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Lecture - 11 - Gas Processing and Polymerization

The document provides an overview of gas processing and polymerization processes in a petroleum refinery. It discusses how light gas streams are produced from various refinery units and classified. Key gas processing units discussed include absorption using naphtha and kerosene to separate ethane and methane. Olefin polymerization is described as producing polymer gasoline to increase octane number, though quality is lower than alkylation products. The polymerization reaction mechanism and operating conditions and an olefin polymerization process flowsheet are presented.

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57 views

Lecture - 11 - Gas Processing and Polymerization

The document provides an overview of gas processing and polymerization processes in a petroleum refinery. It discusses how light gas streams are produced from various refinery units and classified. Key gas processing units discussed include absorption using naphtha and kerosene to separate ethane and methane. Olefin polymerization is described as producing polymer gasoline to increase octane number, though quality is lower than alkylation products. The polymerization reaction mechanism and operating conditions and an olefin polymerization process flowsheet are presented.

Uploaded by

rin karin
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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NPTEL – Chemical – Chemical Technology II

Lecture 11: Gas Processing and Polymerization


11.1 Introduction
- In this lecture, we present an overview of light end processing followed with
gas processing and polymerization processes in the refinery
- Gas fraction is produced from various units. Some of them are
o Crude distillation unit
o Catalytic cracking unit
o Catalytic reforming unit
o Hydrocracking unit
o Coking unit
- The light end streams are classified as
o Streams rich in Butane: Sold as calor gas or LPG. Used internally for
blending and alkylation units (isobutane only)
o Streams rich in Propane
o Light ends rich in olefins.
- We have already studied alkylation and isomerisation as important gas
processing operations. Now we will study the additional units namely gas
processing and polymerization units.

11.2 Gas processing technology ( Figure 11.1)

Figure 11.1 Gas Processing Technology

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NPTEL – Chemical – Chemical Technology II

- The objective of gas processing is to produce ethane and methane.


- The produced ethane and methane is to serve later for fuel gas or hydrogen
production
- The gas processing section consists mainly of two different sections
- Absorption using Naphtha and kerosene:
o First, collected gases are compressed to be fed to an absorption.
o The purpose of naphtha is to absorb heavier hydrocarbons in the gas
fraction. These are C3s and C4s in the feed stream. To carry out
absorption, first the gases are cooled and fed to a phase separator to
facilitate early separation of lighter and heavier fractions.
o From the phase separator two streams emanate namely a gas stream
and a liquid stream.
o The gas stream is fed to an absorber unit where naphtha is used as a
solvent to absorb the left heavier hydrocarbons in the gas.
o The naphtha rich with hydrocarbons is fed to the phase separator so as
to stabilize the naphtha stream.
o The gas from the absorber is fed to a second absorber where lean oil
(such as kerosene) is used as a solvent to absorb any heavier
hydrocarbons other than the methane and hydrogen. Eventually, fuel
gas is produced as the gas product from this absorption. The other
product from the absorber is the rich oil stream
- Naphtha rich stream processing:
o The liquid product from the phase separator is fed to a deethanizer
which generates ethane rich stream as the top product. This stream is
recycled back to the gas processing unit i.e., mixing with the feed and
subjected to cooling followed by phase separator.
o The bottom product from deethanizer is naphtha rich stream with
butanes and propanes.
o This stream is subjected to fractionation using debutanizer,
depropanizer and deisobutanizer to obtain propane, isobutane and
naphtha. The stabilized naphtha can be used for absorption purposes.

11.3 Olefin Polymerization


- Olefin polymerization to yield polymer gasoline is primarily carried out to
obtain polymers with good octane numbers.
- The octane number of the polymer gasoline product is not greater than the
octane number of the products produced from reforming and alkylation.
Instead, comparatively poor quality product is obtained. But for the sake of
enhancing octane number polymerization is carried out.

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NPTEL – Chemical – Chemical Technology II

- On the other hand, polymer gasoline has more vapour pressure than the
corresponding alkylation products. Therefore, in both ways, polymer
gasoline product quality is lower than that obtained from the alkylation unit.
- Typical feedstocks for polymerization process are C3 and C4 olefins that are
obtained from catalytic cracking
- The end product from polymerization reactor is a dimer or a trimer of the
olefins.

11.4 Reaction mechanism&Operating conditions


Reaction mechanism comprises of four basic steps

- Carbonium ion formation (Step 1): Here, olefin reacts with acid catalyst to
yield carbonium ion.
- Additon reaction (Step 2): Carbonium ion reacts with olefin to generate
intermediate carbonium ion
- Regeneration (Step 3): The intermediate carbonium ion converts to the dimer
and generates back the proton on the catalyst surface
- Isomerization (Step 4): Straight chain proton substituted olefins convert to
isomeric carbonium ions.
- Catalysts used: Acid catalysts (H2SO4) are used.
- Temperature: 150 – 220 oC are used. Too high temperatures give tar deposits.
- Pressure: 25 – 100 atms

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NPTEL – Chemical – Chemical Technology II

11.5 Olefin polymerization process technology (Figure 11.2 )

Figure 11.2 Flow sheet of Olefin Polymerization Technology


- Caustic wash: C3-C4 olefin feed subjected to caustic wash to remove H2S and
other sulphur compounds (such as mercaptans). These tend to poison the
catalyst.
- Water scrubbing: Eventually water scrubbing is carried out to remove
dissolved impurities and generate waste water.
- Polymerization reactor: The reaction mixture is heated, compressed and fed
to a polymerization reactor. The reactor design is a shell and tube type design
where catalyst is placed in the tube for the reaction to take place and cooling
water is circulated in the shell side to control the temperature increase due to
the exothermic reaction.
- Fractionation: Subsequently, the reactor product is fed to a depropanizer and
debutanizer to produce propanes, butanes and polymer gasoline. The
polymeric product is further stabilization using hydrogenation stabilizer which
converts any freely available double bonds to single bonds. The end product is
polymer gasoline
- The propane produced is partially recycled to the reactor and the other part
taken out as a product.

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NPTEL – Chemical – Chemical Technology II

11.6 Technical questions


1. Why is the deethanizer top product recycled to the cooler followed with
phase separator?

Ans: The deethanizer top product consists of ethane rich stream but not a
pure product. Therefore, instead of further distillation of the fraction, it is
sent to the phase separator. This means that ethane is not produced as a
product here. This is also practised in the refinery. Also, there are refineries
that produce ethane as a product. It all depends on the subsequent operation
that the refinery plans with the ethane generated.

2. Why the sequence is followed to remove ethane, propane, butane and


isobutene?

Ans: This is an important question that one should understand. From a


mixture of ethane, propane, butane and isobutane in naphtha, the easiest to
separate is ethane followed with propane, butane and isobutane. Therefore,
isobutane separation is the toughest.

3. Why is naphtha rich with heavier hydrocarbons sent to the phase


separator?

Ans: The naphtha stream rich with heavier hydrocarbons is not a stream that
consists of only heavier hydrocarbons. It also consists of lighter
hydrocarbons. This is the problem we face always in chemical industry.
Textbooks always enable a student to understand two component
absorption, but in the real world we deal with multicomponent systems.
The basic problem in multicomponent process is that we cannot dictate the
absorption of a particular component only. For instance, when we absorb a
mixture of NH3 and CO2, we see that both NH3 and CO2 get absorbed. We
cannot dictate to the process to say that only NH3 gets absorbed. Therefore,
since it is possible that naphtha could absorb lighter hydrocarbons also due
to the existing absorption factors for various components. Henceforth, it is
important to note that naphtha rich with hydrocarbons needs to be stabilized.
This stabilization requires either stripping or any other operation. By
bringing in stripping, we are complicating of using another distillation unit
and once again energy requirements for that column. Instead of that, simply
the naphtha is fed to the phase separator to enable the stabilization of
naphtha in the phase separator itself.

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NPTEL – Chemical – Chemical Technology II

4. What modification you can think in the polymerization reactor process


instead of using a shell and tube design?

Ans: Well, this is an important question. If we analyze the shell and tube
design, we want to achieve simultaneous cooling of the olefin stream in the
tube. Instead of cooling, we can also try cold shot technique or diluent in
the stream. When diluents is used, then the diluents or inert carrier needs to
be separated and its an additional task in the process. Therefore, the best
possibility is to target either a cold shot feed or a cold shot product with
recycle. Since conversions are low, doing cold shot with feed is not
beneficial. Therefore, cold shot product will be the optimal arrangement to
replace the shell and tube design. In that case, the product should be cooled
and send back to the reactor.

5. Can optionally propane be fed to the polymerization reactor?

Ans: Few process flowsheets involve propane as well fed to the


polymerization reactor, but conversions are expected to significantly low for
propane. Therefore, as such much gain will not be there by feeding propane
to the polymerization reactor.

References :
Gary J.H., Handwerk G.E., Petroleum Refining: Technology and
Economics, Taylor & Francis, 2005
Jones D.S.J., Elements of Petroleum Processing, John Wiley & Sons, 1995
Ullmann F., Encyclopedia of Industrial Chemistry, Wiley – VCH, 1999-
2012
Kirk R. E., Othmer D. F., Encyclopedia of Chemical Technology, John
Wiley and Sons, 1999-2012

Joint initiative of IITs and IISc – Funded by MHRD Page 78 of 83

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