Professional Documents
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Historical Profile
1. Historical Profile
Ethyl benzene is an organic chemical compound which is an aromatic hydrocarbon (HC). Its major use is in the
petrochemical industry as an intermediate compound for the production of styrene, which in turn is used for making
polystyrene, a commonly used plastic material. Although often present in small amounts in crude oil, ethyl benzene
is produced in bulk quantities by combining the petrochemicals benzene and ethylene in an acid-catalyzed chemical
reaction. Catalytic hydrogenation of the ethyl benzene then gives hydrogen gas and styrene, which is vinyl benzene.
Ethyl benzene is also an ingredient in some paints.
Ethyl Benzene is used almost exclusively as intermediate in the production of styrene monomer. It is produced by
liquid phase alkylation’s or vapor phase alkylation’s of benzene with ethylene. Commercial production started in the
1930s and has grown to over 23 million metric annually (MTA)
The alkylation of HC with olefins in the presence of AlCl3 catalyst was first practiced by M.Balsohn in 1879.
However, Charles Friedel & James M. Crafts pioneered much of early research on alkylation & AlCl3 catalyst .Over
a century later, the process that employ the classic Friedel-Crafts reaction chemistry remain a dominant source of
EB. Ethyl benzene was first produced on a commercial scale in the 1930s by Dow Chemical in US and by BASF in
the Federal Republic of Germany.
Until 1980s , almost all ethyl benzene was manufactured with an aluminium chloride catalyst using a Fridal Crafts
reaction mechanism . A few EB production units employed a different Fridal-Crafts catalyst , boron trifluriede.
Small amount of EB also recovered as a by product from mixed xylenes streams using a very intensive distillation
process. In 1980s ,the first commercial facility using a zeolite based process and the absence of maintenance nad
environmental problems associated with the Fridal-Creafts catalyst havre allowed zeolite catalyst and to completely
displace the order catalyst in all modern production facilities.
The4first zeolite process was based on vapor –phase reactor at temp. of over 4000C. In this temperature rang,
reaction such as isomerisation/cracking and hydrogen transfer produce a number of by products that contaminates
the EB product.
Efforts were made to reduce by-product formation by changing reaction condition , but it as not until the advent of
liquid phase processes operating at temperatures lower than 2700C that zeolite –catalysed processes were truly
capable of producing high purity EB . The first high purity zeolite based on technology developed by UOP and ABB
Lummus Global , started up in the 1990.
The Ethyl benzene- Styrene industry remained relatively insignificant until World War 2. The tremendous demand
for synthetic SBR during world war prompted accelerated technology improvements and tremendous capacity
expansion. This enormous wartime effort led to the construction of several large scale factories, turning styrene
production quickly in to a giant industry. In 1965, 10% of EB production was from super fraction of mixed xylene
streams produced by catalytic reforming of naphtha. In 1986, the world annual production capacity was 14*106 t.
EB was first produced on a commercial scale in the 1930s by Dow Chemical in US and by BASF in the Federal
Republic of Germany.
2
1.3 Natural Occurrences:
Ethyl benzene is a colorless, flammable liquid that smells like gasoline. It is naturally found in coal tar and
petroleum and is also found in manufactured products such as inks, pesticides, and paints.
3
Chapter 2
Applications
4
2. Applications
All commercial EB production is captive consumed for the manufacture of styrene monomer Styrene is used in the
production of poly styrene and a wide range of other plastics. Of the other minor applications, the most significant in
the paint industry as a solvent.
Even smaller volumes go towards the production of acetophenon, diethyl benzene & ethyl anthraquinon.
The product specification on EB is set to provide a satisfactory feedstock to the associated styrene unit.
Objectionable impurities in the EB can be grouped in to two categories:
a) Haliedes
b) Diethylbenzene
Purity 99.5 wt, % min
Benzene 0.1-0.3 %
Toluene 0.1-0.3%
O-xylene +Cumene 0.02% max
m,p- xylene 0.2% max
5
Manufacturing Capacities:
PRODUCER CAPACITY*
Total 14,130
In India:
6
Chapter 3
Economic Scenario
7
3. Economic Scenario
3.1 Current & Projected Demand:
Growth
Historical (1995 - 2000): 0.7 percent per year.
Strength
EB demand runs parallel to that of styrene, and styrene is a mature and stable commodity, used in many
homopolymer, copolymer and terpolymer applications. These applications cover a wide scope in industrial,
consumer and medical products.
Weakness
EB’s major shortcoming is that it is essentially a one market segment product - styrene. Moreover, as the styrene is
produced with captive EB there is not much noticeable market activity.
PRICE
• Historical (1995 - 2000):
High, $0.25 per pound, bulk, f.o.b. Houston, TX, list
($ 0.5511 / Kg)
Price Variations:
The US unit sales value of EB in $/Kg from 1960 – 1986:
8
3.3 Application wise Consumption Pattern:
Application Consumption ( in % )
Styrene Production 99 %
Before any site selection work begins the company should be organized for expansion planning in a way that
depends on the size of the firm. A company may want to utilize a standing committee, a special project team or
planning by one person. In any event the planning function must be clear cut responsibility of one individual.
The basic aim of the site selector is to choose a location that maximizes income and minimizes cost compromises
usually have to be made. No site is ever perfect, and it is the mission of the site selection team to weigh the
alternatives and compromises on the best choice.
Plant layout:
Plant layout involves developing physical equipment for a processing facility. The development must effect a
balance of equipment spacing and integration of specific systems related to facility as a whole. Some of the factors
to be considered for designing the plant layout are:
1. Process
2. Economics
3. Client requirements
4. Operation
5. Erection and maintenance
6. Safety
7. Environment
8. Appearance
9. Expansion
9
In-line plant layouts are made in various arrangements which often are referred to by letter designation. Various
configurations are formed based on the main artery of the process unit i.e. the pipe rack, which contains long process
and the utility lines that connect distant equipment and product piping entering and leaving the plant. Space for
instrument and electrical feeders is allocated in the pipe rack such that they are connected to the related equipment.
This area is kept free of piping and its related supports.
Generally an I shaped plot is used for small process and an H-shape plot for larger units. In developing the plant
layout for a chemical plant, it is essential that the firm decisions are made early as to equipments arrangement. This
eliminates changes, which cost man-hours as the job progresses through engineering and design. The distillation
sections are based on a grade-level process plant layout configuration. The steam generation and power facilities are
housed in a building. The basic arrangement follows the equipment spacing charts and clearance tables.
Based on all above factors we have selected Bombay High as our plant site due to good availability of raw materials
as well as for better market.
10
Chapter 4
Properties
11
4. Properties
Under ordinary conditions, EB is a clear liquid with a characteristic aromatic odor. EB is an irritant to the skin &
eyes and is ordinary toxic by ingestion and skin adsorption.
Identifiers
CAS Number [100-41-4]
RTECS Number DA0700000
SMILES c1ccccc1CC
Molecular Formula C8H10
Molar Mass 106.167 g/mol
Appearance Colourless liquid
M.P. -94.949 0 c
12
Flammability limit ( Upper) -----
LEL 1.2 %
UEL 6.8 %
Commercially, selectivities to styrene range from 89-96%with per rpass conversion 65-70%
13
.
EB Styrene
Another reaction of commercial importance is the oxidation of EB by air to hydroperoxides C
6H5 CH(OOH)CH3 .
The reaction takes place in the liquid phase , with no catalyst required.
With a suitable catalyst EB can be converted to xylenes. Commercial processes for isomerizing xylenes
usually involve the catalytic isomerization or dealkylation of EB.
EB may be dealkylated catalytically or thermally to benzene.
Emergency Overview:
Clear, colourless liquid with a characteristic, sweet, gasoline-like, aromatic odour. FLAMMABLE LIQUID AND
VAPOUR. Liquid can accumulate static charge by flow, splashing and agitation. Vapour is heavier than air and may
spread long distances. Distant ignition and flashback are possible. Liquid can float on water and may travel to
distant locations and/or spread fire. Closed containers may rupture and explode in heat of fire. TOXIC. May be
harmful if inhaled. Central nervous system depressant. Vapour may cause headache, nausea, dizziness, drowsiness,
confusion, unconsciousness and possibly death. SKIN IRRITANT. May cause skin irritation. Aspiration hazard.
Swallowing or vomiting of the liquid may result in aspiration (breathing) into the lungs. POSSIBLE CANCER
HAZARD - may cause cancer, based on animal information.
Inhalation:
Ethylbenzene readily forms high vapour concentrations and should be considered toxic by this route of exposure.
Inhalation of the vapour or mists can irritate the nose and throat and produce symptoms of central nervous system
depression such as mild unsteadiness, headache, nausea, dizziness and a feeling of drunkenness at approximately
100-200 ppm. Much higher concentrations can cause more severe symptoms including unconsciousness and death.
Human volunteers exposed to 85 ppm for 8 hours reported no adverse health effects. Above 100 ppm, mild
unsteadiness, sleepiness and headache were reported. In another report, approximately 100 ppm (cited as 400
mg/m3) produced a slight irritating effect on the respiratory tract, occasional headaches, sleepiness, slight drowsiness
after 8 hours. More pronounced irritation, frequent headaches, sleepiness and a feeling of drunkenness were
observed at 200 ppm (860 mg/m3). At 1150 ppm (5000 mg/m3), irritation of nose and throat was experienced.
Exposure to 1000-2000 ppm (0.1-0.2%) for 6 minutes caused irritation of the nose and throat, fatigue and increasing
unsteadiness, chest constriction and dizziness in 4-6 male volunteers. Exposure to 5000 ppm (0.5%) was considered
intolerable
Skin Contact:
The liquid can cause moderate irritation, based on animal information. Ethylbenzene is absorbed through the skin to
a small extent, but harmful effects are not expected to occur by this route of exposure.
14
Eye Contact:
The liquid can cause mild to moderate irritation, based on limited animal information. Volunteers reported that
exposure to approximately 100 ppm was slightly irritating to the eyes. At 1000 ppm (0.1%) the vapour was very
irritating to the eyes of 4-6 volunteers, producing smarting and burning, accompanied by profuse tearing. This
irritation, gradually decreased until, after a minute or two, it was barely noticeable. At 2000 ppm (0.2%), the
irritation was almost intolerable upon first exposure, but again became less irritating upon continued exposure, while
5000 ppm (0.5%) was considered intolerable.
Ingestion:
Ethylbenzene has relatively low toxicity following ingestion. As a central nervous system (CNS) depressant, it can
cause nausea, vomiting, headache and dizziness. Very large amounts may cause unconsciousness and death.
Ethylbenzene can cause severe lung damage or death if the liquid is accidentally breathed into the lungs (aspirated),
based on physical properties. There are no reports of aspiration occurring in humans.
Ingestion is not a typical route of occupational exposure.
Nervous System:
A number of human population studies involving painters and other occupational groups exposed to a wide range of
solvents, including ethylbenzene, have led to some investigators to conclude that long-term exposure to solvents
may cause permanent effects on the central nervous system (CNS). The signs and symptoms are ill-defined and
include headaches, memory loss, fatigue and altered emotional reactivity. This syndrome is commonly known as
Organic Solvent Syndrome. There are no specific studies that implicate ethylbenzene as a causal agent, although it is
present in many of the paints and other solvent-containing products. The available studies tend to have a number of
deficiencies including concurrent exposure to many different chemicals, and lack of exposure data.
In a limited study, most workers exposed to up to 11.5 ppm (cited as 0.05 mg/L) complained of headaches,
irritability and of tiring rapidly. Functional nervous system disturbances were found in some workers employed for
over 7 years.
Skin:
Repeated or prolonged contact may cause dry, red, chapped skin (dermatitis).
Skin Sensitization:
No allergic skin reaction was observed among 25 volunteers exposed to 10% ethylbenzene in petrolatum.
Hearing:
Studies in rats have shown that simultaneous exposure to ethyl benzene and noise increases the potential for hearing
damage above that for noise exposure alone. Guinea pigs do not appear to be sensitive to these effects.(54,55) The
relevance of these observations to human exposures is not known.
EB is an flammable liquid.
It is stored & transported in steel containers .
The US DOT identification number is UN 1175 .
Foam, Carbon dioxide , dry chemical , halon & water ( fog pattern) are used in fighting EB fires.
The use of NIOSH approved respirators is recommended at high concentration.
Skin contact should be avoided.
15
Chapter 5
Manufacturing Processes
16
5. Manufacturing Processes:
Currently, the primary source of ethyl benzene is the alkylation of benzene with ethylene. The only other source, the
super fractionation of mixed C8 aromatic streams, supplies only a small portion of the ethyl benzene produced. Two
distinct types of ethyl benzene alkylation processes are currently used commercially: liquid- phase alkylation and
vapor-phase alkylation.
Liquid phase aluminum chloride processes have been the dominant source of ethylbenzene since the 1930s. Several
companies have developed variations of this technology. Processes currently in use include those of Dow chemical,
BASF, shell chemical, Monsanto, societe chimique des cahrbonnages, and union carbide/ badger. The Monsanto
process is currently the most modern commercially licensed aluminum chloride alkylation technology. Alkylation of
benzene with in the presence of an aluminum chloride catalyst complex is exothermic (∆H-114 kJ/mol); the reaction
is very fast and produces almost stoichiometric yields of ethy lbenzene. In addition to AlCl3, a wide range of Lewis
acid catalysts, including AlBr3, FeCl3, and BF3, have been used. Aluminum chloride processes generally use ethyl
chloride or hydrogen chloride as a catalyst promoter. These halide promoters reduce the amount of AlCl3 required.
The reaction mechanism has been studied in detail
Alkylation:
In the conventional AlCl3 process (see Fig 1), three phases are present in the reactor. Aromatic liquid, ethylene gas,
and a liquid catalyst complex phase (a reddish brown material called red oil). A mixture of catalyst complex, dry
benzene, and recycled polyalkyl benzenes is continuously fed to the reactor and agitated to disperse the catalyst
complex phase in the aromatic phase. Ethylene and the catalyst promoter are injected into the reaction mixture
through spargers, and essentially 100% of the ethylene is converted. Low ethylene: Benzene ratios are used to give
optimum overall yield of ethylbenzene. Commercial plants typically operate at ethylene: because molar ratios of
ca.0.3-0.35. As the ratio is increased, more side reactions, such as transalkylation and isomeric rearrangement,
occur. Further alkylation of ethylbenzene leads to the reversible formation of lower molecular mass
polyalkylbenzenes. The loss in net yield due to residue is minimized by recycling this material to the alkylation
reactor. In addition, because the reaction occurs close to thermodynamic equilibrium, the traditional processes use a
single reactor to alkylate benzene and transalkylate polyalkylbenzenes.
The reaction temperature is generally limited to 1300C; a higher temperature rapidly deactivates the catalyst and
favors formation of non aromatics and polyalkyllbenzenes, which are preferential absorbed by the highly acidic
catalyst complex, resulting in byproduct formation. Sufficient pressure is maintained to keep the reactants in the
liquid phase. High –alloy materials of construction are also required for the piping and handling systems. The liquid
reactor effluent is cooled and discharged into a settler, where the heavy catalyst phase is decanted from the organic
liquid phase and recycled. The organic phase is washed with water and caustic to remove dissolved AlCl3 and
promoter. The aqueous phase from these treatment steps in first neutralized and then recovered as a saturated
aluminum chloride solution and wet aluminum hydroxide sludge.
Removal of dissolved catalyst from the catalyst from the organic stream has long been a problem for ethylbenzene
producers. Recently CdF chime found that more complete recovery of AlCl3 could be achieved by first contacting
the organic phase with ammonia instead of sodium hydroxide.
17
Separation: Purification of the ethyl benzene product is usually accomplished in a series of three distillation
columns. The unreacted benzene is recovered by the first columns as an overhead distillate. The second column
separates the ethyl benzene product from the heavier polyalkylated components. The bottoms product of the second
column is fed to a final column, where the recyclable polyalkylbenzenes are stripped from non recyclable high
molecular mass residue compounds. The residue or flux oil, consisting primarily of polycyclic aromatics, is burned
as fuel. Because the alkylation mixture can tolerate only minor amounts of water, the recycled benzene and fresh
benzene must be dried thoroughly prior to entering the reactor. Water not only increases corrosion, but also
decreases catalyst activity. Benzene dehydration is accomplished in a separate column.
The improved Monsanto process has distinct advantages compared to conventional AlCl3 processes. The most
important of these is a significant reduction in the AlCl3 catalyst use, thus lessening the problem of waste catalyst
disposal. Monsanto found that by an increase in temperature and by careful control of ethylene addition, the required
AlCl3 concentration could be reduced to the solubility limit, thereby eliminating the separate catalyst complex
phase.. There fore, alkylation occurs in a single homogeneous liquid phase instead of the two liquid phases is earlier
processes.
Monsanto claims that a separate catalyst complex phase may actually prevent the attainment of maximum reactor
yields. With a few exceptions, the flow scheme of the Monsanto process is nearly the same as that of more
traditional processes. The process is also capable of operating with low- concentration ethylene feed. The process is
also capable of operating with low concentration ethylene feed. Typically, the alkylation temperature is maintained
at 160-1800C. This higher operating temperature enhances catalyst activity, with the additional benefit that the heat
of reaction can be recovered as low- pressure steam. Whereas the traditional process accomplishes alkylation and
transalkylation in a single reactor, the homogenous catalyst system must employ a separate transalkylation reactor.
At lower catalyst concentrations, the recycle of substantial amounts of polyalkylbenzenes terminates the alkylation
reaction. Therefore, only dry benzene, ethylene, and catalyst are fed to the alkylation reactor. The recycle
polyethylbenzene stream is mixed with the alkylation reactor effluent prior to entering the transalkylation reactor.
The transalkylation reactor is operated at much lower temperature than the primary alkylation reactor. After
transalkylation, the reaction products are washed and neutralized to remove residual AlCl3. With the homogenous
process, all of the catalyst remains in solution. The catalyst-free organic reaction mixture is then purified using the
sequence described previously for the conventional AlCl3 process. As with other AlCl3 process, the organic residue
is used as fuel and the aluminum chloride waste streams are usually sold, or sent to treatment facilities.
Vapor-phase alkylation has been practiced since the early 1940s, but at that time processes were unable to compete
with liquid-phase aluminum chloride based technology. The alkar process developed by UOP, based on boron
trifluoride catalyst, had modest success in the 1960s, but fell from favor because of high maintenance costs resulting
from the severe corrosion caused by small quantities of water. Nevertheless, some ethylbenzene units continue to
use this process.
The Mobil –badger ethylbenzene process represents the latest and most successful vapor phase technology to be
introduced. The process was developed in the 1970s around Mobil’s versatile ZSM-5 synthetic zeolite catalyst.
Earlier attempts at using zeolite or molecular sieves for benzene alkylation had suffered from rapid catalyst
deactivation because of coke formation and poor transalkylation capabilities. The Mobil catalyst combines superior
resistance to coke formation with high catalytic activity for both alkylation and transalkylation by American Hoechst
Corp. at their 408x10-3/t/a Bayport, Texas plant. Currently nine commercial plants have been licensed, representing
ca. 3x10106 t/a of production capacity.
18
ALKAR PROCESS:
This process produces a high purity ethylbenzene product and can use dilute ethylene feed stock. If the entry of
water into the process is strictly prevented, the corrosion problems associated with aluminum chloride processors are
avoided. However, even small amounts of water (<1mg/kg) hy6drolze the BF, catalyst. The alkyation reaction takes
place at high pressure (2.5-3.5 Mpa; 25-35 bar) and low temperature (100-1500C). Dehydrated benzene, ethylene,
and make up BF3, catalysts are fed to the reactor. Typically, ethylene; benzene molar ratios between 0.15 and 0.2
are used. The reactor inlet temperature is controlled by recycling a small portion of the reactor effluent.
Transalkylation takes place in a separate reactor. Dry benzene, BF3 catalyst, and recycled polyethlybenzene are fed
to the transalkylation reactor. The effluent streams from the two reactors are combined and passed to a benzene
recovery column, where benzene is separated for recycle to the reactors. Boron trifluoride and light hydrocarbons
are taken over head as a vapor stream from which the BF3, is recovered for recycle. The bottom for the benzene
recovery column is sent to a product column, where ethylbenzene of > 99.9% purity is taken overhead. A final
column serves to recover polyethylebenzenes for recycle to the transalkylation reactor.
The alkar process can operate with ethylene feed containing as low as 8-10 mol% ethylene, enabling a variety of
refinery and coke-oven gas streams to be used. However, purification of these streams is necessary to remove
components that poison the BF3 catalyst, e.g., trace amounts of water sulfur compound, and oxygenates.
Mobil-Badger Process:
The fixed –bed ZSM-5 catalyst promotes the same overall alkylation chemistry as those used in the other processes;
however, the reaction mechanism is different. Ethylene molecules are adsorbed onto the Bronsted acid sites within
the catalyst, which activates the ethylene molecule and allows bonding with benzene molecules to occur. Hence, the
range of higher alkylated aromatic byproducts formed by the Mobil – Badger process is some what different than
that for the Friedel Crafts processes. These components do not affect the ethylbenzene product purity and are
recycled to the reactor for transalkylation or dealkylation.
The Mobil-Badger heterogeneous catalyst system offers several advantages when compared to the other
commercially available processes. The most important are that it is noncorrosive and nonpolluting. The catalyst is
essentially silica – alumina, which is environmentally inert. Because no aqueous waste streams are produced by the
process, the equipment for waste treatment and for catalyst recovery is eliminated. In addition, carbon steel is the
primary material of construction, high-alloy materials and brick linings are not required.
The reactor typically operates at 400-4500C and 2-3 Mpa (20-30 bar). At this temperature >99% of the net process
heat input and exothermic heat of reaction can be recovered as steam. The reaction section includes two parallel
multibed reactors, a fired heater, and heat recovery equipment. The high-activity catalyst allows transalkylation and
alkylation to occur simultaneously in a single reactor. Because the catalyst slowly deactivates as a result of coke
formation and requires periodic regeneration, two reactors are included to allow uninterrupted production: one is on
stream while the other is regenerated. Regeneration takes ca. 36h and is necessary after 6-8 weeks of operation. The
catalyst is less sensitive to water, sulfur, and other poisons than the Lewis acid catalysts.
The reactor effluent passes to the purification section as a hot vapor. This steam is used as the heat source for the
first distillation column, which recovers the bulk of the unreacted benzene for recycle to the reactor. The remaining
benzene is recovered from a second distillation column. The ethybenzene product is taken as the overhead product
from the third column. The bottoms product from this column is sent to the last column, where the recyclable
alkylbenzenes and polyalkylbenzenes are separated from heavy nonrecyclable residue. The low-viscosity residue
stream, consisting mainly of diphenylmethane and diphenylethane, is burned as fuel. The Mobil-Badger process also
19
can use dispute ethylene feedstocks. In semi commercial applications, the process has operated on streams
containing as little as 15 mol% ethylene.
Dow Chemical and Snamprogetti are developing a process for making ethylbenzene/styrene from ethane and
benzene. The process combines the dehydrogenation of ethane and ethylbenzene in one unit and integrates the
processes for preparing ethylene, ethylbenzene and styrene. This process is claimed to have lower costs than the
conventional route to styrene, largely stemming from the low cost of ethane in relation to ethylene. A pilot plant has
been operating since 2002 and commercialisation could be possible by the end of the decade.
Although both the alkylation process i.e. liquid phase & vapor phase are of equal use commercially. Yet there are
some differences:
1. In vapor phase alkylation, the reactors operates at higher temperatures(400—4500 c) which causes
catalytic deactivation by fouling as a result catalyst required periodic regeneration.
2. In vapor phase alkylation process two reactors will be required so that processing and regeneration can
proceed alternatively without interrupting production.
3. All the ethylene feedstock is reacted completely in the liquid benzene, thus eliminating off gas recovery
equipment.
4. Ethyl benzene yield is 99.7% in liquid phase alkylation process while in vapor phse alkylation it is around
98%.
6. Up to 99.95wt% product purity in the with no xylene formation, in liquid phase alkylation process.
HAZARDS IDENTIFICATION
20
Chapter 6
Selected Process
21
6. Selected Process:
We have selected liquid phase alkylation process for ethyl benzene production, now we will discuss process under
the followings:
Introduction to process:
Efforts were made to reduce by-product formation by changing reaction condition but it was not until the advent of
liquid phase at temperature lower than 2700 c that zeolite –catalyzed processes were truly capable of producing. The
first high purity zeolite based EB plant , based on technology developed by UOP & ABB Lummus Global started up
in 1990.
Catalyst: Zeolite
Process Effluents: Inert component of ethylene feed which will appear as benzene column vent.
EB made by the alkylation of benzene with ethylene in the presence of zeolite catalyst. Successive alkylation also
occurs to minor extent, producing diethylbenzens, collectively termed polyethylene benzene (PEB)
22
6.2 Process Description
Benzene alkylated with the ethylene to yield a mixture of alkylated benzenes. This mixture is distilled to recover
product EB, and higher ethylated benzenes (PEB).
The liquid phase alkylation reactor consists of multi[le beds of zeolite catalyst operating adiabatically. Process
conditions are selected to keep the aromatic reaction mixture in the liquid phase. Excess benzene is used, and
ethylene is injected before each bed. Multiple ethylene injection points improve selectively and enhance catalyst
stability. In the alkylation reactor, ethylene reacts completely, leaving only the inert constituents of the feed, such as
ethane. These inters pass through the reactor and are from the plant at a convenient point.
The alkylation effluents are fed to the benzene column, where benzene is taken as the over head product for recycle
to the reactor. The benzene column bottoms feed the ethyl benzene column. Here EB is taken as the overhead
product.
The reboiler of the distillation columns may used hot oil, high-pressure steam, or direct firing. Overhead vapors are
condensed in waste heat boilers, generating valuable steam useful in a downstream SM or propylene oxide/styrene
monomer plant. The EB unit has considerable flexibility to mmet a verify of local site conditions in an efficient
manner. If no stream export is required, the net heat import can be reduced considerably.
The Ethyl benzene plant capacity is 1000MTPY(109 kg per year) based on:
• As well as other capacities of other Ethyl benzene operating plants (or projected plants).
23
6.4 Process Flow Diagram:
H-1 Heater
C-1 Cooler
24
Chapter 7
Mass & Energy Balances
25
Mass & Energy Balances
2. Stream (2) – ethylene contains 7 mole % ethane as impurity. Ethane dose not react but
moves in the process as inerts and vent in the light column.
7. Stream(11) –
Ethyl benzene = 99.9% wt
Benzene = 0.1% wt
26
7.2 Mass balance Calculations:
Since we are using liquid phase alkylation process for ethyl benzene production, for which yield and conversion are
as follows:
Yield=99.7%
Stream (11)
Reactor
R1
27
Now we know that:-
here,
and
It means that all ethylene had converted in to ethyl benzene and rest ethylene converted in to diethyl benzene.
Now
= 9548 kmol/hr
=1193.5/0.93
= 1283 kmol/hr
= 89.5 k moles/ hr
= 9548-1193.5
Inputs:
Outputs:
29
Diethyl benzene = 3.5 kmol
Reactor
R1
Stream:-(6)
30
Stream 7
Lights Column
L-1
Stream 6
Stream 8
31
Material balance of Benzene Column:
EB 0.6 mol
EB 1186.5 mol
Benzene Column
DEB 3.5 mol
EB 1186.5 mol
32
Now consider Ethyl benzene (EB) column:
Stream no :(10)
Stream (11):
EB = 1186.5 mol
Stream (12):
Benzene = 4 mol
33
Thus finally EB column is:
Stream 11
EB = 1186.5 mol
Benzene= 0.15 mol
Stream 10
EB Column
EB= 1186.5 mol
DEB= 3.5 mol
Benzene= 4.15 mol
Stream 12
Thus finally :
For Reactor
Input :
Stream:
Total 778665
Output:
Stream:
Total 778665
35
For Light Column:
Input:
Stream:
Total 778665
Output:
Stream:
Total 2685
&
Stream:
Total 775980
36
For Benzene Column:
Input:
Stream:
Total 775980
Output:
Stream:
Total 649416.3
&
Stream:
Total 126563.7
37
For Ethyl Benzene Column:
Input:
Stream:
Total 126563.7
Output:
Stream :
Total 125779.7
&
Stream:
Total 784
38
7.3 Energy Balance Calculations:
Stream 3
Heater
I/P O/P
543K
Q = Q out – Q in
= (Q B + Q E + Q I )out – (Q B + Q E + Q I )in
where QB ,
QB =[ nB ( ∫ c p dT + λ)
Now we
perform similar calculations for all the I/P components:
Thus
4 Total 0 690.228
39
Energy Balance Calculations across Reactor:
Qr = Qout - Qin
= 1305.06 – 1441.28
= - 136.22 MJ/hr
So we need dowtherm as an utility to make reactor at operating condition, which would be:
Qr = mw * cp * ∆T
mw = 2173 Kg/ hr
Q c = Qout – Qin
= -357.697 MJ
Qc = mw * cp * ∆T
mw = 5677.73 Kg/ hr
R = 1.5
Thus in L:
B= 12494 mol
I= 134.25 mol
& in V:
B = 20823.16 mol
I= 223.75 mol
40
So condenser duty will be:
Qc = QL + QD - QV
= -658.55 MJ /hr
Qc = mw * cp * ∆T
mw = 10453 Kg/ hr
QR - QC = QD + QB - QF
QR = 699.06 MJ/hr
R = 1.5
Thus in L:
EB = 1779.75 mol
B= 1.2495 mol
& in V:
B = 2966.13 mol
I= 2.0825 mol
Qc = QL + QD - QV
= -117.12 MJ/hr
41
Thus requirement of water as utility will be:
Qc = mw * cp * ∆T mw = 1868.38 Kg/ hr
QR - QC = QD + QB - QF
QR = 63.167 MJ/hr
ms = 24.95 Kg/hr
(Kg/hr)
(Condenser)
(Reboiler)
(Condenser)
(Reboiler)
42
Chapter 8
Detailed Equipment Design
43
8. Detailed Equipment Design
8.1 Fixed Bed Catalytic Reactor Process Design:
Benzene 742.56
Ethylene 33.42
Inerts 2.685
Total 778.665
Reaction: C6 H6 + C2 H4 C6 H5 – C2 H5
Catalyst: Zeolite
Type of reactor: Shell and tube heat exchanger type in which catalyst is placed inside the tube.
=126.2626 Kg/h
Mass of catalyst;
W/FA0= ………………………………………………………..(1)
-ra = KrCE/(1+KEB.CEB)
44
Where;
Kr =0.69*106exp[(-6.344*104)/RT]
KEB= -1.5202*10-2exp[(-3.933*103/RT]
W = 2541 Kg
=2541/630
= 4.03 m3
= 5.76 m3
= (778.3/3600)/0.55
= 0.3935 m2
Tube OD = 50.8mm
Tube ID = 43.28 mm
nt = 0.3935/(∏/4)(0.04328)2 =267.48
=268 tubes
= 4.03 *4/268*3.14*(.04328)2
=10.22m
=10m
Aav = nt ∏d0 L
= 268*3.14*0.0508*10
45
=427.49 m2
Qt =114123*33.42/28
= 37.837 KW
dp=0.002565m
G= 0.55 kg/m2 .s
k= 0.04 W/m.k
µ=0.015mPa
On Calculation ;
hi =31.49w/m2 C
hi dp/k = 3.6(dpG/µε)0.365
hi*0.002565/0.04 =3.6(0.002565*0.55/0.02*10-3*0.3)
hi =457.51W/m2 0C
=1.25*0.0508
= 0.0635 m
= 1.1/0.0508[0.06352 – 0.907*0.05082]
46
= 0.03663 m
Qt =m*CL∆t
Property Value
CL 2.5832 KJ/kg 0C
µ 0.135 mPa .s
K 0.098 W/m 0C
Let
∆t=2 0C
m=37.837/2.5832*2)
= 7.323 Kg/s
Ρ =0.709 Kg/L
= 37.18 m3 /hr
Db = 50.8(268/0.319)1/2.142
= 1171.3mm
47
Db = 15 mm
Baffle spacing
=( 0.0635-0.0508)/0.0635(1.186*.474
= .1124 m2
Gs=m/As
= 7.323/.1124
= 65.1512 kg/m2 s
=(0.03663*65.1512)/0.135*10-3
=17677.90
Prandtl number;
,Pr = CLµ/k
= (2.5832*0.135*10-3*103)/0.098
=3.558
( h0 *0.03663)/0.098 =0.0046*17677*3.5580.33
h 0 =336.50 W/m2 0 C
U0 = 24.47 W/m2 0C
48
∆ps =8 Jf(Ds/de)(L/Bs)(ρsus2/2)(µ/µ w)0.14 us= Gs/ρs =65.152/3.831
= 8*0.0046*(1.186/0.03663)(10/0.474)(3.831*172/2) = 17.006
= 13.91 KPa
Re = ρumdi/µ
= (810*0.0014*0.04328)/0.015*10-3
= 3271.968
= [ 1.58 ln 3271.968-3.28]-2
= 0.0110
Atp =( πdi2/4)(Nt/2)
= 3.14*(0.04328)2/4*(268/2)
= 0.19 m2
Um = mt/ρt Atp
= 778.665/(810*0.19*3600)
= 0.0014 m/s
= 0.011240 KPa
49
8.2 Mechanical Design for reactor
Data;
Number of shells - 1
Number of passes - 1
Fluid - Dowtherm A
Inlet temperature - 25 0C
Head
50
= 0.25*75/9\(2*87-0.25)
= 0.1080 mm
Adding corrosion allowance
tn = 4mm
Head thickness(th) = PCrW/2fJ
W=1/4(3+(Rc/R1)1/2 )
= 1/4(3+(1200/120)1/2)
= 1.54
J=1
th=2.431mm
adding corrosion allowance
th=5.431mm
Using thickness same as for shell i.e 8 mm
Transverse Baffles
Spacing between baffles= 0.4Ds
= 0.4*1200
=480 mm
Thickness of baffls = 5mm
Tube Side
Thickness of tube;
tf =PD0/(2fJ+P) J=1 (seamless tube)
=3.6*50.8/(2*87*0.85)+0.36
= 1.233 mm
No corrosion allowance , since the tubes are of stainless steel.
Use a thickness of 2 mm
b0 = ½(1240-1200)/2 = 10mm
=7.90mm
= 3.14*7.9*(1240+1200)/2*(11.2)
51
= 338949.184
At operating condition,
Wm2=3.14(2b)GMP+3.14G2P
=3.14*2*7.9*(1240+1200)/2(0.25)+3.14/4(1240+1200)2/2(0.25)
= 322361.82
= 49 bolts
= [(59/49)/49*(4/3.14)]1/2
= 1.533 cm
= (2*3.14*1220**11.2*20)/58
= 292 Cm2
N- Width of Gasket
fa – permissible stress.
=1335mm
K= 1/[0.3+1.5WmhG/HG]
= 1/[0.3+(1.5*322361.82*(1335-1220)/2]/(3.14/4)*12202*0.25*1220]
= 3.17
52
putting all the values in equation (2)
tf = 38.15
Tube Side:
Thickness of tube;
=3.6*50.8/(2*87*0.85)+0.36
= 1.233 mm
Use a thickness of 2 mm
Thickness of nozzles
tn= pD/(2fJ-p)
J= 1 ( seamless pipe)
tn= 3.6*75/(2*95-3.6)
=1.448 mm
tn= 5mm
53
8.3 Process Design of Benzene Distillation Column
In Benzene column, a product stream from reactor is coming which consists of benzene, ethyl benzene & some
amount of di-ethyl benzene. Since it is more than two component case, hence we will perform multicomponent
distillation in order to separate benzene from mixture and recycle it back to reactor.
EB 0.6 mol
EB 1186.5 mol
Benzene Column
DEB 3.5 mol
EB 1186.5 mol
Here Benzene is light key component and EB is heavy key component. The column is operating at 1 atm.
54
Now first of all we will calculate bubble point & dew point temperature.
Now will do trail & error untill we get a value of temperature for which yi = 1.
At T= 112 0 c ( 385 K)
Component A B C
B 15.9008 2788.51 -52.36
EB 16.0195 3272.47 -59.95
DEB 16.1140 3757.22 -71.18
*All the values of Antonie’s cofficient of A,B,C are taken from Coulson & Ricardson Vol. 6, Appendix D, page no.
947 - 967.
55
Calculation of Minimum reflux ratio (Rm):-
(αi can be calculaed as αi = ki/khk which is 5.714, 1, 0.1836 correspondingly for B, EB, DEB.)
Component Xf Xd Ki αi
B 0.8750 0.9999 1.12 5.714
EB 0.1246 0.0001 0.196 1.000
DEB 0.0004 0.0000 0.036 0.1836
Φ = 1.52
∑[(αi xid)/( αi –φ )] = Rm + 1
Rm = 0.242
Ro = 1.5 Rm = 0.363
Nmin = 8
We have,
N = 19
Flow Rates:
Mav = ∑xi Mi
F = 9.52 kmol/hr
D = 8.33 kmol/hr
B = 1.194 kmol/hr
Now molar flow rates of vapor & liquid at top in enriching section:
57
Calculation of tower diameter:
V = 11.349 kmol/hr
L = 3.0225 kmol/hr
Density of vapor:
Corresponding Cf = 0.06
(from Introduction to Process Engineering & Design by S.B. Thakore & B.I Bhatt, Chapter 6, Process Design of
distillation column, Page no. 448)
= 1.126 m/sec.
Di = {(4*Ac)/∏}0.5 = 0.375 m
= 32.767 kpa
V’ = 11.349 kmol/hr
L’ = 12.543 kmol/hr
Density of vapor:
59
Tray spacing = 0.3 m (assumed)
Corresponding Cf = 0.06
= 0.811 m/sec.
Di = {(4*Ac)/∏}0.5 = 0.400 m
K constant can be obtained from Fig 8.19 (Introduction to Process Engineering & Design by S.B. Thakore &
B.I Bhatt, Chapter 6, Process Design of distillation column, Page no. 449) or Fig. 4 of appendix. ,is a function
of (hw + how),
where
weir height (hw) = 50 mm
hole diameter(dh) = 5 mm
Plate thickness (t) = 5mm
60
(a) For enriching section :
height of liquid crest over the weir
Lm = 0.7*L*Mav = 0.7*(11.349/3600)*78
= 0.172 kg/sec
lw = 0.77* Di
= 0.77* 0.375
= 0.2885
Now putting all the values ,
how = 6.075 mm
Thus (hw + how) = 56.075 mm
corresponding K value from Fig 8.19:
K = 30.2
Thus finally
vh,min = 4.62 m/sec
Actual vapor velocity holes at actual vapor flow rate :
vh,a = (0.7* Qv)/ Ah ……………………………………………………………………………………………..(a)
Thus in enriching section minimum operating rate is well above weep point.
Lm = 0.7*L*Mav = 0.7*(12.543/3600)*106
= 0.259 kg/sec
lw = 0.77* Di
= 0.77* 0.400
= 0.308
61
ρl = 879 kg/m3
Now putting all the values ,
how = 23.19 mm
Thus (hw + how) = 75.19 mm
corresponding K value from Fig 8.19:
K = 30.68
Thus finally
vh,min = 5.8533 m/sec
Actual vapor velocity holes at actual vapor flow rate :
vh,a = (0.7* Qv)/ Ah ……………………………………………………………………………………………..(b )
Thus in stripping section minimum operating rate is well above weep point.
hd = 51(vh/C0)2(ρv/ρl) ………………………………………………………………………………………..(c)
62
how = 750 (Lm/ρl*lw)
= 750{(0.172/0.7)/(867*0.288)}
= 23.36 mm
Residual Pressure drop:
hr = (12.5*103)/ρl = (12500/867) = 14.41 mm
hd = 51(vh/C0)2(ρv/ρl) ………………………………………………………………………………………..(c)
Type of downcomer: Straight & segmental downcomerarea, Ad = 0.12Ac (for both sections)
63
(a) For enriching section:
Vapor velocity based on net area (vn) = Q’/ An = 0.0924 / 0.973 = 0.95 m/sec.
ψ = 0.11
or 11%
% Flooding = 85%
Flv = 0.0785
ψ = 0.053
or 5.43%
65
8.4 Mechanical Design of Benzene Distillation Column used in Ethyl Benzene Production
Shell Thickness:
but for high vessels under external pressure take shell thickness ts= 8mm
Head:-
Torispherical heads
Cs = ¼[3 + (Rc/Rk)0.5]
Take Rc = 400 mm ; J = 1
On solving Cs = 71.24
Therefore Rk = 5.026x10-3mm
66
Shell Thickness at different Height:-
fap = 18 kg/cm2
67
wind pressure = 125 kg/m2 = 125x10 -6 kg/mm2
solving for X ;
X = 17.6
Support:-
68
69
Chapter 9
Cost Estimation
70
9. Cost Estimation
Therefore cost of plant in 2008 = Cost in 1965x {(cost index in 2008)/ (cost index in1965)}
71
9.2 Estimation of total product cost:
General Expenses:
X = 22.657 crores
Assuming a profit margin of 20% so selling price of the product = Rs. 273
Gross annual earnings = total annual sales – total annual product cost = Rs. 4.6 crores
= 32.714/ 2.76
= 11.85 years (12 year approx)
73
Chapter 10
Conclusion
74
Conclusion:
Nearly all commercial ethylbenzene is produced by alkylation of benzene with ethylene. Earlier processes were
based on liquid phase alkylation using an aluminum chloride catalyst but this route required disposal of aluminum
chloride waste.
In the early 1980s, Mobil/Badger developed an alternative zeolite-based process using vapor phase alkylation,
offering higher yields and purity. More recently, liquid phase processes using zeolite catalysts have been introduced.
These latest technologies offer low benzene-to-ethylene ratios, which reduces the size of equipment, and lowers the
production of byproducts.
Nearly all the ethylbenzene (EB) produced is used in the manufacture of styrene monomer (SM) with the remainder,
at less than 1%, used in solvent applications. In addition, most of the EB is used captively, leaving a small merchant
market for the product. Hence, EB demand runs in parallel to that of styrene.
Here we have designed a plant for 1000 MTA, with a techno-economic feasibility report which is started with a
need, demand & supply analysis and by going through a process of mass, energy balances and detailed design of
equipments in the process.
75
References
76
References:
• Chapter 8, Process Design of distillation Column, Introduction to Process Engineering & Design, Second
reprint 2009, Published by, Tata-McGraw-Hill Publishing Company limited, New Delhi.
• Chapter 6, Costing & Project Evaluation, Coulson & Richardson’s volume 6, Third Edition, Chemical
Engineering Design, By R.K.Sinnot, Publisher by Butterworth- Heinemann Publications.
• Chapter 11, Separation Columns, Coulson & Richardson’s volume 6, Third Edition, Chemical Engineering
Design, By R.K.Sinnot, Publisher by Butterworth-Heinemann Publications.
• Chapter 10, Process Design of Reactors, Introduction to Process Engineering & Design, Second reprint
2009, Published by, Tata-McGraw-Hill Publishing Company limited, New Delhi.
• Process Equipment Design, By M.V. Joshi & V.V. Mahajani, Third edition, published by McMillan India
Limited.
• Hydrocarbon Processing.
• Basic Principals & Calculations in Chemical Engineering, David M. Himelblau, 6th Edition, PHI
Publication.
77
Appendices
78
(A) Figures:
Figure 1
79
Figure 2
80
Figure 3
Figure 4
81
Figure 5
82
(B) MSDS:
83
84
85
86
87
88