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Ethyl Benzene Plant Design
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This document provides a report on the design of an ethyl benzene plant. The plant uses liquid
phase alkylation of benzene and ethylene over a zeolite acid catalyst to produce ethyl benzene.
The separation system consists of a flash drum and three distillation columns to separate ethane,
benzene, ethyl benzene, and diethyl benzene. The design variables of benzene to ethylene ratio,
benzene split to transalkylator, and transalkylator temperature were optimized. The optimal
design produces 84086 tonnes of ethyl benzene annually for a capital cost of $2.5 million and
annual profit of $17.02 million.
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258083088 Ethyl Benzene Plant Design

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SaveSave 258083088 Ethyl Benzene Plant Design For Later

Ethyl Benzene Plant DesignProject ReportDuration:12th Aug, 2014 - 12th Nov, 2014Department
of Chemical EngineeringIIT KanpurSubmitted by :Rohit Kakkar|Salman Ahmad Khan|Shivang
SharmaRohan Bishnoi|Himanshu Bareja|Nikhil KumarUmang Arora1|Page

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Table of Contents1. Acknowledgement¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼32.

Executive Summary¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼..43.
Introduction¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼...43.1 General Philosophy
behind design of chemical processes¼¼¼¼¼¼¼¼¼¼¼.43.2 Introduction to Ethyl
Benzene¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼63.3 Ethyl Benzene Reaction
System¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼.63.4 Reaction
Kinetics¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼73.5 Commercial methods for
production of Ethyl Benzene¼¼¼¼¼¼¼¼¼¼¼¼..84. Process
Simulation¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼94.1 Fluid Property
Package¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼...94.2 Process
Description¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼114.3 Process flow
diagram¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼.124.4 Degrees of
freedom¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼134.5
Optimization¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼...134.6 Idea for heat
integration¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼. 174.7 Complex Column
Configuration¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼174.8 Control
Structure¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼214.9 Controller
Performance¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼..245.
Economics¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼275.1 Size of the Heat
Exchangers¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼...275.2 Size, Capital Costs and Operating
Cost of the equipments¼¼¼¼¼¼¼¼¼¼¼285.3 Objective
function(J)¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼..296.
References¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼¼292|Page

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AcknowledgementWe are highly indebted to Prof. Nitin Kaistha for making us learnsimulations
and then challenging us by giving an open ended designproject which truly tested our skills,
patience, team work andcommitment towards a particular task. We would also like to thank
Sirand Mr. Vivek Kumar for their guidance and supervision during theentire period of
project.We are really grateful to all the Teaching Assistants and Lab staff whodirectly or
indirectly helped us in completion of our project since itwould not have been possible without
their strong support and cooperation.3|Page

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2 Executive SummaryAn ethyl benzene plant was designed using the liquid phase alkylation of
benzene with ethyleneover zeolite acid catalyst. Fresh ethylene was assumed to have 5% ethane
impurity while freshbenzene had 0.01% toluene impurity. Alkylation reactions, which led to the
formation of ethylbenzene and a side product diethyl benzene and transalkylation reaction in
which diethylbenzene with benzene formed ethyl benzene, were all carried out in the packed bed
reactors. Tolimit the formation of side products, alkylator was run at high benzene to ethylene
ratio.The separation system consisted of a flash drum and 3 distillation columns. Vapor stream
fromthe flash drum was separated into ethane from the vent and benzene in the bottoms by
firstdistillation column. This benzene mixed with the liquid stream from the flash drum and
thecombined stream went to second distillation column. Second column separated benzene in
thedistillate and mixture of ethyl benzene and diethyl benzene at the bottoms. A part of
benzenefrom distillate was recycled to the alkylator and rest of it was sent to transalkylator.
Thirdcolumn took bottoms of the second column as feed and gave ethyl benzene in the distillate
anddiethyl benzene in the bottoms which was recycled to the transalkylator.The dominant design
variables were benzene to ethylene excess ratio, split ratio of benzene sentto the transalkylator
and temperature of transalkylator. Each of them were varied with theobjective function (J) which
determined the annual profit of the plant. We mostly obtained bellshaped curves and the values
of variables at which the J got maximized were used in the finalflowsheet.The plant capacity is
84086.64 tonnes of ethyl benzene per annum. The overall capital cost of theplant came out to be
$2.5 million and it consumed yearly raw materials worth $67.2 million andyearly energy of
$4.63 million. The revenue from the plant was calculated to be$89.74 millionper annum and the
annual profit was $17.02 million.3 Introduction3.1 General philosophy behind design of
chemical processes[1]The chemical process industry is mainly involved in manufacturing of
wide rangeof productswhich improves the quality of life of humankind and generates
employment. Chemical engineersdeal with a lot of obstacles while designing a process especially
when substances involved havehigh chemical reactivity, high toxicity, and high corrosivity
operating at highpressures andtemperatures.4|Page

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Designing of the plant involves a thorough understanding of the reactions taking place in
theprocess with the major emphasis on reaction kinetics. Most of the time before starting
thesimulation goes in testing the reaction kinetics and choosing a relevant thermodynamic
packagewhich satisfies the experimental vapor liquid equilibrium data and enthalpy data of
components.Douglas[2,3] has proposed a hierarchical approach to the conceptual design in
which designprocess follows a series of decisions and steps. The decisions are listed as
follows:1.2.3.4.5.Decide whether the process will be batch or continuous.Identify the
input/output structure of the process.Identify and define the recycle structure of the
process.Identify and design the general structure of the separation system.Identify and design the
heat-exchanger network or process energy recovery system.High efficiency of usage of raw
material is a requirement of the majority of chemical processes.The extent of recycling of the
unused reactants depends on the ease with which they can beseparated from the products and the
single pass conversion of the reactors. We can recycle theunreacted raw materials in three
ways:1. Separate and purify unreacted feed material from products and then recycle.2. Recycle
feed and product together and use a purge stream.3. Recycle feed and product together and do
not use a purge stream.Specifications of streams and process conditions are influenced by
physical processes as well aseconomic conditions. The conditions used in the process generally
represents a trade-off betweenprocess performance and capital and operating cost of the
equipment. Final selection of theoperating conditions should be made only after the economic
analysis of the process.On operating at higher pressure (>10 bar), we would be needing thicker
walled more expensiveequipment while at pressure lower than ambient tends to make equipment
large and may requirespecial construction techniques to prevent inward flow of outside
impurities, thus increasing thecost of equipment.Several critical temperature limits apply to the
chemical processes. At higher temperatures, thereis a significant drop in the physical strength of
the common construction materials (primarilycarbon steel) and it must be replaced by a costly
material. There should be a rational explanationfor selecting particular operating conditions
which should be supported by economic analysis.Most of the commercial reactions involve
catalysts and the competence of a company is often the

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result of a unique catalyst they use.Choosing the best physical method is an extremely important
part of any simulation. Wrongproperty package will lead to incorrect simulation results which
could not be trusted. Everything5|Page

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ranging from volumetric flow rates to energy balances to separation in the equilibrium stageunits
depends on correct thermodynamic data.In general, seven steps are involved in simulating any
chemical process in a software. They areselection of chemical components, thermodynamic
models, process topology, feed streamproperties, equipment parameters, output options and
convergence criteria.For optimizing a problem, we look for decision variables, objective
function, constraints, globaloptimum and minimum optimum.3.2 Introduction to Ethyl
BenzeneEthyl Benzene (EB), compound with a chemical formula of C6H5CH2CH3 is used as
anintermediate in the making of styrene[4]. Styrene is a building block in the manufacturing
ofpolystyrene which is used for producing disposable plastic cutlery and dinnerware, CD
ªjewelºcases, smoke detector housings and so on. EB and styrene units are generally installed
togetherin order to facilitate the energy economy by integrating energy flows of the
two units.Ethyl Benzene is mainly manufactured via liquid phase alkylation or a gas
phasealkylation ofbenzene. The traditional method used in industries is the liquid phase
alkylation of benzene withethylene over AlCl3 as the catalyst. It has been observed that in case
of liquid phase alkylation,temperature is lower while selectivity of ethyl benzene and pressure
required is higher comparedto gas phase alkylation.[5]A major difficulty faced during
manufacturing of EB is that ethyl benzene is more reactivecompared to benzene with respect to
ethylene due to lower activation energy andthus it leads tothe formation of diethyl benzenes
(DEBs). To limit the formation of DEBs and other polyethylbenzene (PEBs) we use a large
excess ratio of Benzene to Ethylene in the feed to the alkylationreactor. However, large excess
ratio leads to higher equipment, separation and recycle cost.3.3 Ethyl Benzene Reaction
SystemEthyl Benzene is produced by reacting benzene with ethylene in liquid phase over AlCl 3
as thecatalyst. Ethylene contains impurities of ethane while benzene contains slight impurities
oftoluene. Ethane does not participate in the reaction while toluene reacts with ethylene to
formethyl benzene and propylene but we are assuming only 0.01% toluene in the freshbenzene
andthus the amount of EB produced using toluene has been considered negligible.Ethylene on
reacting with benzene forms ethyl benzene and ethyl benzene on reacting furtherwith ethylene
forms diethyl benzene. Diethyl benzene again on reacting with ethylene formstriethyl benzene.
The activation energy for the reaction between ethyl benzene and ethylene islower than the
activation energy of ethylene reacting with benzene and thus if reaction is allowed

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to proceed without any restriction, we will get more diethyl benzene than ethylbenzene. Diethyl6|
Page

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benzene is an undesirable product because most of the ethyl benzene is used in the making
ofstyrene and for styrene process, fresh ethyl benzene should have less than 2ppmdiethyl
benzene.So to limit the formation of diethyl benzene and other polyethyl benzenes, we use a high
benzeneto ethylene ratio in the alkylation reactor. The reactions that take place in the entire
process areas follows:C6H6+ C2H4®BenzeneEthyleneC6H6Benzene+
2C2H4®Ethylene¼¼¼¼¼¼¼¼.1C6H4 (C2H5)2Diethyl
Benzene.....¼¼¼¼¼¼¼.2C2H4Ethylene®C6H4 (C2H5)2DEB¼¼.¼¼¼¼¼¼.3+ C6H5
(C2H5)2DEB®2
C6H5C2H5EB¼¼..........................4C6H5C2H5EBC6H6BenzeneC6H5C2H5EB+2
C6H5C2H5EB

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®C6H6+BenzeneC6H4 (C2H5)2DEB......¼¼¼¼¼¼¼5Reactions 4 and 5 is basically an

equilibrium reaction and is called trans-alkylation reaction.Reactions 1, 2 and 3 occur in
alkylation reactor while 4 and 5 occur in transalkylation reactorboth of which are packed bed
reactors. Catalysts used for the alkylation reactions are differentfrom that of the transalkylation
reaction and so we can safely ensure that first three reactionsoccur in alkylator while 4 and 5
occur in transalkylator.3.4 Reaction Kinetics[6,7]Chemical kinetics is the study of rate of
chemical processes. It is one of the most fundamentalthing that is researched out before
designing a process. Getting relevant kinetics is considered asone of the major success for
designing a process.During the course of our project, we faced a lot of hardships in finding
kinetics for ethyl benzeneprocess. Some papers considered transalkylation as an equilibrium
reaction while some did not,value of A(Arrhenius constant) in different papers were of different
order of magnitudes, and theone we chose finally also doesn't gives us practical results. The
kinetics used is as follows:r1 = 0.084*exp(-9502/RT)CE1.0CB0.32r2 =
0.603*exp(-15396/RT)CE1.3CB0.337|Page

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r3 = 0.00085*exp(-20643/RT)CE1.77CEB0.35For reaction 4 and 5, we regressed data for CBZ0
and CDEB0 and initial rates and obtained rateconstant of the forward reaction. Alternatively,
chemical equilibrium constant for 4th reaction is:K = XBXDEB/XEB2At 571.15 K, K is 0.883.
At ordinary temperature T, K can be obtained the relationship

1 11ln ()=(
-)

571.15



571.15Using the equilibrium constant and forward rate constant, we found out the backward
rateconstant. From the above kinetics, we were able to do the reaction with 100%
ethyleneconversion even at 60° C but the literature, encyclopaedias and actual plant datatells us
that thetemperature should be in the range of 200° C

300°C for 100% ethylene conversion. Thus weobtained a wide deviation from the experimental
data which proved our kinetics to be incorrect.3.5 Commercial Methods for Production of Ethyl
Benzene[7]There are primarily two sources to produce ethylbenzene. The major being alkylation
of benzeneand other being superfractionation of C8 aromatic streams. The alkylation of benzene
is furthercarried out commercially bya) liquid phase alkylationb) gas phase alkyllationLIQUID
PHASE ALKYLATION:Alkylation of benzene in liquid phase using aluminium chloride as
catalyst is the most usedmethod for ethylbenzene production. Different companies like shell,
union carbide, Dowchemicals use this methodThe reaction is exothermic in nature (∆H

114 kJ/mol), kinetically fast and produce good yieldsof ethylbezene. Generally hydrogen
chloride or ethyl chloride is used as a catalyst promoterwhich decreases the amount of
aluminium chloride needed. Instead of AlCl3 lewisacidscatalysts, BF3,FeCl3, AlBr3 are also
used.VAPOR

PHASE ALKYLATION:Earlier vapor phase alkylation were not able to compete with liquid
phase alkylation. Thealkylation process using boron trifluoride as catalyst had little success and
suffered drawbackslike high maintenance costs caused by corrosion from small amount of
water.8|Page
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However the Mobil Badger process is the most modern and successful vapor phase process
forproduction of ethylbenzene. The process uses ZSM

5 synthetic zeolite catalyst.Zeolites were used earlier for alkylation process but they deactivated
quickly because of cokeformation and low catalytic activity. The catalyst used by Mobil had
larger resistance to cokeformation and high catalytic activity for transalkylation and
alkylation.Liquid phase alkylation of benzene with ethylene over zeolite acid catalyst hasbeen
used in ourproject.4 Process Simulation4.1 Fluid Property PackageVapor liquid equilibrium data
of Benzene and Ethyl Benzene for SRK, Peng Robinson, LeeKesler and UNIFAC was obtained
in Aspen Plus. Then it was compared with the data obtainedfrom Dechema, Volume 7 which
basically represents the experimental data. Following resultswere obtained :Table 4.1.: Root
Mean Square difference between the values obtained from 2 dataPackageSRKPeng
RobinsonUNIFACLee KeslerRoot Mean Square Difference.0377.0392.0387.03949|Page
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(a)(b)(c)10 | P a g e

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(d)Figure 4.1.1 : Blue line represents Y and red line reprsents X of experimental data from
Dechema whileGreen line represents Y and Purple line represents X of Aspen Plus data. 1(a)
Plot for UNIFAC, 1(b) Plotfor Lee Kesler method, 1(c) Plot for SRK, 1(d) Plot for Peng
Robinson4.2 Process DescriptionStream containing mostly ethylene with an impurity of ethane
(~5%) and stream having benzenewith a slight toluene impurity (~0.01%) were used as fresh
feeds. Fresh feed containing ethylenewas passed through compressor to raise the pressure to 50
bars since it was in the gas phasewhile fresh benzene was passed through a pump which raised
its pressure to 50 bar. Both thesefresh feeds passed through a valve which reduced their pressure
to around 40 bars. Pump andcompressor were supplied with the required amount of
electricity.Fresh benzene mixed with recycle benzene and the combined stream along with fresh
ethylenewith some ethane was used as the feed to the alkylation reactor. The feed passed through
a heaterwhich was used for controlling the temperature before sending to the reactor.Output of
the alkylator reactor mixed that of the transalkylator and the combined stream passedthrough a
cooler followed by a valve to reduce pressure to 1 atm. This stream entered theseparator which
was used to separate liquid and vapor components of the inlet stream. It wasused because ethane
in the vapor phase made the separation difficult and if theinlet stream wasdirectly send for the
distillation, then it would have significantly enhanced the reboiler duty ofthe column.11 | P a g e
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