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Ethyl Benzene Project Report

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Ethyl benzene is produced commercially using a liquid phase process with zeolite catalyst. It is
used almost exclusively to produce styrene monomer, which is then used to make polystyrene
plastic. Global production of ethyl benzene has grown steadily since the 1930s when it was first
produced commercially, reaching over 14 million metric tons annually by the late 20th century.
Site selection and plant layout for ethyl benzene production facilities consider factors like
markets, transportation, energy availability, and safety.
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Chapter 1
Historical Profile

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1. Historical Profile

1.1 Introduction to Ethyl Benzene (EB):

1.2 Ethyl benzene is an organic chemical compound which is an aromatic hydrocarbon (HC).
Its major use is in thepetrochemical industry as an intermediate compound for the
production of styrene, which in turn is used for makingpolystyrene, a commonly used
plastic material. Although often present in small amounts in crude oil, ethyl benzeneis
produced in bulk quantities by combining the petrochemicals benzene and ethylene in an
acid-catalyzed chemicalreaction. 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 byliquid phase alkylation’s or vapor phase
alkylation’s of benzene with ethylene. Commercial production started in the1930s and
has grown to over 23 million metric annually (MTA)
1.2

History of Ethyl Benzene:

The alkylation of HC with olefins in the presence of AlCl
3
Catalyst was first practiced by M.Balsohn in 1879.However, Charles Friedel & James M. Crafts
pioneered much of early research on alkylation & AlCl
3
Catalyst .Overa century later, the process that employ the classic Friedel-Crafts reaction
chemistry remain a dominant source ofEB. 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 Craftsreaction 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 distillationprocess. In 1980s ,the first
commercial facility using a zeolite based process and the absence of maintenance
nadenvironmental problems associated with the Fridal-Creafts catalyst havre allowed zeolite
catalyst and to completelydisplace the order catalyst in all modern production facilities.The4first
zeolite process was based on vapor –phase reactor at temp. of over 400
0
C. In this temperature rang,reaction such as isomerisation/cracking and hydrogen transfer
produce a number of by products that contaminatesthe EB product.Efforts were made to reduce
by-product formation by changing reaction condition , but it as not until the advent ofliquid
phase processes operating at temperatures lower than 270
0
C that zeolite –catalysed processes were trulycapable of producing high purity EB . The first
high purity zeolite based on technology developed by UOP and ABBLummus Global , started up
in the 1990.The Ethyl benzene- Styrene industry remained relatively insignificant until World
War 2. The tremendous demandfor synthetic SBR during world war prompted accelerated
technology improvements and tremendous capacityexpansion. This enormous wartime effort led
to the construction of several large scale factories, turning styreneproduction quickly in to a giant
industry. In 1965, 10% of EB production was from super fraction of mixed xylenestreams
produced by catalytic reforming of naphtha. In 1986, the world annual production capacity was
14*10
6
T.EB was first produced on a commercial scale in the 1930s by Dow Chemical in US and by
BASF in the FederalRepublic of Germany.
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1.3 Natural Occurrences:
1.4 Ethyl benzene is a colorless, flammable liquid that smells like gasoline. It is naturally
found in coal tar andpetroleum and is also found in manufactured products such as inks,
pesticides, and paints.
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Chapter
󰀲

Applications

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2. Applications
2.1 Current Applications:
All commercial EB production is captive consumed for the manufacture of styrene monomer
Styrene is used in theproduction 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.
2.2 Product Specification
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) Haliedesb)
DiethylbenzenePurity 99.5 wt, % minBenzene 0.1-0.3 %Toluene 0.1-0.3%O-xylene +Cumene
0.02% maxm,p- xylene 0.2% maxAllylbenzene 0.2% maxDiethylbenzene 20mg/kg maxTotal
Chlorides 1-3 mg/kg maxTotal organic sulpher 4 mg/kg maxReactivity density @ 15o c 0.869-
0.872APHA colour 15 max

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Manufacturing Capacities:
PRODUCER CAPACITY*
BP Chemicals, Texas City, TX 1,100Chevron, St. James, LA 1,800Cos-Mar, Carville, LA
2,200Dow, Freeport, TX 1,900Huntsman, Odessa, TX 350Lyondell Chemical, Channelview, TX
3,000Nova, Bayport, TX 1,400Sterling, Texas City, TX 2,000Westlake, Lake Charles, LA
380Total 14,130*Millions of pounds per year of Ethyl benzene (EB).
In India:
From Chemical Weekly Buyers Guide 2005- Vol.3
Pashim Petrochem Ltd.
Amol Chemicals & PolymersChemaroma Drug HouseChemicoForum EnterprizesGanesh
Trading Co.Manish ChemicalsMikit ChemicalsOm Chemi PharmaPerfect
ChemicalsSolvchemTanay Corporation

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Chapter 3
Economic Scenario

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2. Economic Scenario

3.1 Current & Projected Demand:Demand ( till 2004):

1999: 13,193 million pounds2000: 13,444 million pounds2004: 14,552 million pounds
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 manyhomopolymer, 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 isproduced with captive EB there is not much noticeable market
activity.
3.2

Price & Price Variations:PRICE

Historical (1995 – 2000):

High, $0.25 per pound, bulk, f.o.b. Houston, TX, list($ 0.5511 / Kg)


By Friday 8 August, 2008:

EB was valued at $1,554-1,570/tonne FOB NEW.($ 1.554—1.570 / Kg)
Price Variations:
The US unit sales value of EB in $/Kg from 1960 – 1986:
Year

Sales ( $/Kg)
1960 0.131965 0.091970 0.091973 0.111974 0.371975 0.201978 0.241979 0.351980 0.511983
0.501986 0.48—0.51
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3.3 Application wise Consumption Pattern:Application Consumption ( in % )Styrene Production
99 %Paint industry as a solvent < 1%Production of Acetophenon,Diethylbenzene, Ethyl
anthraquinon< 1%3.4 Site Considerations:
Before any site selection work begins the company should be organized for expansion planning
in a way thatdepends on the size of the firm. A company may want to utilize a standing
committee, a special project team orplanning by one person. In any event the planning function
must be clear cut responsibility of one individual.
Site Selection Factor:
1. Markets2. Work force3. Unionization4. Transportation5. Energy6. Business climate7.
Water and waste systems8. Living conditions9. TopographyThe basic aim of the site
selector is to choose a location that maximizes income and minimizes cost
compromisesusually have to be made. No site is ever perfect, and it is the mission of the
site selection team to weigh thealternatives and compromises on the best choice.
Plant layout:
Plant layout involves developing physical equipment for a processing facility. The development
must effect abalance of equipment spacing and integration of specific systems related to facility
as a whole. Some of the factorsto be considered for designing the plant layout are:1. Process2.
Economics3. Client requirements4. Operation5. Erection and maintenance6. Safety7.
Environment8. Appearance9. Expansion

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In-line plant layouts are made in various arrangements which often are referred to by letter
designation. Variousconfigurations are formed based on the main artery of the process unit i.e.
the pipe rack, which contains long processand the utility lines that connect distant equipment and
product piping entering and leaving the plant. Space forinstrument 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 plantlayout for a chemical plant, it is essential
that the firm decisions are made early as to equipments arrangement. Thiseliminates changes,
which cost man-hours as the job progresses through engineering and design. The
distillationsections are based on a grade-level process plant layout configuration. The steam
generation and power facilities arehoused 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 materialsas well as for better
market.
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Chapter 4

󰁐󰁥󰁴󰁩󰁥󰁳

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4. Properties
4.1 Physical 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.The properties
are as follows:
IUPAC Name Ethylbenzene
Other names Ethylbenzol, EB, PhenylethaneIdentifiersCAS Number [100-41-4]RTECS Number
DA0700000SMILES c1ccccc1CCMolecular Formula C8H10Molar Mass 106.167
g/molAppearance Colourless liquidDensity (at 150 c) 0.87139 g/ccDensity ( at 200 c) 0.8669
g/ccDensity ( at 250 c) 0.86262 g/ccM.P. -94.949 0 cB.P. ( at 101.3 K Pa) 136.860 cRefractive
index (at 200 c) 1.49588Refractive index ( at 250 c ) 1.49320Critical pressure 3609 K Pa (36.09
bar)Critical temperature 344.02 0 cFlash point 150 cAuto ignition temperature 4600
cFlammability limit ( lower) 1.0%

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Flammability limit ( Upper) -----Latent heat ( fusion) 86.3 j/kgLatent heat ( vaporization) 335
j/kgHeating value ( gross) 42999 j/kgHeating Value ( net) 40928 j/kgKinematic viscosity (at 37.8
0 c ) 0.6428 * 10 -6 m2 / sKinematic viscosity (at 98.90 c ) 0.390 * 10 -6 m2 / sSurface Tension
28.48 mN/mSpecific heat capacity ( ideal gas,250 c )1169 kg-1 K-1Specific heat capacity
( liquid, 25 0c)1752 kg-1 K-1Acentric factor 0.3011Critical compressibility 0.264LEL 1.2
%UEL 6.8 %
4.2 Chemical Properties:
The most important chemical reaction of EB is its dehydrogenation to Styrene.The reaction is
carried out at:1.

High temprature ( 600-6700 c)2.

Usually over an iron oxide catalyst3.

Steam is used as dilutentCommercially, selectivities to styrene range from 89-96%with per rpass
conversion 65-70%

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.EB Styrene


Another reaction of commercial importance is the oxidation of EB by air to hydroperoxides C

6
H
5
CH(OOH)CH
3
.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
xylenesusually involve the catalytic isomerization or dealkylation of EB.


EB may be dealkylated catalytically or thermally to benzene.

4.3

Environmental & Health Effects:Emergency Overview:

 Clear, colourless liquid with a characteristic, sweet, gasoline-like, aromatic odour.
FLAMMABLE LIQUID ANDVAPOUR. Liquid can accumulate static charge by flow, splashing
and agitation. Vapour is heavier than air and mayspread long distances. Distant ignition and
flashback are possible. Liquid can float on water and may travel todistant locations and/or spread
fire. Closed containers may rupture and explode in heat of fire. TOXIC. May beharmful 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 CANCERHAZARD – may cause cancer, based on animal
information.
Potential Health effects:Effect of short Term Exposure:
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 systemdepression such as mild unsteadiness, headache, nausea,
dizziness and a feeling of drunkenness at approximately100-200 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,
mildunsteadiness, sleepiness and headache were reported. In another report, approximately 100
ppm (cited as 400mg/m
3
) produced a slight irritating effect on the respiratory tract, occasional headaches, sleepiness,
slight drowsinessafter 8 hours. More pronounced irritation, frequent headaches, sleepiness and a
feeling of drunkenness wereobserved at 200 ppm (860 mg/m3). At 1150 ppm (5000 mg/m
3
), 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 increasingunsteadiness, chest
constriction and dizziness in 4-6 male volunteers. Exposure to 5000 ppm (0
.5%) was consideredintolerable
Skin Contact:
The liquid can cause moderate irritation, based on animal information. Ethylbenzene is absorbed
through the skin toa small extent, but harmful effects are not expected to occur by this route of
exposure.

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Eye Contact:

The liquid can cause mild to moderate irritation, based on limited animal information. Volunteers
reported thatexposure to approximately 100 ppm was slightly irritating to the eyes. At 1000 ppm
(0.1%) the vapour was veryirritating to the eyes of 4-6 volunteers, producing smarting and
burning, accompanied by profuse tearing. Thisirritation, gradually decreased until, after a minute
or two, it was barely noticeable. At 2000 ppm (0.2%), theirritation was almost intolerable upon
first exposure, but again became less irritating upon continued exposure, while5000 ppm (0.5%)
was considered intolerable.
Ingestion:

Ethylbenzene has relatively low toxicity following ingestion. As a central nervous system (CNS)
depressant, it cancause 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.
Effects of Long-Term (Chronic) Exposure:
Nervous System:

A number of human population studies involving painters and other occupational groups exposed
to a wide range ofsolvents, including ethylbenzene, have led to some investigators to conclude
that long-term exposure to solventsmay cause permanent effects on the central nervous system
(CNS). The signs and symptoms are ill-defined andinclude headaches, memory loss, fatigue and
altered emotional reactivity. This syndrome is commonly known asOrganic Solvent Syndrome.
There are no specific studies that implicate ethylbenzene as a causal agent, although it ispresent
in many of the paints and other solvent-containing products. The available studies tend to have a
number ofdeficiencies 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 forover 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 hearingdamage above that for noise exposure alone. Guinea pigs do not appear to be
sensitive to these effects.(54,55) Therelevance of these observations to human exposures is not
known.
4.4 Handling, Storage & Transportation:


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.

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Chapter 5
Manufacturing Processes

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5. Manufacturing Processes:

Currently, the primary source of ethyl benzene is the alkylation of benzene with ethylene. The
only other source, thesuper fractionation of mixed C8 aromatic streams, supplies only a small
portion of the ethyl benzene produced. Twodistinct types of ethyl benzene alkylation processes
are currently used commercially: liquid- phase alkylation andvapor-phase alkylation.
5.1 Liquid Phase Alkylation:
Liquid phase aluminum chloride processes have been the dominant source of ethylbenzene since
the 1930s. Severalcompanies 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 Monsantoprocess is currently the most modern commercially
licensed aluminum chloride alkylation technology. Alkylation ofbenzene with in the presence of
an aluminum chloride catalyst complex is exothermic (
∆
H-114 kJ/mol); the reactionis very fast and produces almost stoichiometric yields of ethy
lbenzene. In addition to AlCl3, a wide range of Lewisacid catalysts, including AlBr3, FeCl3, and
BF3, have been used. Aluminum chloride processes generally use ethylchloride 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, drybenzene, and recycled polyalkyl benzenes is continuously fed
to the reactor and agitated to disperse the catalystcomplex phase in the aromatic phase. Ethylene
and the catalyst promoter are injected into the reaction mixturethrough spargers, and essentially
100% of the ethylene is converted. Low ethylene: Benzene ratios are used to giveoptimum
overall yield of ethylbenzene. Commercial plants typically operate at ethylene: because molar
ratios ofca.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 masspolyalkylbenzenes. The loss in net yield due to residue is
minimized by recycling this material to the alkylationreactor. In addition, because the reaction
occurs close to thermodynamic equilibrium, the traditional processes use asingle reactor to
alkylate benzene and transalkylate polyalkylbenzenes.The reaction temperature is generally
limited to 1300C; a higher temperature rapidly deactivates the catalyst andfavors formation of
non aromatics and polyalkyllbenzenes, which are preferential absorbed by the highly
acidiccatalyst complex, resulting in byproduct formation. Sufficient pressure is maintained to
keep the reactants in theliquid phase. High –alloy materials of construction are also required for
the piping and handling systems. The liquidreactor effluent is cooled and discharged into a
settler, where the heavy catalyst phase is decanted from the organicliquid phase and recycled.
The organic phase is washed with water and caustic to remove dissolved AlCl3 andpromoter. The
aqueous phase from these treatment steps in first neutralized and then recovered as a
saturatedaluminum chloride solution and wet aluminum hydroxide sludge.Removal of dissolved
catalyst from the catalyst from the organic stream has long been a problem for
ethylbenzeneproducers. Recently CdF chime found that more complete recovery of AlCl3 could
be achieved by first contactingthe organic phase with ammonia instead of sodium hydroxide.