Assignment 1

Submitted To: Sir Salman Raza Naqvi

Daneal Ahmad Shafiq | Chemical Process Technology | 28th Feb 2019
 Naphtha Cracking for Ethylene & PVC
Production
Introduction to olefins and steam cracking

Olefins are major building blocks for petrochemicals. Because of their reactivity and
versatility, olefins like ethylene, propylene, butenes, butadiene, etc., have been
growing in demand. Olefins are finding wide application in the manufacture of
polymers, chemical intermediates, and synthetic rubber. Ethylene itself is basic
building block for large number of petrochemicals and is normally quoted as king of
chemicals.

The steam cracker remains the fundamental unit and is the heart of any
petrochemical complex and mother plant and produces a large number of products
and byproducts such as olefins and pyrolysis gasoline. The choice of the feedstock for
olefin production depends on the availability of raw materials and the range of
downstream products. Naphtha has made up about 50-55% of ethylene feedstock
sources since 1992.
Process Flow Diagram for Pyrolysis of Naphtha
Modern ethylene plants incorporate following major process steps: cracking
compression and separation of the cracked gas by low temperature fractionation.
The nature of the feed stock and the level of pyrolysis severity largely determine the
operating conditions in the cracking and quenching section. Various steps involved in
the pyrolysis of naphtha and separation of the products are discussed below.

Hot Section

It consists of convection zone and radiant zone. In the convection zone, hydrocarbon
feed stock is preheated and mixed with steam and heated to high temperature. As a
result, rapid rise in temperature and pyrolysis reaction take place. The addition of
dilution steam enhances ethylene yield and reduces the coking tendency in the
furnace coils. The production of the pyrolysis reaction consists of a wide range of
saturated and unsaturated hydrocarbons.

Convection Zone Feed stock is pyrolised and the effluent conditioned

Radiation Zone The product formed are separated and purified

Quench To avoid subsequent reaction, the effluents are fixed in

their kinetics development by sudden quench.
Indirect Quench Indirect quench by water to 400-500OC, generation of high
pressure steam
Direct Quench Direct quench by heavy residue by-product of pyrolysis

Primary Separation of light products of pyrolysis as top and bottom

Fractionation as pyrolysis product
Column

Compression Compression of light products

Caustic Scrubbing Scrubbing with caustic followed by molecular sieve

and Drying adsorption to remove sulphur compounds, mercaptan, etc.

Quench Section

To avoid subsequent reaction, the effluent is suddenly quenched initially by indirect

contact with water to 400 – 450oC in a transfer line exchanger or quench boiler. This
is a large heat exchanger that is a bundle of metal tubes through which the gases
pass and around which is circulated water under pressure. The hot water produced is
used to generate steam for use in the plant. In the next step the quench is done by
heavy products of pyrolysis.
Cold Section

After compression, caustic scrubbing is done and the dried, light effluents enter the
cold section of the unit which performs the separation of:
(I) hydrogen to various concentration
(II) ethylene containing 99.4%
(III) 95% propylene
(IV) A C4 fraction containing 25-50% butadiene
(V) Pyrolysis gasoline which is rich in aromatic hydrocarbons. The complexity of
the separation section of a cracker increases markedly as the feed changes
from ethane.

De-methaniser Methane condensed at top – 1000C, 32 Pa

De-ethaniser Separation of C2 fraction (Ethane and ethylene)

Catalyst : Palladium or Nickel
40-80oC, 3 kPa

Separation of Ethylene Ethylene is fractionated and unreacted ethane recycled

De-propaniser C3+ fraction from bottom of de-ethaniser is fractionated.

C3 cut from top of de-propaniser is selectively
hydrogenated to remove methyl acetylene and
propandiene.
Propylene content 95%.
Removal of propane Separation in supplementary column for more pure
from propylene propylene.

Debutaniser Separation of C4 stream from C5+ stream

REACTIONS IN STEAM CRACKING

The reactions involved in thermal cracking of hydrocarbons are quite complex and
involve many radical steps. The thermal cracking reaction proceeds via a free radical
mechanism. Two types of reactions are involved in the thermal cracking:
(i) primary cracking where the initial formation of paraffin and olefin takes place
(ii) secondary cracking reaction where light products rich in olefins are formed.
The total cracking reactions can be grouped as follows:
 Initiation reaction.  Isomerization reaction.
 Propagation reaction.  Termination reaction.
 Addition reaction.  Molecular cyclization reaction
 OPERATING VARIABLES OF STEAM CRACKING
The main operating variables in the pyrolysis of hydrocarbon are composition of feed
stock, reaction temperature, residence time, hydrocarbon partial pressure and
severity.

Composition of Feed Stock

Naphtha are mixture of alkane, cycloalkanes, and aromatic hydrocarbons depending

on the type of oil from which the naphtha was derived. The group properties of these
components greatly influence the yield pattern of the pyrolysis products. A full range
naphtha boiling range approximately 20 to 200oC would contain compound, with
from 4-12 carbon atoms. Short naphtha boiling point range from 100-140oC and long
chain naphtha boiling point lies around 200-220oC. The steam cracking of the
naphtha yields wide variety of products, ranging from hydrogen to highly aromatic
heavy liquid fractions. The thermal stability of hydrocarbons increases in the
following order: paraffins, naphthenes, aromatics. Yield of ethylene as well as that of
propylene is higher if the naphtha feed stock is rich in paraffins. It may be seen that
relative production of ethylene decreases as the feed stock becomes heavier.

Furnace Run Length

Furnace run length can be calculated from the equation:

Run length = ;
∆ /
where Tmd = maximum allowable tube skin temperature,
∆Tm /day= Average rise in tube skin temperature per day,
Tmc = maximum metal skin temperature in the clean, uncoked condition.

For any feedstock the heater section run length depends on the pyrolysis coil
selectivity, cracking severity and transfer line exchanger design. Run length varied
between 21 - 60 days for gas based furnaces and 21-40 days for liquid feed based
furnace.

Pyrolysis temperature and Residence Time

The effluent exit temperature is generally considered a significant indicator of the

operation of a furnace. As the furnace exit temperature rises, the yield also rises.
With respect of ethylene yield, each furnace exit temperature, correspond to an
optimum. The highest ethylene are achieved by operating at high severely, namely,
around 850oC with residence time ranging from 0.2 to 0.4s However, operating at
high temperature results in high coke formation.
Partial Pressure of Hydrocarbon and Steam to Naphtha Ratio

Decrease into the partial pressure of hydrocarbons by dilution with steam, reduces
the overall rate reaction rate, but also help to enhance the selectivity of pyrolysis
substantially in favour of the light olefins desired. Other role of steam during
pyrolysis is
 to increase the temperature of feed stock
 reduction in the quantity of heat to be furnished per linear meter of tube in
the reaction section
 to remove partially coke deposits in furnace tubes.
The ethylene yield decreases as the partial pressure of hydrocarbon increases. For
economic reason a value of 0.5 to 0.64 of steam per tonne of naphtha is generally
adopted as the upper limit.

Severity and Selectivity Concept

Severity is often used to describe the depth of cracking or extent of conversion. In

the case of steam cracking of naphtha, it is convenient to express the severity of the
operating conditions in terms of feed conversion. The ratio of ethylene yield
increases with severity, which hence favors the formation of ethylene. At very high
severities, the ethylene yield level off. Modern ethylene plants are normally designed
for near maximum cracking severity because of economic considerations.

TRENDS IN TECHNOLOGICAL DEVELOPMENTS OF STEAM CRACKERS FOR

PRODUCTION OF ETHYLENE

From the late 1960s through the 1970, the petrochemical industry built a generation
of new steam crackers with an ethylene capacity of several million tonnes capacity.
Older plant consists of typically 10-17 small furnaces with radiant coils having
residence time 0.4-0.6 sec, thermal efficiency below 90%, central waste heat
recovery system and nitrogen oxide (NOX) emissions 75-100 ppm. Present day olefin
plants have capacity more than 1,000,000 tonnes per year ethylene produced with 5-
7 modern cracking furnaces using twin-cell designs. Short residence time and radiant
coil smaller diameters increase yields. The higher selectivity of modern coils reduces
specific energy consumption. The modern olefin plants have better ethylene
selectivity and improved health, safety and environment standards by incorporating
current emission and safety standards.
 PVC PRODUCTION FROM ETHYLENE
 Chlorine, which is found in salt extracted from sea water, gains an additional
electron during the process of electrolysis. By sending a strong current of
electricity through salt water solution – strong enough to change its molecular
structure – chlorine is separated, then extracted from the mixture.
 When ethylene and chlorine are reacted, ethylene dichloride (EDC) is created. This
passes through another thermal cracking process, which produces vinyl chloride
monomer (VCM).
 VCM is sent through a catalyst-containing reactor where polymerization occurs. In
lay terms – chemicals cause the VCM molecules to react until they link together.
 The linking of VCM molecules creates PVC resin – which is where all vinyl
compounds begin.

Process flow diagram for PVC production

 Questionnaire:
1. What are the top 10 ethene production plants in the world?
2. If heavier feedstock is used, will we require more steam?
3. What are the energy requirements for other olefins?
4. What is the temperature and pressure of the steam used in the process?
5. What type of heat exchanger is used in order to utilize excess heat from reactor?
6. Which type of boiler is used to produce BFW? Fire tube or Water tube boiler?
7. What is the acceptable limit of Sulphur components in the products?
8. Is the primary fractionation column in the form of packing materials or in the form
of trays? How many trays are used if so?
9. What are the design parameters of the ethylene furnace where pyrolysis takes
place? What are the measures that can be taken to improve efficiency?
10. High thermal efficiency furnace design can contribute greatly to overall plant
utility costs. How can efficiency be optimized while keeping costs to a bare
minimum?
11.What are the decoking measures that need be employed to overcome coke
deposition while pyrolysis in the tubular reactor?
12.How does coke deposition affect the overall heat transfer coefficient?
13.What parameters does the coke formation mainly depend on?
14.What are the principle differences between mechanical decoking and steam air
decoking?
15.Does frequent decoking have any effect on plant operation? How often should it
be carried out?
16.What is the phase of the catalyst used in the de-ethaniser?

References:
https://nptel.ac.in/courses/103107082/module7/lecture2/lecture2.pdf
https://en.wikipedia.org/wiki/Cracking_(chemistry)
www.essentialchemicalindustry.org/.../cracking-isomerisation-and-reforming.html
https://pubs.acs.org/doi/abs/10.1021/ed054p154?journalCode=jceda8