butane is a saturated hydrocarbon, or alkanes, with the chemical formula C4H10 of the
paraffin series. It is also used as a collective term for n-butane together with its only other isomer,
isobutane (also called methylpropane), CH(CH3)3 (Butane | chemical compound, n.d.). In room
temperature, butane is a colourless gas with a faint petroleum-like odor. In the structure of butane,
the carbon atoms are joined in an open chain. In n-butane the chain is continuous and unbranched. It
is highly flammable, hence when oxygen is enough or excess, butane will undergoes complete
combustion to form carbon dioxide and vapour, meanwhile if oxygen is limited(incomplete
combustion), carbon (soot) or carbon monoxide may also be formed(PubChem – Butane, 2021).
Moreover, n-Butane able to undergoes free radical chlorination to form both 1-chloro- and 2-
chlorobutanes, as well as more highly chlorinated derivatives. The relative rate of the chlorination is
partially explained by the differing bond dissociation energies, 425 and 411 kJ/mol for the two types
of C-H bonds. The two central carbon atoms have the slightly weaker C-H bonds (Butane Molecule -
- Chemical and Physical Properties, n.d.).

2C4H10 + 13O2 --> 8CO2 + 10H2O Complete Combustion

2C4H10 +18O2 --> 8CO + 10H2O Incomplete Combustion

Table 1.8: Physical and Chemical Properties of Butane

Property Name Properties

Chemical formula C4H10

Molar mass 58.12 g mol−1

Appearance Colorless gas

Odor Gasoline-like or natural gas-like

Density 2.48 kg/m3 (at 15 °C, 59 °F)

16
Liquid density 0.573 at 25 °C

Vapor density (air = 1) 2.1

Vapor Pressure 760 mm Hg at 31.1 °F ; 1823 mm Hg at 77° F;

1820 mm Hg at 25 °C

Melting point −140 to −134 °C; −220 to −209 °F

Boiling point −1 to 1 °C; 30 to 34 °F

Solubility Soluble in water, 61 mg L−1 (at 20 °C, 68 °F);

Very soluble in ethanol, ethyl

ether, chloroform

Explosive limits 1.9–8.5% v/v in air

Atmospheric OH Rate 2.54e-12 cm3/molecule*sec

Constant

Autoignition Temperature 550 °F; 365 °C

Corrosivity Has no corrosive action on metals

Heat of Combustion 19,512 BTU/lb; -10,840 cal/g=; -453.85x10+5

J/kg

Heat of Vaporization 2.39 kJ/mol at normal Boiling Point

Surface Tension 14.7 dynes/cm at 0 °C

Ionization Potential 10.63 eV

Odor Threshold Butane's odor can be detected between 2.9 and

14.6 mg/m3 and in water at 6.2 ppm.

17
 Refractive Index 1.3326 at 20 °C/D

1.3 Market Survey

1.3.1 Market Size and Forecast

As at 19 March 2020 a total of 236,420 global confirmed cases have reached. With Covid-19
initially come out in Wuhan the number of cases confirmed by Hubei Province was the highest in
china. The confirmed cases number in Iran and Italy has risen steadily to 18,407 and 41,035,
respectively. In Asian countries, after a large number of governments limited travel from regions and
countries where COVID-19 is rapidly spreading and creating obstacles for entry to prevent and
reduce spread inside the region and hence new cases has slowed. The global concern has increased as
COVID-19 spreads rapidly in Europe. Furthermore, there are thousands of confirmed cases in
Germany, Spain, France and cases in other EU countries are also growing rapidly.

The US government declared travel restrictions from Europe and on the other side, each
country as well restricts its internal travel within Europe region. Travel restrictions will decrease
traffic between countries considerably. Yet this will directly influence on the demands for C4s and
derivative products such as synthetic and natural rubber, butadiene, and acrylonitrile-butadiene-
styrene (ABS). The COVID-19 global spread has decreased labor availability and disrupted global
supply chains, and hence impacting and affecting manufacturing plants globally (IHS MARKIT,
2020).

During the forecast period, the global market of 1,3-butadiene will prosper with a high
compound annual growth rate (CAGR). Moreover, over the forecast period 2017-2024 global market
of 1, 3-butadiene is expected to achieve an assessment of approximately USD 33.5 Billion. The main
factors for the growth of global 1,3 butadiene are expected to include factors such as increased
demand for good tires due to the increasing automotive sector and increased preference for butadiene
in consumer production (Kenneth, 2020).

Geographically, global 1,3-butadiene market has been segmented into five major regions
such as North America, Europe, Asia Pacific, Latin America and Middle East & Africa region which
illustrated in Figure 1.5.

18
 Figure 1.5: Global Butadiene Demand, by Region - 2018 (Consulting ,2018)

Based on Figure 1.5, the region of Asia-Pacific had dominated the global market of 1,3-
butadiene since this region occupied the highest ratio of 1,3-butadiene demand in the worldwide. It
occupied around 56% of the global 1,3-butadiene demand which is estimated to be around 6882.9
kilo tons and in 2014 this demand has grown from 5963.9 kilo tons. The declared capacity additions
in the area are not enough to meet the demand increase as 1,3-butadiene derivatives are highly
consumed in China and India (Consulting, 2019). The downstream market in Asia-Pacific witnessed
a huge spur in the past few years, due to the higher requirement of the 1,3-butadiene in this region,
(Intelligence, 2018).

In the Asia-Pacific region China represents about 48% of the 1,3-butadiene demand. It also
occupied around 28% of the global market demand of 1,3- butadiene. In China the total installed
capacity is predicted to rise from 4463 kilo tons in 2018 to around 5063 kilo tons by 2025 in order to
minimize import in the long-term forecast. In China the increase of the 1,3-butadiene market was
from 2927 kilo tons in 2014 to approximately 3408 kilo tons in 2018. Thus China is expected to lead
the global butadiene market demand in the future, since most of the major industries where butadiene
derivatives are consumed keep increasing in this country (Consulting, 2019).

19
 Subsequently, the region of the North America occupied 17% of the global market demand of
1,3-butadiene. The 1,3-butadiene global demand was estimated to around 2084.3 kilo tons and has
grown from 2028.3 kilo tons in 2014 (Consulting, 2019). An extraordinary growth in North America
is predicted to experience over the forecast period due to the rising demand for instance elastomers in
tires and different consumer goods (Nester, 2019).

Furthermore, the total 1,3-butadiene demand in Western Europe has been estimated to be
around 1884.7 kilo tons and it rose from 1727.8 kilo tons in 2014. On the other hand, the total 1,3-
butadiene demand in Central & Eastern Europe has been estimated to around 982.7 kilo tons and has
grown from 782.7 kilo tons in 2014. Europe region is expected to grow at a satisfactory pace during
the forecast period owing to increasing application of 1,3-butadiene in tire industries and in other
downstream applications in this region. Historically Western Europe is a major exporter of butadiene
to the world. It is expected to follow same trend in the future but with some decline in export as other
regions bring on new butadiene capacities (Consulting, 2019).

Last but not least, the region of Middle Eastern & African has emerged to be one of the
largest suppliers 1,3-butadiene globally, benefiting from the low-cost feedstock and proximity to
large markets like Asia and Western Europe. The total butadiene demand in Middle East & Africa
has been estimated to around 254.4 kilo tons and has grown from 144.5 kilo tons in 2014. Not
forgotten to estimate the total1,3 butadiene demand in Central & South 11 America was around
207.2 kilo tons and has grown from 200.7 kilo tons in 2014 (Consulting, 2019).

Figure 1.6 illustrates the global demand of 1,3 butadiene by applications at the year of 2020.
From the Figure 1.3 shown, Polybutadiene captures the highest portion of the major end-use
applications and derivatives market. It occupies 28% of the market share and this large volume of the
1,3-butadiene derivative are expected to have the average growth rate of 3.3% annually. The second
largest portion of the 1,3-butadiene derivatives market was dominated by SBR with 26% of the
market share. The increasing demand of PBR was due to the rising number of automobiles across the
world. This is due to its high cold resistant property and hence the automotive industry uses PBR for
non-tire applications for instance gaskets, belt, hoses and other automotive components (Jesse, n.d).

Subsequently, the derivatives of Acrylonitrile Butadiene Styrene (ABS) were the third largest
domination of the market with the share of 13%. The fourth largest market share of the 1,3-butadiene
derivative was the SB latex. It occupied 9% of the market share and it was expected to have the
average growth rate of 2.7% annually. The derivative of the adiponitrile occupies the market share of
6% followed by the adiponitrile with 1% of the market share.

20
 Figure 1.6: Global Butadiene Demand, by Application - 2020 (IHS, 2020)

Butadiene Prominent players

Prominent players in the global 1,3 Butadiene market are Shell Chemical LP, BASF, Exxon
Mobil Corporation, TPC Group, Lanxess, Lyondellbasell, Ineos, Sabic, Dow, LG Chem, YEOCHUN
NCC CO., LTD., Reliance Industries, Jiutai Energy Inner Mongolia Co., Ltd., Bangkok Synthetics
Co. Ltd, JSR and Braskem, amongst others. The 1,3-Butadiene market is fragmented with the
presence of diversified global and regional players with global vendors ruling the market (Fact, n.d).

Some of the major capacity expansions in 1,3 Butadiene market include:

1. In May 2019, Jiutai Energy Inner Mongolia Co., Ltd. announced expansion of its production
capacity to 70,000 tons/annum by mid may.

2. In Feb 2019, Bangkok Synthetics Co. Ltd, a petrochemical company has announced the
expansion of 1,3 butadiene to 80 kilo tons/year in 2021.

3. In August 2018, Yeochun NCC Co., a naptha cracking firm in South Korea announced
capacity expansion from 240 kilo tons/year to 370 kilo tons/year 2020(Fact,n.d).

21
1.3.2 Supply and Demand

In the forecast period (2019-2024) the butadiene market is predicted to record a CAGR of
3.96 %. The market will be driven by rapidly expanding automotive production. The Compound
annual growth rate (CAGR) as long as profit was returned at end of each year of lifespan, is the rate
of profit which would be required for an investment to grow from its initial balance to its final
balance. As the CAGR was increased, the market demand of that substance rising also. The global
market of Butadiene in 2018 is currently 13.2 million metric tons. The global market for Butadiene is
predicted to achieve 14.8 million tons by 2022. Butadiene is primarily utilized for polybutadiene
rubber (PBR), and styrene-butadiene rubber (SBR) which is used for plastic and tires materials. The
growing use of tires and plastics in car manufacturing is thus the largest driving force on the market
(Nexant, 2020).

Global butadiene growth unfortunately, decreased by nearly zero in 2019 and is predicted to
decrease by about 5 percent by 2020. In 2010 and 2017. Growth peaked was close to 5%. Some of
the recent butadiene demand peaks have resulted from the interaction between butadiene derivatives
with the natural rubber market, although low oil prices significantly enhance the competitive
efficiency of butadiene products such as BR and SBR when scope is available. The corona-virus
pandemic impact on demand for butadiene was profound and immediate, initiating tire and vehicle
manufacturing plants are being closed, replacement tires and the new vehicle sales and gradually
being undermineded. Major automotive companies and tire including Goodyear, Bridgestone, BMW,
Michelin, Ford, Daimler, Honda, General Motors, Toyota and Nissan have shuttered their facilities
and stopped their operations worldwide on the middle of the border closures, lock downs, movement
restrictions and traveling bans imposed to reduce the virus spread. Meanwhile, demand for synthetic
(SR) and acrylonitrile butadiene styrene (ABS) systems was robust in the fourth quarter of 2020,
with higher demands mostly being met at increased pace. The automotive industry rebounded in Asia,
while strong global demand for household goods amid the shift to working from home, saw the
respective SR and ABS plants in Asia running at near full rates during the quarter (Nexant,2020).

On the other hand, in 2019, the supply of butadiene was very steady, kept in check with low
demand and restricted production of ethylene in some liquid-cracking areas like Western Europe.
Logistic bottlenecks again left the US with an abundance of propane and butane, falling prices and
growing usage in steam crackers, in turn making crude C4s available for butadiene extraction better.
Although the demand side did not justify higher butadiene production, this left lower demands for

22
imported C4s. High imports of ethane in Western Europe and low total production of ethylene
undermined butadiene production in 2019.

Supply has increased in almost all other fields with another year of growth in the main Asian
cracking industry and there has been no major change to lighter feedstock. Supply was well-balanced
to tight during 4th quarter of 2020. A succession of cracker hiccups limited crude C4 feedstock to
some extent amid some longer-term BD unit outages. Naphtha was the preferred feedstock and
crackers were incentivised to run as hard as possible as demand for cracker co-products ethylene and
propylene was much stronger than anticipated for the period (Nexant, 2020).

Figure 1.7 shows that the increasing trend of the 1,3-butadiene demand from the year of 2014
to 2025. The growth of the global butadiene consumption would robustly rely on the economic
growth, the car industry and fluctuations in the energy market. The rate of growth in major regions of
the world would be drastically different. The mature 15 economies such as Western Europe and
Japan are expected to experience lower marginal growth, and Asia-Pacific countries like China and
India are expected to experience higher growth over the projected period until 2025 than the world
average. The growth of butadiene in the mature economies would rely on the advancements and
future improvements predicted on the butadiene extraction process and catalyst technologies
(Consulting, 2019).

Figure 1.7: Global Butadiene Supply and Demand, 2000- 2045 (Consulting, 2019)

23
1.3.3 Targeted Customers

Demand will rise robustly in areas where downstream markets such as Asia still develop. The
country's position as world's largest butadiene producer and consumer will be secured by the
sustained growth of China's economic and demand growth. Growth is much slower or even
decreasing over the projected year in North America, West Europe and Japan's mature markets. Asia
became the world's most active butadiene market with rapid development in China and new
capacities are developed near naphtha-fed steam crackers and downstream derivatives production
rapidly increasing. However, under the current economic conditions, companies are also cautious in
their preparations and execution of the new capacity expansion, with uncertainty in the price of both
naphtha and butadiene. (IHS, 2019).

1.4 Site Study

Site study is a significant criterion in the process where we survey on a possible location for
the plant to be built at its minimum operating cost, higher profitability and scope for future
expansion. There are a few factors need to be considered in 1,3-butadiene production site selection
include:

i. Availability of raw material

ii. Availability of land and climate

iii. Transportation and other facilities

iv. Availability of infrastructure, labor and utilities

v. Environmental impact and effluent disposal

After conduct a survey regarding to such criteria, we decide that Kerteh, Terengganu,
Malaysia is an ideal location to build our plant site due to existing infrastructure oil and gas
industrial and its location near to the port.

24
1.4.1 Availability of Raw Material

Kerteh, Terengganu is an apt choice of plant due to the availability of raw material for 1,3-
butadiene, butane may be obtained easily from Gas Processing Plant Kerteh (GPK). GPK is a
division of Petronas Gas Berhad in Terengganu and it is known for its production on ethane, propane,
butane and other sales gas. All those productions may provide raw material to a whole lot more
petrochemical industry. This GPK is located 4.8km from our plant, Industrial Land at Polymer Park
as shown in Figure 1.8.

Figure 1.8: Travel Distance from Gas Processing Plants Kertih to Polymer Park Kertih
(Kerteh to Gas Processing Plants Kertih, 2021)

25
1.4.2. Availability of Land and Climate

The chosen plot is located in Polymer Park, 24300 Kerteh, Terengganu with land size of
24.85 acres or 1,045,440 m2, larger than the minimum plant layout requirement to build a
petrochemical plant. It also has extra space for future expansion.

Figure 1.9: 1,3-Butadiene Production Plant Location (24.85 acres Industrial Land at Polymer
Park, Kerteh Terengganu, 2020)

The average price for the industrial land in Polymer Park is approximately RM19.13 per
square meter. Kerteh is a situated in a tropical region where the climate change experiences extreme
seasonal variation in monthly rainfall as shown in Figure 1.10. Even in the driest month there is a lot
of rain. The average annual temperature in this selected site is 28.89℃ – 23.89℃. In a year, the
rainfall is 8.3 inch.

26
Figure 1.10: Average Monthly Rainfall at Kertih, Terenganu (Average Weather in Kertih,
Malaysia, Year Round - Weather Spark, n.d.)

Figure 1.11: Annual Average High and Low Temperature at Kertih, Terenganu (Average
Weather in Kertih, Malaysia, Year Round - Weather Spark, n.d.)

27
1.4.3. Transportation and other facilities

Good transportation facility will ease the transportation to customer and minimum the
transportation cost. The location of our plant is 6-7 mins drive away from Kerteh port which can
export the product to other country through shipping. Kertih Terminals Sdn Bhd (KTSB) is
petrochemical logistics company located within the Petronas Petroleum Industrial Complex in Kertih,
Terrenganu. KTSB manage the storage and logistic portion of nearby industrial company. According
to the research, it provides tank storage, vessel service, truck service and drumming to customer’s
plant through pipeline system (Kertih Terminals, 2018).

Kerteh Airport is essential facility for investor and business worker to travel to site faster. It
is convenient and efficient for business traveler. The distance of airport to our plant is 17.8km.
However, the Airport is local airport which can travel only within peninsular Malaysia. Most of the
flight in Kerteh Airport fly to KLIA which is international airport can interchange the flight to global.
This airport mostly used for offshore personnel transfer to oil and gas platform.

Other than existing facilities, there is a future transportation facility, East Coast Rail Line
which has announced by the government Malaysia in 2026 (Cuenca, 2020). This can reduce the cost
of transportation for long distance shipping of chemical. The route of this railway is connected to the
Port Klang which can export the product. This can reduce the transportation cost and shorten the
distance to export the product to western country. With this future develop railway, our plant can
expand our market to western country in future. The product can easily ship to Port Klang through
rail way and then export the product through sea shipping to western country. Other than export, it
also reduces the transportation cost to local customer.

28
1.3.4. Availability of Infrastructure, Labor and Utilities

Availability of infrastructure, labor and utilities are important factors which contribute to the
site selection. Infrastructure refers to medical centre or hospitals as well as education centre as both
medical and education are vital to the employee and their family. Figure 14 shows the number of
medical welfare available around Kertih District.

Figure 1.12: Medical Welfare Centres around Kertih District (Kerteh, Terengganu Medical,
2021)

When comes to labor, skilled construction labor normally will get from outside the site area
while skilled labor can easily get locally. But, at Kerteh, labor and expertise that are suitable for
training to operate the plant may be hired from several nearby institutions like MARA University of
Terengganu, Institut Latihan Perindustrian, Terengganu Advanced Technical Institut, University
Malaysia Terengganu and Insititut Teknologi Petroliam. The expertise and consultant service can
also get from other nearby industrial company. The development of plant has created large amount of
job opportunity and improve the quality of life nearby the area.

29
 Table 1.9: Industrial Electricity Tariff by Tenaga National Malaysia (Tariff Book, 2006)

Tariff Category Current rate

Tariff D-Low Voltage Industrial Tariff

For first 200 kWh (1-200kWh) per month 38.00 sen/kWh

For next kWh (201kWh onwards) per month 44.10 sen/kWh

Minimum monthly charge RM 7.20

Tariff E1-Medium Voltage General Industrial Tariff

For each kilowatt of maximum demand per 29.60 RM/kWh

month

For all kWh 33.70 sen/Kwh

The minimum monthly charge RM600.00

Tariff E2-Medium Voltage Peak/Off-Peak Industrial Tariff

For each kilowatt of maximum demand per 37.00 RM/kWh

month during peak period

For all kWh during peak period 35.50 sen/kWh

For all kWh during the off-peak period 21.90 sen/kWh

The minimum monthly charge RM600.00

Tariff E3-High Voltage Peak/Off-Peak Industrial Tariff

For each kilowatt of maximum demand per 35.50 RM/kWh

month during peak period

For all kWh during peak period 33.70 sen/kWh

For all kWh during the off-peak period 20.20 sen/kWh

The minimum monthly charge RM600.00

30
 A plant needs large quantity of stable electric and water supply to operate the production line.
Therefore, the plant site must near with the available electricity and water supply area. Tenaga
National Malaysia is responsible to supply the electricity in Terengganu. There is different rate
according to tariff category. The industrial electricity tariff is shown in Table 1.9.

Table 1.10: Industrial Water Rate Supply by Syarikat Air Terengganu (SATU) (Jadual Kod
Tarif, 2021)

Category Usage Water usage per m3 Minimum charge/month

Industrial Normal rate RM 1.15 RM 50.00

However, the water in Terengganu is mainly supplied by Syarikat Air Terengganu (SATU).
The water rate supply for industrial has shown in Table 1.10.

31
1.4.5. Environmental impact and effluent disposal

Every industrial process will produce waste to environment. The wastes normally cause
negative impact to environment. It is very important to consider the allowance level for the disposal
of waste to land, water and air which excess level will lead to environmental pollution and health
problem of community. Therefore, the handling and disposal of waste need to be consideration in the
site survey. The waste must be disposed in safe manner.

Terengganu employs an integrated environmentally friendly waste management system for

industrial wastes to reach the international best level practices. The disposal of toxic waste is carried
out by Kualiti Alam depend on the type and quantity of waste. It will be charge according to type and
quantity of waste. The waste must pack in standard which is 200-liter drums or 1m3 PP bag. Table
1.11 show the type of waste and charging rate.

Table 1.11: The Type of Waste and Charging Rate (Anon., n.d.)

Type of waste Charging rate

Pumpable Liquid per tonne Range from RM810.00 – RM3, 150.00 (USD

253.13 – USD 984.38) depend on type of waste. (Example

mineral oil, organic chemical waste, waste containing
mercury, pesticide wastes, inorganic wastes and
miscellaneous wastes.)

Solid waste per tonne Range from RM2,790.00 – RM3,600.00

(USD 871.88 – USD 1,125.00)

Bulk Wastes

Pumpable Liquid per tonne Ranges from RM630.00 – RM1,800.00

(USD 196.88 – USD 562.50)

Solid waste per tonne RM2,700.00 (USD 843.75)

32
1.3 Process Selection

1.3.1 Alternative Processes

There are five alternative processes in producing 1,3-butadiene. Each process produces 1,3-
butadiene from different raw materials, which are naphtha, n-butane, butene, ethanol and propylene
respectively. They posse different reactions, catalysts, conditions, yield, byproducts and economic
potentials which are the important criteria in evaluating and selecting the most feasible process.

(a) Production of 1,3-Butadiene from Naphtha (Steam Cracking Process)

Steam cracking process is mainly used for ethylene production, but it produces 1,3-butadiene
as by-product as well. Steam cracking process involves breaking down of saturated hydrocarbon
together with steam at very high temperature produce a mixture of light and mainly unsaturated
hydrocarbons, followed by a series of distillation steps to isolate the crude C4 stream which consists
of 1,3-butadiene. The amount of the 1,3-butadiene in the crude C4 stream vary with the selected
feedstock. Table 1.9 shows the typical steam cracking yield of different feedstock. In order to yield
higher amount of 1,3-butadiene, heavier feed such as naphtha is often used to produce higher amount
of crude C4 (White, 2007).

Table 1.12: Typical Yield of Steam Cracking (Akah and Al-Ghrami, 2015)

Yield by weight Ethane (%) Propane (%) Butane (%) Naphtha (%) Gasoil (%)
Hydrogen and methane 13 28 24 26 18
Ethylene 80 45 37 30 25
Propylene 2 15 18 13 14
Butadiene 1 2 2 5 5
Mixed butenes 2 1 6 8 6
C5+ 2 9 13 8 7
Benzene 0 0 0 5 5
Toluene 0 0 0 4 3
Fuel oil 0 0 0 2 18

Steam cracking of naphtha consists of 4 sections, including pyrolysis furnace, quench,

compression, and product recovery/purification as shown in Figure 1.8. Naphtha fed to the pyrolysis
furnace is first preheated to 650°C by a series of heat exchangers in the convection section, followed
by mixing with steam. It is then passed through the radiant section of pyrolysis furnace with

33
residence time of less than 0.25 second. In radiant section, naphtha is heated by burner and cracked
at temperature of 750 to 900°C to produce pyrolysate which consists of ethylene, propylene and
other by-products, including 1,3-butadiene. After leaving the pyrolysis furnace, the pyrolysate is
quenched by a circulating water stream. Fuel oil with high boiling is extracted while the remaining
pyrolysate is then passed through a multi-stage compressor train at 15–100°C to remove C5+
components as raw pyrolysis gasoline. The remaining pyrolysate undergoes a series of to isolate
hydrogen, methane, ethylene and propylene, leaving the crude C4 which can be used as the feed to
produce 1,3-butadiene in extractive distillation unit (Ren, Patel, and Blok, 2006).

Figure 1.13: Flow Diagram of Steam Cracking Process (American Chemistry Council, 2019)

34
(b) Production of 1,3-Butadiene from n-Butane (Lummus Catadiene Process)

Lummus Catadiene process is a catalytic dehydrogenation process for the production of 1,3-
butadiene. It produces 1,3-butadiene via one-step dehydrogenation of n-butane in the presence of
chromium/alumina catalyst. The butadiene yield can achieve up to 64% with selectivity of 65%.
Hydrogen is produced as by-products which can be recovered at high purity and sold (Olah and
Molnar, 2003).

Table 1.13: Chemical Reaction for Production of 1,3-Butadiene from n-Butane

Main Reaction C4H10 → CH2 CHCHCH2 + 2H2

Butane 1,3-Butadiene Hydrogen
Side Reaction C4H10 → C4 H8 + H2
Butane Butene Hydrogen

Lummus Catadiene process consists of 2 sections, including reaction section and recovery
section as shown in Figure 1.9. n-Butane feed is first combined with unconverted butane and butene
recycled from the recovery section and preheated to 600°C before entering to a series of fixed-bed
reactors containing shallow bed of catalyst held at temperature and pressure of 600-620°C and 0.1-
0.4 atm respectively. The first reactor is on-line for about 5-10 minutes. The feed is then passed to
the next reactor so that the catalyst in the first reactor can be regenerated. During the regeneration
process, the reactor is thoroughly purged with steam, thereby stripping residual hydrocarbons from
the catalyst and reactor. Reheat/regeneration air is supplied typically by a gas turbine or an air
compressor. Air is heated in the regeneration air heater before passing through the reactors. The
regeneration air restores the temperature profile of the catalyst bed to its initial on-stream condition
and oxidizes the small amount of coke which deposits on the catalyst during the on-stream period.
When reheat/regeneration is completed, the reactor is re-evacuated and the catalyst is reduced with
fuel gas for the next on-stream period. At least three reactors are required: one on stream, one being
regenerated and one being steam purged after regeneration. Meanwhile, hot effluent from the
reactors is cooled by generating steam and by direct contact with a circulating quench oil stream
before entering the product recovery section. In recovery section, the effluent undergoes an
absorber/stripper system, followed by debutanizer to produce butadiene-rich product stream which
can be sent to butadiene extraction unit to produce a high-purity of 1,3-butadiene (Meyers, 2109).

35
Figure 1.14: Flow diagram of Lummus Catadiene Process (CPMA, 2012)

36
(c) Production of 1,3-Butadiene from Butene (TPC/UOP OXO-D Process)

TPC/UOP OXO-D process is a catalytic oxidative dehydrogenation process for the

production of 1,3-butadiene. It produces 1,3-butadiene via oxidative dehydrogenation of butenes.
Butene is reacted with molecular oxygen to form butadiene and water, with air being the most
readily available source of oxygen. The main by-products are the combustion products, including
carbon monoxide and carbon dioxide.

Table 1.14: Chemical Reaction for Production of 1,3-Butadiene from Butene

Main Reaction 1
C4 H8 + O → CH2 CHCHCH2 + H2 O
2 2
Butene Oxygen 1,3-Butadiene Water
Side Reactions C4 H8 + 4O2 → 4CO + 4H2 O
Butene Oxygen Carbon Water
Monoxide
C4 H8 + 6O2 → 4CO2 + 4H2 O
Butene Oxygen Carbon Water
Dioxide

Figure 1.10 shows a simplified process flow diagram for the TPC/UOP OXO-D process.
Butenes, steam, and air are first mixed and fed into a two-stage reactor system, in which the reactors
are operated at pressure between 0.1 and 0.3 MPa with inlet temperatures from 300 to 400°C and
outlet temperatures from 500 to 600°C. In order to maximize butene conversion, additional air is
introduced in between stage 1 and stage 2 reactors. The reactor effluent is then sent to a quench
tower to condense both the dilution steam added to the feed and the additional water vapor generated
via the oxidative reactions. Condensed water is recovered and vaporized to provide all of the reactor
steam requirements. Net water produced by the process is sent to water treatment. After removing
bulk water, the net product vapor is compressed and sent to an aldehyde scrubber to remove trace
aldehydes and other oxygenates. The rich solvent from the aldehyde scrubber is sent to the aldehyde
stripper to generate a lean solvent for reuse and a vent stream containing the oxygenate contaminates.
The contaminant-free vapor from the aldehyde scrubber is sent to the product absorber, where C4+
hydrocarbons are absorbed in a circulating solvent. The rich solvent from the product absorber is sent
to the degasser to remove any absorbed light species, and then sent to the product stripper for
recovery overhead of the crude butadiene product, which is typically in the range of 55 to 65% of

37
1,3-butadiene. Lean solvent from the product stripper is recycled to the product absorber. Solvent
regeneration is included to remove by-products accumulated in the solvent. The crude butadiene is
then sent to an extractive distillation unit to produce high-purity 1,3-butadiene (Meyers, 2109).

Figure 1.15: Flow Diagram TPC/UOP OXO-D Process (Meyers, 2109)

38
(d) Production of 1,3-Butadiene from Ethanol (Ostromislensky Process)

Ethanol can be used to produce 1,3-Butadiene via Lebedev process and Ostromislensky
process with the different of one-step and two-step process respectively. However, two-step process
is preferred over one-step process because it provides higher yield up to 64% and its catalyst used is
cheaper as well. In Ostromislensky process, ethanol is first dehydrogenated to form acetaldehyde,
followed by reaction between ethanol and acetaldehyde to produce 1,3-butadiene.

Table 1.15: Chemical Reaction for Production of 1,3-Butadiene from Ethanol

1st Reaction CH3 CH2 OH → CH3 CHO + H2

Ethanol Acetaldehyde Hydrogen

2nd Reaction CH3 CH2 OH + CH3 CHO → CH2 CHCHCH2 + 2H2 O

Ethanol Acetaldehyde 1,3-Butadiene Water

Overall Reaction 2CH3 CH2 OH → CH2 CHCHCH2 + 2H2 O + H2

Ethanol 1,3-Butadiene Water
Hydrogen

Ostromislensky process consists of 5 sections, including dehydrogenation of ethanol,

hydrogen separation system, catalysis of acetaldehyde-ethanol, butadiene separation system and
Dowtherm heating system as shown in Figure 1.11. Ethanol is first reacted over copper-chromite
catalyst in a packed-bed reactor to produce acetaldehyde and hydrogen. Since the reaction is
endothermic, heating source is need to maintain the temperature at optimum condition of 595°F. A
hydrogen separation system with a series of change in pressure and temperature is then used to
remove the hydrogen from the product stream before sending to the second reactor. In second
reaction, the heavy products which mainly consists of acetaldehyde are reacted with additional
ethanol over tantala-silica catalyst in a packed-bed reactor to produce 1.3-butadiene and water.
Similar to first reaction, heat source is needed as well for the endothermic reaction to maintain the
temperature at 662°F. The Dowtherm heating system is used to provide the heat source for both first
and second reaction. Eventually, the product stream enters 1,3-butadiene separation system with a
series of distillation steps to separate the 1,3-butadiene from the by-product as well as recycle the
unreacted ethanol and acetaldehyde back to the second reactor (Burla et. al., 2012).

39
Figure 1.16: Flow Diagram of Ostromislensky Process (Burla et. al., 2012)

40
(e) Production of 1,3-Butadiene from Propylene

1,3-Butadiene can be produced from propylene via metathesis, followed by oxidative

dehydrogenation. Metathesis is a reaction of converting two propylene to form ethylene and 2-butene.
Due to the absence of catalyst which can improve the selectivity, butenes, pentenes and hexenes are
produced as the by-products from the side reactions. After separating the ethylene and by-products,
oxidative dehydrogenation is the used to convert butene to 1,3 butadiene.

Table 1.16: Chemical Reaction for Production of 1,3-Butadiene from Propylene

1st Reaction 2C3 H6 → C4 H8 + C2 H4

Propylene Butene Ethylene
Side Reactions C4 H8 → C2 H4 + C6 H12
Butene Ethylene Hexene
C3 H6 + C4 H8 → C2 H4 + C5 H10
Propylene Butene Ethylene Pentene

2nd Reaction 1
C4 H8 + O → CH2 CHCHCH2 + H2 O
2 2
Butene Oxygen 1,3-Butadiene Water
Side Reactions C4 H8 + 4O2 → 4CO + 4H2 O
Butene Oxygen Carbon Water
Monoxide
C4 H8 + 6O2 → 4CO2 + 4H2 O
Butene Oxygen Carbon Water
Dioxide

Overall Reaction 1
2C3 H6 + O → CH2 CHCHCH2 + C2 H4 + H2 O
2 2
Butene Oxygen 1,3-Butadiene Ethylene Water

Production of 1,3-butadiene from propylene consists of 5 sections, including metathesis,

distillation, oxidative distillation and extractive distillation as shown in Figure 1.12. Propylene is first
fed to a reactor in which metathesis occurs at temperature of 302°F and pressure of 29 psi. A mixture
of ethylene, 2-butane, 1-butene, pentene and hexene is produced. The mixture is then passed through
a series of distillation steps to separate the ethylene in the first column, recycling the excess

41
propylene to the first reactor in the second column, as well as recovering the butenes from the by-
products in the third column. The recovered butenes and fresh air are then sent to a packed-bed
reactor with Mo12BiFe0.1Ni8ZrCr3K0.2O53 catalyst at temperature of 752°F and pressure of 44 psi.
Oxidative hydrogenation occurs to produce 1,3-butadiene with the by-products produced from
combustion reaction. They are eventually sent to a column to vent the non-condensable vapors,
followed by extractive distillation for 1,3-butadiene recovery (Nestlerode, Ngo and Haidermota,
2015).

Figure 1.17: Flow Diagram of Production of 1,3-Butadiene from Propylene (Nestlerode, Ngo
and Haidermota, 2015)

42
1.3.2 Economic Potential

Table 1.17: Unit Price of Chemicals.

Component Formula Unit price ($/kg) Source

n-Butane C4 H10 0.53 (3MCO,2021)
Butene C4 H8 1.296 (INTRATEC, 2021)
1,3-Butadiene CH2CHCHCH2 1.245 (statista, 2021)
Ethanol 2CH3 CH2 OH 0.572 (TRADING ECONOMICS, 2021)
Ethylene C2 H4 1.155 (statista, 2021)
Hydrogen H2 0.7955 (Ammonia Energy Association, 2019)
Propylene C3 H6 1.142 (ECHEMI.com, 2021)

Table 1.18: Economic Potential of Production of 1,3-Butadiene from n-Butane

�� ��� → ���������� + ���

kmol 1 1 2

MW (kg/kmol) 58.12 54.0916 2.016

kg 58.12 54.0916 4.032

kg/kg ���������� 1.0745 1 0.0745

$/kg 0.53 1.245 0.7955

Gross profit = 1(1.245) + 0.0745(0.7955) – 1.0745(0.53) = 0.7348 $/kg ��� �������

43
 Table 1.19: Economic Potential of Production of 1,3-Butadiene from Butene

�� �� + �. ��� → ��� ������� + �� �

kmol 1 0.5 1 1

MW (kg/kmol) 56.11 32 54.0916 18.01528

kg 56.11 16 54.0916 18.01528

kg/kg 1.0373 0.2958 1 0.3331

��� �������

$/kg 1.296 0 1.245 0

Gross profit = 1(1.245) + 0.3331 (0) – 1.0373 (1.296) – 0.2958(0) = – 0.0993 $/kg ��� �������

Table 1.20: Economic Potential of Production of 1,3-Butadiene from Ethanol

������� �� → ���������� + ��� � + ��

kmol 2 1 2 1

MW (kg/kmol) 46.069 54.0916 18.01528 2.016

kg 92.138 54.0916 36.03056 2.016

kg/kg 1.7034 1 0.6661 0.0373

��� �������

$/kg 0.572 1.245 0 0.7955

Gross profit = 1(1.245) + 0.6661 (0) + 0.0373 (0.7955) – 1.7034 (0.572) = 0.3003 $/kg
��� �������

44
 Table 1.21: Economic Potential of Production of 1,3-Butadiene from Propylene

��� �� + �. ��� → ��� ������� + �� �� + �� �

kmol 2 0.5 1 1 1

MW (kg/kmol) 42.08 32 54.0916 28.05 18.01528

kg 84.16 16 54.0916 28.05 18.01528

kg/kg 1.5559 0.2958 1 0.5186 0.3331

��� �������

$/kg 1.142 0 1.245 1.296 0

Gross profit = 1(1.245) + 0.5186 (1.296) + 0.3331 (0) – 1.5559 (1.142) – 0.2958 (0) = 0.1403 $/kg
��� �������

The information provided in Table 1.6 shows the unit prices for all the chemical required in
the alternative processes to calculate their respective economic potentials, except for production from
naphtha since it does not have a specific balance equation. Economic potential computes the gross
profit by deducting the cost of product with the cost of raw materials without considering the cost of
equipment, utility and operation. It is useful in process selection to eliminate the not profitable
process. In this case, based on Table 1.7 to Table 1.10, the production of 1,3-butadiene from butene
is eliminated since it has negative gross profit (– 0.0993 $/kg CH2 CHCHCH2 ). On the other hand, the
production of 1,3-butadiene from n-butane has the highest gross profit of 0.7348 $/kg
��� ������� due to lower price of raw material (n-butane), followed by production from ethanol
and propylene with gross profits of 0.3003 and 0.1403 $/kg ��� ������� respectively. Higher
gross profit is favorable for process selection due to high profit value.

45
1.3.3 Comparison between Alternative Processes

Table 1.22: Comparison between Alternative Processes

Production from Production from n- Production from Production from Production from
Naphtha Butane Butene Ethanol Propylene
Reaction Steam cracking Dehydrogenation of Oxidative (i) Dehydrogenation (i) Metathesis
n-butane dehydrogenation of of ethanol (ii) Oxidative
butene (ii) Catalysis of dehydrogenation of
acetaldehyde-ethanol butene
Energy transfer Endothermic Endothermic Exothermic (i) Endothermic (i) Endothermic
(ii) Exothermic (ii) Exothermic
Raw material Naphtha n-Butane Butene Ethanol Propylene
Byproducts Hydrogen, Methane, Butene, Hydrogen Carbon monoxide, Butanol, Butene, Ethylene, Butene,
Ethylene, Propylene, Carbon dioxide Ethylene, Acetic Pentene, Hexenes
Mixed butene, C5+, acid, Ethyl acetate,
Benzene, Toluene, Diethyl ether,
Fuel oil Hexadiene
Yield 5% 63% 70-75% 64% 90%
Catalyst No Chromium/alumina TPC Group OXO-D (i) Copper-chromite (i) W03/Si02
catalyst system (ii) Tantala-silica (ii) Mo12BiFe0.1Ni8
ZrCr3K0.2O53
Reaction 750-900°C 600-620°C 500-600°C (i) 595°F (i) 302°F
Temperature (ii) 662°F (ii) 752°F
46
Pressure 1 atm 0.1-0.4 atm 0.1-0.3 MPa (i) 35 psi (i) 29 psi
(ii) 93 psi (ii) 44 psi
Product recovery Extractive distillation Extractive distillation Extractive distillation Distillation Extractive distillation
Economic Potential - 0.7348 – 0.0993 0.3003 0.1403
($/kg CH2 CHCHCH2 )

Table 1.23: Summary of Advantages and Disadvantages for each Alternative Process
Alternative Processes Advantages Disadvantages
Production from Naphtha  Produce wide range of products  Low 1,3-butadiene yield (5%)
(Steam Cracking Process)  No catalyst required  High energy consumption
Production from n-Butane  Raw material (n-butane) is abundant  Low butane conversion (38%)
(Lummus Catadiene Process)  Moderate 1,3-butadiene yield (63%)
 Produce valuable by-product (hydrogen)
 Highest gross profit
Production from n-Butene  Moderate 1,3-butadiene yield (75%)  Produce carbon dioxide and carbon monoxide
(TPC/UOP OXO-D Process)  Less energy consumption  Raw material (butene) is difficult to obtain
 Negative gross profit
Production from Ethanol  Use of renewable raw material  Many side reaction and byproducts
(Ostromislensky Process)  Moderate butadiene yield (64%)
Production from Propylene  High butadiene yield (90%)  Many side reaction and byproducts
 Costly multi-metal oxide catalyst
 No commercial plant
47
 After comparing and summarizing the five alternative processes as shown in Table 1.19 and
Table 1.20, production of naphtha and butene are first eliminated due to low butadiene yield and
negative gross profit respectively. Although the conversion of n-butane is low, the production of 1,3-
butadiene from n-butane can achieve yield up to 63%. The conversion can be improved by recycling
the unconverted n-butane. Besides, it has the highest gross profit as compared to other alternative
processes. Instead of having cheaper price, n-butane feedstock is also widely available in Malaysia.
As compared to production from ethanol and propylene, it has lesser side reactions and produces
valuable byproducts such as hydrogen. Therefore, production of 1,3-butadiene from n-butane via
catalytic dehydrogenation is selected as the most feasible process.

48
 CHAPTER 2

Process Synthesis Of Process Flow Diagram(PFD)

2.1 Process Database

2.1.1 Material Safety Data Sheet
2.1.1.1 n-Butane
Butane is used in cigarette lightning and other chemicals, as a fuel, an aerosol propellant.
Frostbite of butane and easily flammable when it is contacted with liquid. Its vapour are heavier than
air thus, it could move long distances until it finds a substance which ignites it and then return back
to its source at lightning speed. Either liquid or gas may be any leak. The containers will rupture and
hence violently explosion under prolonged fire or intensive heat exposure.The lower and upper
explosive limit by volume are 1.6-8.4% by volume respectively.Although, when used properly, the
health risks of butane are very low, a highly inflammable and toxic gas causes major problems if
improperly handled. There are great and fatal risks of incorrect use of butane .Large exposure results
in drowsiness, but no other systematic evidence.The upper and lower flammable limit are 1.9 % and
8.5% by volume respectively. In the presence of an oxidizing gas such as air butane will be
flammable. It can be well ignited by sparks , heat or flames. Butane forms explosive mixtures with
air.Butane critical temperature and pressure are 153.2 °C and 525 psi respectively.The auto-ignition
temperature is at 365℃.Normally butane is in gas phase due to the boiling point of it is at −0.5℃
which the boiling point is lower than room temperature.The melting point of butane is at is at
−138℃ moreover,its flash point at -60℃.

49
 Table 2.1: Physical and Chemical Properties of n-Butane.(PubChem, n.d)

Properties
Chemical structure C4H10

Physical description Odourless colorless compressed liquefied

gas

Boiling Point -0.5 °C

Melting Point -138 °C

Flash Point -60 °C

Solubility In water, 61.2 mg/L at 25 °C

Gas density (lb/ft3 ) 0.1554

Vapor Density 2.1

Vapor Pressure 213.7 KPa at 21.1 °C

Autoignition Temperature 365℃

Decomposition It emits acrid smoke and fumes when

heated to decomposition

Viscosity 7.5 at 300 K or 9.9 at 400 K ( uPa.s) (gas)

Corrosivity On metals has no corrosive action

Heat of Combustion -453.85x105 J/kg

Heat of Vaporization 22.39 kJ/mol at normal BP

50
Surface Tension 14.7 dynes/cm at 0 °C

Refractive Index 1.3326 at 20 °C

Molecular Weight 58.12 g/mol

Ionization Potential 10.63 eV

Odor Faint and disagreeable odor

Specific Volume 6.435 (ft3 /lb)

51
 Table 2.2: Safety and Hazard Properties of n-Butane.(PubChem, n.d)

Lower and Upper Explosive Limit (LEL) 1.8-8.4 In air

& (UEL) % (by volume)

Flammable Limits % (by volume) 1.9- 8.5

Critical Temperature 153.2 °C

Physical Dangers The gas is heavier than air and could

move along the ground and distant
ignition is attainable. The gas is heavier
than air and in lower areas it can
accumulate causing a lack of oxygen.

OSHA Standards Vacated 1989 OSHA PEL TWA 800 ppm

(1900 mg/ m3) is still implemented in
some countries

NIOSH Recommendations Recommended Exposure Limit: 10 Hour

Time-Weighted Average: 800 ppm (1900
mg/m3).

Health Hazards High exposure induces drowsiness but no

other systematic evidence.

Fire Hazards Highly flammable. Gas and air mixtures

are explosive.

GHS Classification Danger

Critical Pressure 525 psi

52
2.1.1.2 1,3-butadiene
1.3-butadiena is an aromatically odorless gas. It is delivered under its gas pressure as a
liquefied gas. Contact with the liquid may result in frostbite and It is easily ignited. flames can very
easily flash back to the leak source and this is occurred due to Its vapors are heavier than air . by the
air movement, It can be asphyxiated . For shipping, 1.3 butadiene needs to be inhibited because of
the polymerisation. It can violently rupture,If polymerization happens in the container. The
containers will rupture violently and rocket under prolonged exposure to either heat or fire .The
lower and upper flammability limits in mixture are 2 and 12% by volume whereas, the upper and
lower explosive limit in air are1.1-16.3 % by volume.It is used to make synthetic rubber and plastics,
and to make other chemicals.When prolong exposure to human,it could result in cancer and genetic
defect . The boiling point and melting point of 1,3-butadiene is -4.5 ℃ and -109 ℃. The boiling
point is lower than room temperature, so normally it is gas phase. 1,3-butadiene is avoid from hot
surfaces, flames, electrostatic charges or sparks. Critical temperature of and pressure 1,3-butadiene
are 161.8℃ and 42.6 atm respectively. The auto-ignition temperature is 414℃ and its flash point is -
76 ℃.

53
 Table 2.3: Physical and Chemical Properties of 1,3-butadiene.(PubChem, n.d)

Properties

Chemical structure C4H6

Physical description Odourless colorless compressed liquefied

gas

Boiling Point -4.5 °C

Melting Point -109 °C

Flash Point -76 °C

Solubility 0.735 mg/mL at 25 °C

Not soluble in water but soluble in

organic solvents such as carbon
tetrachloride

Density 0.615g/cm3 at 25 °C

Vapor Density Relative vapor density (air = 1): 1.9

Vapor Pressure 273.6 KPa at 25 °C

Autoignition Temperature 414℃

Decomposition May decompose explosively when heated

54
 above 200 °C/ 1 kbar and once heated to
decomposition it produce acrid smoke
and fumes

Viscosity 0.00754 cP Gas at 20 °C, 101.325 kPa or

0.33 cP Liquid at -40 °C:

Corrosivity Non-corrosive

Heat of Combustion -2541.5 kJ/mol (gas)

Heat of Vaporization 20.86 kJ/mol 25 °C

Surface Tension 13.4 dynes/cm at 20 °C

Refractive Index 1.4292 at 25 °C

Molecular Weight 54.09 g/mol

Ionization Potential 9.07 eV

Odor Mildly aromatic odor

Specific Volume 7.1942 (ft3 /lb)

55
 Table 2.4: Safety and Hazard Properties of 1,3-butadiene.(PubChem, n.d)

Lower and Upper Explosive Limit (LEL) 1.1-16.3 in air:

& (UEL) % (by volume)

Flammable Limits % (by volume) 2.0-12

Critical Temperature 161.8 °C

Physical Dangers The gas is heavier than air and can move
along the ground thus distant ignition
possible. Vapours are uninhibited and
could polymerize, resulting in vents
being blocked.

OSHA Standards No employee is exposed to the airborne

concentration, measured as an eight (8)-
hours average time weighted average of
1,3-butadiene for one part per million
parts of air (ppm)..

NIOSH Recommendations 1.3-butadiene is considered to be a

possible occupational cancer by NIOSH.

Health Hazards At high concentrations,little anesthetic

effect ,resulting in frostbite from skin
contact and slight irritation to nose and
eyes

Fire Hazards Extremely flammable. Gas and air

mixtures are explosive.

56
 GHS Classification Danger

Critical Pressure 42.6 atm

2.1.1.3 Hydrogen

Hydrogen is a colorless, odorless gas and can be smoothly ignited.When it has been ignited,
the flame is blue and almost invisible. Butane vapour is lighter than air. It is flammable over a
spectrum of air or vapor concentrations. Hydrogen is not toxic, but merely asphyxiates by moving
oxygen into the air. The containers can be ruptured violently and rocket under prolonged exposure
to heat or fire . Hydrogen is utilized to produce other chemicals and in oxyhydrogen welding and
cutting.The lower and upper flammability limits in mixture are 4-75% by volume and similarly for
explosive limit is 4-75% by volume in air.The auto-ignition temperature is at 560℃ moreover, the
critical temperature and pressure are -239.9 °C and 12.8 atm respectively.The boiling and melting
point is -253 ℃ and -259 ℃.

57
 Table 2.5: Physical and Chemical Properties of Hydrogen.(PubChem, n.d)

Properties

Chemical structure H2
Physical description Odourless colorless compressed liquefied
gas

Boiling Point -253 °C

Melting Point -259 °C

Flash Point N/A

Solubility Solubility in water, mg/l at 21 °C: 1.62

(very poor)

Density 0.082 g/L

Vapor Density Relative vapor density (air = 1): 0.07

Vapor Pressure 165320 kPa at 25 °C

Autoignition Temperature 560 °C

Decomposition N/A

Viscosity 0.00754 cP Gas at 101.325 kPa & 20 °C

or 0.33 cP Liquid at -40 °C

Corrosivity Non-corrosive

Heat of Combustion -285.8 kJ/mol

Heat of Vaporization 0.90 kJ/mol at -252.87 °C

58
Surface Tension N/A

Refractive Index 1.0001493

Molecular Weight 2.016 g/mol

Ionization Potential Ionization potential of H atom is 13.59

electron volts; 1 L of gas at 0 °C weighs
0.08987 g
Odor Odorless

Specific Volume 12.0482 (ft3 /lb)

59
 Table 2.6: Safety and Hazard Properties of Hydrogen.(PubChem, n.d)

Lower and Upper Explosive Limit (LEL) 4-75 in air:

& (UEL) % (by volume)

Flammable Limits % (by volume) 4- 75

Critical Temperature -239.9 °C

Physical Dangers The gas mixes well with air, explosive

mixtures are easily formed. The gas is
lighter than air

OSHA Standards N/A

NIOSH Recommendations N/A

Health Hazards Vapors can result in dizziness or

asphyxiation without warning.At high
concentrations it can cause irritating if
inhaled . Fire could generate irritating
and toxic gas.

Fire Hazards Extremely flammable. Many reactions

may cause fire or explosion. Gas and air
mixtures are explosive.

GHS Classification Danger

Critical Pressure 12.8 atm

60
2.1.1.4 n-Butene

n-Butene is highly flammable liquid and could cause frostbite or burns when in contact with
skin and eyes.An asphyxiant or a slight anesthetic can be occurred at high concentration. It is slightly
aromatic odor and colorless compressed liquefied gas.The boiling point and melting point of Butene
is -6℃ and -185 ℃. The boiling point is lower than room temperature, so it is in gas phase. It has the
flammability limit at 1.6-10.0% by volume and similarly for the explosive limit at 1.6-10.0% by
volume in air . The auto-ignition temperature is 385℃.. It has critical temperature at 146.60 °C and
its flash point at -80℃. Decompose toxic fume such as CO and NO van be caused by heating and
burning will .Butene has a flash point at -80℃ and it is soluble in water at 25 °C

Table 2.7: Physical and Chemical Properties of n-Butene .

Properties

Chemical structure C4H8

Physical description Odourless colorless compressed liquefied

gas

Boiling Point -6 °C

Melting Point -185 °C

Flash Point -80℃

Solubility In water, 221 mg/L at 25 °C

Density 0.588 g/cm3 at 25 °C, 1 atm

Vapor Density Relative vapor density (air = 1): 1.93

61
Vapor Pressure kPa at 21 °C: 464

Autoignition Temperature 385 °C

Decomposition When heated to decomposition it emits

acrid smoke and fumes.

Viscosity N/A

Corrosivity Noncorrosive

Heat of Combustion -2719.1 kJ/mol at constant pressure and

temp

Heat of Vaporization 20.31 kJ/mol at 298.15 K

Surface Tension 0.0121 dyn/cm at 298.15 K

Refractive Index 1.3962 at 20 °C

Molecular Weight 56.11 g/mol

Ionization Potential N/A

Odor Slightly aromatic odor

62
 Table 2.8: Safety and Hazard Properties of n-Butene.

Lower and Upper Explosive Limit (LEL) 1.6-10.0 in air

& (UEL) % (by volume)

Flammable Limits % (by volume) 1.6- 10.0

Critical Temperature 146.60 °C

Physical Dangers The gas is heavier than air and may travel
along the ground; distant ignition
possible

OSHA Standards N/A

NIOSH Recommendations N/A

Health Hazards An asphyxiant or a slight anesthetic at

high concentrations. It could also cause
eye irritation. This material can be
narcotic in high concentrations

Fire Hazards Extremely flammable. Gas and air

mixtures are explosive.

GHS Classification Danger

Critical Pressure 4.023 MPa

63
2.2 Process Synthesis Approaches and Heuristics

Heuristics are "rules of thumb" that often used when designing a chemical plant to aid the
selection of operating and process conditions in the preliminary process synthesis. They are used to
identify the assessable of overall process and use them to plan process flow. According to Seider et
al. (2017), there are total of 53 heuristics for process synthesis. It is important that not all heuristics
are applicable, but the appropriate heuristics corresponding to the process to be designed are selected.

There are five alternative processes to produce 1,3-butadiene from different raw materials
such as naphtha, butane, butene, ethanol and propylene. In process selection, production of 1,3-
butadiene from butane via catalytic dehydrogenation was selected to reduce the handling and storage
of hazardous and toxic chemicals which achieves Heuristic 1. This is because catalytic
dehydrogenation of butane produces the least by-products (hydrogen and butene) as compared to
other alternative processes. However, proper storage and handling of butane, butene and hydrogen
are necessary since they are highly flammable. Since they are usually existing as liquid under
moderate pressure, explosion could occur when if they are heated. Therefore, storage and handling of
these chemicals must always keep away from heat sources, sparks, open flames, hot surfaces as well
as any oxidants compounds to avoid any causes of fire (HollyFrontier, 2017).

Heuristic 5 stated that do not purge valuable species or species that are toxic and hazardous,
even in small concentrations. Instead of purging, the valuable by-products such as hydrogen and
butene produced from the catalytic dehydrogenation of butane are recovered since they can be used
or sold as fuel and feedstock. Meanwhile, the unconverted butane is recovered as well and further
recycle back to the reactor. Since dehydrogenation of butane is a reversible reaction, it will only
achieve equilibrium instead of complete conversion. According to Le Chatelier's principle, recycling
of butane tends to increases the concentration of reactant, hence shifting the equilibrium to the right
to form more products (chemrevise, 2018). In order to eliminate differences in composition,
temperatures and flow rates, the recycled butane is combined with fresh butane before entering to the
reactor.

For the catalytic dehydrogenation of butane, the main reaction is the conversion of butane to
1,3-butadiene and hydrogen while the side reaction is the conversion of butane to butene and
hydrogen. According to Heuristic 7, for competing reactions that occur in the catalytic
dehydrogenation of butane, the temperature, pressure and catalyst used should be adjusted
accordingly to obtain high yields of desired product. In this case, the temperature and pressure are

64
maintained at 600-620°C and 0.1-0.4 atm respectively with the catalyst of chromium/alumina in
order to achieve yield of 1,3-butadiene yield of 64% and selectivity of 65% (Olah and Molnar, 2003).

Sufficient amount of heat exchangers should be provided for heating or cooling process fluid
streams. Based on Heuristic 25, since the reaction temperature exceeds 400°C, furnace is used
instead of heat exchanger to heat the feed before entering the reactor. Heat exchanger is then
employed after the reaction in order to cool the stream to the desired temperature, with cooling water
in an external shell and tube heat exchangers using counter-current flow. Besides, since catalytic
dehydrogenation of butane is an endothermic reaction, the temperature decreases as the reaction
occurs. In order to maintain the optimal temperature, a heating jacket is installed around the reactor
to provide the necessary heat of reaction in accordance with Heuristic 24.

The effluent leaving the reactor consists of 1,3-butadiene, hydrogen, butene and unreacted
butane. Since the effluent is in vapor phase, Heuristic 10 is first applied to partially condense the
effluent to vapor-liquid mixture with cooling water. The vapor effluent which mainly consists of
hydrogen can be separated easily from the mixture in a phase separator. The remaining liquid
mixture can be then separated by extractive distillation as stated in Heuristic 9 to recover the desired
product of 1,3-butadiene. The 1,3-butadiene, butene and unreacted butane in the liquid mixture have
very low relative volatilities, which makes a conventional distillation sequence nearly impossible.
Therefore, an extractive distillation in presence of a solvent, which increases the relative volatilities
is used to separate 1,3-butadiene from the butane and butene (Meyers, 2019). There are two columns
in series used to first separate butane, followed by 1,3-butadiene from the mixture, while the
remaining unreacted butane is then recycled back to the reactor. When recycling the butane,
Heuristic 43 is applied as the pressure of the recycle stream is increased by pumping a liquid instead
of compressing a gas. This is because it is far less expensive to pump a liquid rather than
compressing a gas. Generally, the power needed to increase the pressure of a gas stream is usually
higher than liquid streams. If acquire a pump, it approximately works at 10 Hp. However, if using a
compressor, a comparable compressor that can be acquired should be of 1000 Hp and are far more
expensive to purchase and install.

65
2.3 Preliminary Screening Process

Due to the economic potential calculation from previous chapter, catalytic dehydrogenation of
butane is selected as it has good performance on the gross profit, low unit price of raw materials and
a high yield of butadiene which up to 64%. In this capstone project the design concept for the
production of 1,3 butadiene is based on the review of existing process design and the reviewed
process is LUMMUS CATADIENE process. LUMMUS CATADIENE process, having two main
sections of process, including reaction section and recovery section as shown in Figure 1.9.

2.3.1 Literature Review on Catalytic Dehydrogenation Process Based on Licensors

In the CATADIENE process, dehydrogenation of n-butane is done over a catalysts. Overall, the
whole process can be separated into 3 sections. The 3 sections are the reaction section, compression
section, and recovery section.

Reaction Section

Fresh butane is entered as feed and combined with recycle butane from the mixer settler unit.
The total feed is then brought to reaction temperature in the gas fired charge heater and sent to the
reactors.Fresh butane is entered as feed and combined with recycling butane from the mixer settler
unit. The total feed is then brought to reaction temperature in the gas-fired charge heater and sent to
the reactors. Inside the reactors, the operating pressure is in the range of 0.14-0.24 bar absolute
pressure. While the system is still under vacuum, the reactor is thoroughly purged with steam,
thereby stripping residual hydrocarbons from the catalyst and reactor into the recovery system.
Recovery of the catalyst done reheating and generally takes place at slightly above atmospheric
pressure. Typically, the gas turbine and air compressor are used to supply the reheating air and the
catalyst is heated to the required temperature by direct-fired. The reheat air leaves the reactors is used
to generate and super-heats high-pressure steam.

Compression Section

In this section, the cooled effluent gas from the quench tower flows to the product compressor
train where it is compressed in several successive stages to a suitable pressure for the operation of
the recovery section. The selected compression ratio is used to optimize compressor performance of
each stage and the gas temperature maintained as low in order to prevent polymer formation.
Interstage knock-out drum separates the water that condenses after each stage of compression. The

66
cooled compressor discharges vapor and the flash drum used to separate the resulting vapor-liquid.
Condensed reactor effluent and the uncondensed reactor effluent vapor stream both flow to the
recovery section.

Recovery Section

Inert gases and light hydrocarbons from the compressed reactor effluent in absorber operating at
1 atm pressure and feed temperature are removed in this section. Naphtha is used as a solvent in the
absorber which absorbed the other hydrocarbons except for H2 and C3. Stripper is used to recover
the and naphtha and able be recovered 99.99%

2.3.2 Catalyst Selection

Catalyst play important role in the dehydrogenation of n-butane as it offers lower activation
energy for the reaction and giving improve the conversion, selectivity, and yield of catadiene. In the
selection of catalyst, the noble metal catalyst was the first choice as it exhibits the high catalytic
capability, however, the high cost and low utilization of precious metals have greatly limited
application in such commercial production, butadiene production. In contrast, non-precious metals
are more favored by commercial production on account of the abundant resources on earth and low
price, even though their catalytic property is not as good as noble metals.

Among all the various available catalysts for butane dehydrogenation, the two most outstanding
catalysts are the chromium-based catalyst and platinum-based catalyst, additionally both catalysts
able to form an ultra-thin oxygen layer that is impermeable to oxygen by collecting oxygen atoms
(O), and form bonding with the toxic carbon monoxide (CO), in order to create the less hazardous
carbon dioxide (CO2). However, platinum-based catalyst has low resistance to corrosive and
sensitivity to the impurities in the feed. Whereas, the chromium-based catalyst has characteristics of
high resistance to heat and corrosion. Meanwhile, during the Catadiene process sulfiding agent is
added to the total reactor feed in order to passivate the metals in the alternating oxidizing and
reducing atmosphere in the reactors. About 15 ppm of maximum addition rate, if the fresh and
recycle feeds contain no sulfur. However, this may cause corrosion on the platinum-based catalyst as
it has weak resistance and this brings chromium-based catalyst ahead of a platinum-based catalyst.
Moreover, the largest problem on the surface of the catalyst which is the coke formation also able to
be reduced by nanocasting of support materials.

Support materials play an important role for supported metal catalysts in bringing out the
capability of the supported metal as a catalytically active center by getting better surface

67
dispersion(Nanomaterials for Green Energy, 2018). Moreover, the chemical and physical properties
of surfaces affect the activation of supported metals to generate the characteristic properties of the
supported metal catalysts. Important functions provided by supported materials:

1. The support with its large surface area allows the active component to spread thus exposing a large
proportion of the latter to the reactants. This minimizes the amount of the active component needed
and is particularly important when the active component is expensive.
2. The support holds on its surface the micro-crystalline particles of the active component and
prevents its sintering.
3. The support surface may interact with the active component to form surface complexes that have
better catalytic activity and selectivity than either that of the support or the active component.
4. The porous nature of the support may control the transport of the reactant and the product
molecules affecting the overall conversion.
The commonly used support materials include various kinds of carbon, alumina, and silica.
And through the features, advantages, and disadvantages of these support materials, alumina is
selected as support to the chromium based catalyst. And Chromium Oxide/alumina catalyst will be
chosen. Chromium alumina is chosen not only it providing high conversion and selectivity, but also
nanocoating of Chromium Oxide by alumina has reduced the much amount of coke formation
compared to other catalysts. Furthermore, once the catalyst becomes spent, its ingredients can be
utilized as raw material for metal industry and refractory applications. Uses include the production of
ferro-chromium and other alloys for the specialty steel industry, as an additive or conditioner for
slags, and as an ingredient in the production of refractory. Besides that, chromia-alumina catalyst has
a long life span which expected 1 to 2.5 years. Lastly, it is non toxicity, people are able to be exposed
to chromium through breathing, eating or drinking and through skin contact safely.

68
 Table 2.9 Type of support material (Ali, Rahman, Sarkar and Hamid, 2014)

Type of support material

Alumina Features
1. Good hardness
2. High thermal conductivity
3. High melting point and compression
strength
4. Good abrasion resistance and
chemical resistance
Advantages
1) Thermally stable
2) High surface area and pore volume
3) Well-ordered pore
4) Narrow pore size
Disadvantages
Hydrolysis rate of aluminum precursors
hard to be control
Silica Features
1. Tendency to form a large network
2. Available in nature and living
organism
3. Good in hardness
Advantages
1) Highly efficiency, selectivity, stable
in reaction
2) Good mechanical strength
Disadvantages
1. Low compatibility
2. Aggregates/agglomerates formation
Zeolite Features
1) Micropores
2) High inertness
3) Excellent in electron conductivity

69
 Advantages
1. Highly effective
2. Corrosion resistance
3. Nonhazardous
4. Highly thermal stable
5. Easy set-up of continuous process
6. High adaptability to all types of
catalysts
Disadvantages
1) Adsorption or steric blockage of
heavy secondary products are
irreversile
2) Microporosity unable be used
3) Shae selectivity is hard to be
exploited
Carbon Features
1. Nonmetallic
2. Tetravalent
3. Porous structure
Advantages
1) Large surface area
2) High mechanical strength
3) Excellent electron conductivity
4) High thermal stability
5) Inertness
6) Good in elasticity
7) High-temperature physical activation
Disadvantages
1. High cost or expensive
2. Non environmentally friendly,
emission of greenhouse gasses
during pyrolysis.

70
 Tubular fixed-bed catalytic reactor is selected, after comparing both types of reactor. This is due
to the lower capital and operating cost. High pressure condition are required to be operated for
reactions involved in the butadiene production. The required volume for tubular fixed bed catalytic
reactor is smaller compared to fluidized bed reactor for high pressure operation, hence offer a lower
capital cost. The high operating cost for fluidized bed reactor is because well mixed condition of gas
phase reactant and catalyst is hard to be maintained if it is operated in high pressure. Besides, there
will be losses in catalyst if fluidized bed reactor is selected. The losses in catalyst are resulted from:
catalyst will settle at the bottom of the reactor if it is not well mixed with the gas phase reactant,
catalyst fine might be generated during the operation of the reactor when the catalyst hit on the wall
of the reactor or through attrition. The catalyst fine will be brought to the downstream of the process
when together with the product stream. Moreover, tubular fixed-bed catalytic reactor offer a lower
maintenance cost .Also it is no need to require the plant shut down in order to have the maintenance
however this will be required by fluidized bed if fouling found at the pipeline and equipment
downstream.

71
2.3.3 Reactor Selection

The selection of reactor design plays a very important role in the success on optimizing the
operation. For a single reaction, highest concentration of feed is used to maintain the highest rate of
reaction (Smith, 2005). Based on the design guidelines for reactors by Douglas, 1998 stated that in
order to maximize the conversion, reactor that always maintains the highest concentration should be
selected. The ideal packed bed reactor (PBR) is chosen for all three reactors because it always
maintains higher concentration of the reactant.

Table 2.10: Advantages and Disadvantages of Packed Bed and Fluidized Bed Reactor

Type of reactor advantages and disadvantages

Fixed Bed Catalytic Reactor Advantages

 It gives the highest conversion per

weight of catalyst of any catalytic
reactor.

 Used for high pressure reaction

where smaller diameter cylinder
vessels is used to allow usage of
thinner vessel walls.

Disadvantages

 Difficult to control the temperature

because heat loads vary through the
bed.

 Temperature in the catalyst becomes

locally excessive, which may lead to
undesired product and catalyst
deactivation.

 The catalyst is usually troublesome

72
 to replace.

 Channeling of the gas flow occurs,

resulting in ineffective use of parts of
the reactor bed.

Fluidized Bed Reactor Advantages

 High heat transfer due to rapid

motion of catalyst.

 The temperature is relatively uniform

throughout the catalyst, thus avoiding
hot spots.

 Can handle large amounts of feed

and solids and has good temperature
control.

Disadvantages

 High cost of the reactor and catalyst

regeneration equipment.

 Attrition of catalyst can cause

generation of catalyst fines which
could be carried over and lost in the
system, and may cause fouling in
pipelines and equipment
downstream.

 Preferable for gas-solid noncatalytic

reactions.

Tubular fixed-bed catalytic reactor is selected, after comparing both types of reactor. This is due
to the lower capital and operating cost. High pressure condition are required to be operated for
reactions involved in the butadiene production. The required volume for tubular fixed bed catalytic

73
reactor is smaller compared to fluidized bed reactor for high pressure operation, hence offer a lower
capital cost. The high operating cost for fluidized bed reactor is because well mixed condition of gas
phase reactant and catalyst is hard to be maintained if it is operated in high pressure. Besides, there
will be losses in catalyst if fluidized bed reactor is selected. The losses in catalyst are resulted with
catalyst will settle at the bottom of the reactor if it is not well mixed with the gas phase reactant,
catalyst fine might be generated during the operation of the reactor when the catalyst hit on the wall
of the reactor or through attrition. The catalyst fine will be brought to the downstream of the process
when together with the product stream. Moreover, tubular fixed-bed catalytic reactor offer a lower
maintenance cost .Also it is no need to require the plant shut down in order to have the maintenance
however this will be required by fluidized bed if fouling found at the pipeline and equipment
downstream.

74
2.3.4 Heat Exchanger selection

Typically heat exchanger is used for preheating and intermediate cooling for the process and 1,3
butadiene is not excepted. Selection of heat exchanger must take consideration on the pressure drop
of the operation process and that should be controlled in the range of 0.2 to 0.3 bar, therefore plate
heat exchanger can be the best choice. However, the materials for the plate heat exchanger are
titanium hence it has disobeyed the concept of low CapEX design, therefore, the shell and tube heat
exchanger (materials made of lower cost such as stainless steel) is selected. The pressure drop issue
can be solved by some modification of the shell and tube heat exchanger.

Table 2.11 Modification of shell and tube heat exchanger part

Modification

Shell side Increasing shell diameter, tube flow area

will be increased and number of tubes is
increased thereby reduces of tube flow
velocity hence tube side pressure drop is
reduced.

Tube side According to John E. Edwards in “Design

and Rating Shell and Tube Heat
Exchangers” arranging the tubes in a
square pattern tends to lower the shell-
side pressure drop.

Tube pitch Lower the tube pitch in order to limit the

pressure drop on the shell-side by
slowing down the flow rate and
maximizes heat transfer.

Besides, in order to maximize the rate of heat transfer, a counter-current flow in the heat
exchanger is selected. As a more uniform temperature difference between the fluids, over the entire
length of the fluid path, thus TEMA F Shell is selected. After all of the consideration and
modification, the most fulfilled shell and tube heat exchanger is the Fixed Tube Sheet Heat

75
Exchanger, hence it is selected. The advantages and limitations of it will be shown on the Table 2.
below. Moreover, coke formation on heat exchanger is unable be avoided hence cleaning process is
required. According to the Japan patient, JP-A 2011-001341, the excessive frequency of interruption
of the process to clean the heat exchanger can be avoided by two heat exchangers arranged in
parallel, which are each alternately operated or rinsed (called NB operation mode)(Arnold et al.,
2010).

Table 2.12 Advantages and Limitations of shell and tube heat exchanger part

Advantages Limitations

Less costly than removable bundle heat Shell pass cannot be cleaned with the
exchangers. mechanical method, only by chemical
means and the maintenance is difficult.

Provides maximum heat transfer surface Outer surface of tube cannot be cleaned
per given shell and tube size. manually or mechanically.

Provides multi-tube-pass arrangements. Shell and tube sheet material should be

weldable together.

76
2.3.5 Separation

Separation is a process that 1,3 butadiene production must undergo in order to obtain the pure
1,3 butadiene by removing other by-products. Generally, the separation of 1,3 butadiene is done by
the extraction distillation. It performs the separation of close boiling components or azeotropes in the
presence of a miscible, high boiling, the relatively non-volatile component that forms no azeotrope
with the other components in the mixture(Computer Aided Chemical Engineering, 2014).

2.3.5.1 Distillation Column selection

In general, in the selecting of separation method, an engineer must understand and determine
five key design elements for the process. In order to have successful separation, the following critical
steps must be follow:

Table 2.13 Critical Steps for Distillation Column design

Step

1 Determination of vapor-liquid equilibrium

2 Determination of column operating objectives

3 Determination of operating pressure

4 Determination of R/Dmin and Nmin and feed stage estimation

5 Optimizing of diameter and height of the column

Since dehydrogenation reaction is reversible, hence there may incomplete conversion in the
reaction process, thus the reactor effluents will consist of the by-products and unreacted reactants, so
the separation is the step for purifying the butadiene. As the volatility of the desired product,
butadiene is similar to the side product, butene and unconverted feed butane, hence the extraction
system required to have two extraction distillation columns. The similar volitility of these three
components, hence high pressure condition is to be operated. And this extraction system design must
follow the critical steps shown on Table.

The separation of butadiene is starting by effluents from the reactor are in the vapor-liquid
mixture, the VLE for butadiene and n-butane changes due to the solubility variance of butadiene in
distillation solvent when the solvent is introduced at the top of the extractive distillation column in

77
the liquid phase. The operating temperature was decreased by the solvent and this able to prevent
butadiene being oligomerized and reducing operating costs (reduce the cost of installation of a
condenser). In the extractive distillation column, butadiene, butene and butane are be separated
where most of the n-butene (OFFGAS) is transported to the top side. Subsequently, part of the
butadiene and butane (heavy key) are discharged to the bottom of the column. The highly-purified
butadiene( typically inhibited with tertiary butyl catechol, TBC) is then separated from the second
distillation column as distillate. And all of these separation process parameters such as operating
pressure and temperature able be simulated by the Aspen plus and this helping select the type of
column being used. According to Perry’s Chemical Engineers’ Handbook, packed columns usually
are chosen for the process that involving very low allowable pressure drops, and for small-scale
operations requiring diameters of less than 0.6 m or 2 ft. Tray columns are more economically
favorable for large-scale operations, hence is chosen for this project.

In order to maximize the mass and heat transfer between the liquid and vapor phases in the
column, column internals selection is important as it will provide intimate contact between both
phases. Sieve tray is chose as it offer advantages of low fouling tendency when compared to other
conventional trays. Besides, sieve tray is simple and easy to fabricate, and is relatively inexpensive
compared to other mass transfer trays.

2.3.5.2 Solvent selection

As the solvent is the heart of extractive distillation, the selection of potential solvents should be
taken more considered. The degree of unsaturation of hydrocarbon will directly affect the affinity to
polar solvent. Hence, a highly unsaturated hydrocarbon will be more soluble in a polar solvent, and
the solvent decreases the volatility of the hydrocarbon. According to the Perry‟s Handbook, several
features are essential:

1.The chosen solvent must able to affect the liquid-phase behavior of the key components differently;
or else no enhancement inseparability will occur.

2.The solvent must be relatively nonvolatile and higher boiling than the key components of the
separation in the extractive column, in order to remain largely in the liquid phase.

3.The additional azeotropes should not be formed by solvent with the components in the mixture to
be separated.

4. The extractive column must be a double-feed column, with the solvent feed above the primary
feed; the column must have an extractive section.

78
 Moreover, effects of the solvents used must taken into consideration. Several solvents are able to
be used in extractive distillation to separate butadiene, the examples of solvents have acetonitrile,
dimethylformamide (DMF), and n-Methyl-2-Pyrrolidone (NMP). The investigation has been done on
using acetonitrile and DMF to recover butadiene, however, the application of acetonitrile is not
favored due to its toxicity. DMF can be hydrolyzed into formic acid during this process, which is
corrosive to carbon steel which is the main material for most of the column. Besides, DMF is
hazardous, it able to causes threats not only to human health but also to the environment. Hence,
NMP, a colorless hygroscopic liquid with characteristic odor, with boiling point of 202ºC and flash
point of 96ºC is widely used to recover butadiene due to its high solubility and selectivity toward
unsaturated hydrocarbons. However, NMP also can cause dry, redness and maybe absorbed to skin,
but NMP is the most acceptable solvent to be used in the process as it causes least harm to the
environment and human.

Table 2.14 Type of Solvent and Effect

Solvent Hazard
Effect
Identification
n-methyl-2pyrrolidone (NMP)  Stable, but decomposes upon exposure to
light.
 Combustible

Dimethylformamide (DMF)  Hazardous

 DMF has been linked to cancer in
humans, and it is thought to cause birth
defects

Acetonitrile (ACN)  Toxic and flammable.

 It is metabolized into hydrogen cyanide
and thiocyanate

79
2.4 Development Of Base Case Flowsheet And Plant Layout

2.4.1 Block Flow Diagram

Pump

Mixer Furnace

FBR Heat
Exchanger Compressor Flash
(Cooler)
Drum

Extraction Distillation

Extraction Distillation
Shell and

Column 1

Column 2
Tube Heat
Exchanger
(Heater)

Figure 2.1 Block Flow Diagram (Equipment units)

80
 OFFGAS(HYDROGEN, BUTENE)

FEED CATALYTIC COMPRESSION RECOVERY

( N-BUTANE) DEHYDROGENATION PROCESS PROCESS

N-BUTANE PURIFICATION

PROCESS

1,3 BUTADIENE

Figure 2.2 Block Flow Diagram

81
 The Block Flow Diagram, Figure 2.1 and 2.2 above shows the 1,3-butadiene production plant flow with 4 process, catalytic
dehydrogenation of n-butane to 1,3-butadiene, compression process, recovery process and removal of off gas and purification of 1,3-butadiene,
which consist of 10 unit operations starting from the feed (n-butane) till the product extraction at (1,3-butadiene) from Extraction Distillation
Column 1 and 2 while the byproduct (butene) is recycled back to the mixer as feed from Extractive Distillation Column 2. In this process Fixed
Bed Reactor and Flash Drum are chosen be equipped. The production flow is aid by heater, cooler and pump.

2.4.2 Process Flow Diagram

Figure 2.3 Process Flow Diagram

82
 Table 2.15 Equipment's name in Block Unit

Block Unit Equipment

B1 Mixer
B2 Furnace
B3 Fixed Bed Reactor
B4 Shell and Tube Heat Exchanger(Cooler)
B5 Compressor
B6 Flash Drum
B7 Shell and Tube Heat Exchanger(Heater)
B8 Extraction Column 1 (Distillate Butene)
B9 Extraction Column 2 (Distillate Butadiene)
B10 Pump (Recycle n-Butane)

83
2.4.3 Process Description

Process flow diagram in Figure 2.1 above described details flow of butadiene process.
Basically for the PFD diagram, the major and minor include together except the controller system
that explained details in process safety studies. First of all, by referring the Figure 2. , it knew that
this process is a continuous cyclic process, the detail of the process will be explained following. In
this process, there is only 1 basic chemical which is n-butane. The n-butane will pass through the
pipeline and enter the first equipment B1, Mixer. The fresh n-butane, S1 will undergo mixing with
the unconverted n-butane, S14, and the temperature of the mixture, S2 will be slightly higher than
the fresh feed due to the heat brought by the recycle feed. Then S2 will enter the furnace heat
exchanger, B2. The furnace heat exchanger is selected rather than a normal fired-furnace as the
furnace heat exchanger offers a higher efficiency of heat transfer to the reactant compare to the
furnace. The preheated feed, S3, entering the third equipment, B3, Fixed Bed Reactor, and undergoes
the catalytic dehydrogenation with an operating temperature of 600°C and pressure of 1bar. In the
reactor, heterogeneous catalyst, chromia-alumina catalysts are used to speed the reaction by
lowering the activation energy and increasing the conversion rate of n-butane to 1,3 butadiene. After
the reaction occurred, the effluent will be cooled down by the cooler, B4, to the temperature of 40°C
by lowering the conversion for side-product, butene since the reaction is endothermic. Next, the
cooled effluent, S5, will be compressed by using a compressor, B5. The compressor is in a single
stage as the pressure increase is lower than 100 psi and it is much economic compared to two stages
compressor. The compressed effluent, S7, will be sent to the flash drum in order to remove the
Hydrogen produced in the reactor from the C4 mixture. The Hydrogen, S7 will be stored and sold as
a valuable product. The C4 mixture will be separated and discharged as bottom products, S8, and be
sent to the heating by a heat exchanger, B7 in order to partially vaporized the C4 mixture. The heat
C4 mixture will be sent to the first Extraction Distillation Column with make-up solvent NMP. In
this column, butene will be extracted out as the light key component, S10 and same as S7, will be
stored and sold as a product. The butane-butadiene mixture, S11 will be discharged as heavy- key
and be sent to the second column, B9 for purification, in order to obtain the pure 1,3 butadiene. The
purified butadiene will be separated as a light key and being stored and sold as a product. The
unreacted/unconverted butane will be discharged as heavy key, S13, and undergoes a decrease in
pressure by the pump, B10. The unconverted n-butane, S14 then will recycle to the Mixer and
combine with fresh n-butane.

84
2.4.3 Plant Layout
Plant Layout
1. Administrative Office Main
2. Engineering Office
1 FLB
3. Meeting room
4 2
4. Laboratory
5. Clinic 3

6. Product Quality Assurance Development 5 6

7. Control Room
8. Utilities & Equipment Storage 8 7 12
9. Feedstock Tank Farm 10
10. Operating Plant
11. Product Tank Farm
12. Utilities & Equipment Storage
* All entrances are built with guard house
and tight security system.
* FLB: Feed Loading / Unloading Bay
* PLB: Product Loading / Unloading Bay

Figure 2.3 Plant Site Layout

85
 This Plant Layout is majorly designed with site layout factors concern. The factors mainly are
economic considerations (construction and operating cost), process requirements, operation
convenience, maintenance convenience, future expansion, modular construction and safety. Now, in
this plant layout, we placed administrative office, engineering office, meeting room, laboratories and
clinic is mainly located away from the operating plant. The utilities and equipment room is located
right next to the control room and in a position where the piping system between the process unit is
minimized. Moreover, the principal ancillary buildings are sited not much far from the plant in order
to reduce motion and time. Finally, we have loading and unloading bay near for both feed and
product tank farm with the utility and equipment storage placed in-between the plant (Zhuang, 2016) .

86
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