Assignment 1
Assignment 1
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.
Quench 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.
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.
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.
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.
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