Beruflich Dokumente
Kultur Dokumente
CHAPTER 1
INTRODUCTION
Ethylbenzene, also known as phenyl ethane and ethylbenzol, C6H5CH2CH3, is a single
ring, alkyl aromatic compound. It is almost exclusively (> 90%) used as an intermediate for
the manufacture of styrene monomer, C6H5CH=CH2, one of the most important large-volume
chemicals. Styrene production, which uses Ethylbenzene as a starting raw material, consumes
ca. 50% of the worlds benzene production. Less than 1% of the Ethylbenzene produced is
used as paint solvent or as an intermediate for the production of Diethylbenzene and
acetophenone.[9]
1.2 PROPERTIES:
1.3 USES:
CHAPTER 2
There are different manufacturing processes available for Ethylbenzene .Some these are
listed below:
PROCESS:[2,9]
2.1.1 Introduction:
Liquid phase aluminum chloride processes have been the dominant source of
Ethylbenzene since the 1930s to about 1980. Several companies have developed variations of
this technology. Processes currently in use include those of Dow chemical, BASF, Shell
chemical, Monsanto and union carbide/ badger. The Monsanto/Lummus technology is
currently the most modern commercially licensed aluminium chloride alkylation technology.
2.1.2 Description:
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 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.
The unreacted benzene is recovered by the first columns as an overhead distillate. The
second column separates the ethylbenzene 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.
a : Reactor d: EB Column
[2,3,9]
2.2 VAPOUR -PHASE ZEOLITE CATALYST PROCESS:
2.2.1 Introduction:
Vapour-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 favour 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 vapour phase technology to be introduced. The process was developed in
the 1970s around.
2.2.2 Description:
The reactor typically operates at 400-4500C and 2-3 MPa (20-30 bars). 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 36 hrs and is necessary after 6-8
weeks of operation. The catalyst is less sensitive to water, sulphur, and other poisons than the
Lewis acid catalysts.
The reactor effluent passes to the purification section as a hot vapour. 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 Ethylbenzene 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 no recyclable
residue.
2.3.1 Introduction:
2.3.2 Description:
A typical EBMax based plant flow diagram is shown below. The alkylation reactor is
maintained in liquid phase and uses multiple bed catalyst beds ethylene injection. The
ethylene conversion is essentially 100% in the alkylator reactors and the reactor nearly
operates adiabatically. The exothermic heat of reaction is recovered and used to produce
steams or as heat duty in the distillation columns.
The transalkylator reactor in an EBMax plant can be either vapour phase or liquid phase.
More recently, the transalkylation reactor has been designed as liquid phase because of its
improved energy efficiency .The transalkylation reaction is conducted in the liquid phase
using Mobil TRANS-4 catalyst.
The alkylation and transalkylation reactor effluent stream are sent to the distillation
section which consist of primarily of three distillation columns .The first column is a benzene
column and it separates unconverted benzene into the overhead stream for recycle to the
reactors. The benzene column bottom stream feeds the EB column. The EB column recovers
the EB product in the overhead stream and the bottom stream of the EB column feeds the
PEB column where PEB is fractionated overhead and recycle to the transalylation reactor.
The bottom stream of the PEB column is removed as the residue stream and is generally used
as fuel in an integrated styrene.
2.4.2 Description:
The CDTECH alkylation reactor consist of two main sections a catalytic distillation
section and a Standard distillation section as shown in figure. Benzene is feed to the top of
alkylation Reactor and Ethylene is fed as a vapour below the Catalytic Distillation Section
creating a counter current flow of the Alkylation reactants through the catalytic distillation
section throughout the catalytic distillation section a vapour liquid equilibrium is established
is largely concentrated in the vapour phase. The Ethylene that dissolves into the liquid phase
rapidly alkylates benzene on the catalyst active sites to produces EB. The rapid reaction of
Ethylene in the liquid phase creates a driving force for additional Ethylene to dissolve into
the liquid phase where the alkylation reaction occurs on the catalyst active site .The
exothermic heat of reaction creates the vaporisation necessary to effect distillation the
alkylation reaction product, mainly EB, Diethylbenzene and similar amounts of other by
products are continuously fractioned and removed from the catalytic distillation section .in
the lower section of alkylation reactor standard distillation occurs and the bottom stream
contains primarily EB,PEB and other high boiling by-products.
a : Alkylator e : EB Column
d : Benzene Column
CHAPTER 3
PROCESS SELECTION
3.1ADVANTAGES:
Liquid phase zeolite catalyst process (EB-MAX) & Liquid-Vapour phase zeolite
catalyst process (CDTech EB) both dont have disadvantages.
From above advantages & disadvantages for different processes we select Mixed
Liquid-Vapour Phase Zeolite Catalyst process (CDTech EB). Since it has more advantages
over other existing manufacturing process for Ethylbenzene. Also it requires less pure
benzene & ethylene. Less harm full to environment also.
CHAPTER 4
PROCESS DESCRPTION
The Mixed Liquid-Vapour Phase Zeolite Catalyst process is selected for the manufacture of
Ethylbenzene on following considerations:
4.1 MANUFACTURE:[9]
Raw materials for the production of Ethylbenzene by Mixed Liquid-Vapour Phase Zeolite
Catalyst process are:
1. Ethylene
2. Benzene
4.1.1 Ethylene:
1. From coal
2. Form petroleum
3. Hydrodealkylation
4. Disproportionation
This process operates under alkylation reactor, which combines catalytic reaction with
distillation into a single operation. Reaction temperature is 1500 C 1950 C & operating
pressure of, 1.62.1 MPa of pressure. The selectivity was above 83% (only benzene feed) and
even higher than 99% (benzene plus transalkylation feed).
The alkylation reactor consists of two sections catalytic distillation and standard
distillation section. Benzene is fed at the top of the reactor and ethylene is fed as a vapour at
the bottom in catalytic distillation section creating counter-current flow of reactants in the
catalytic distillation section. In this section ethylene dissolves into the liquid phase rapidly
heat of reaction creates the vapour isation necessary to effect the distillation. The alkylation
products mainly ethylbenzene, di-ethylbenzene and other products are continuously
fractioned and removed from the catalytic distillation section.
In bottom section standard distillation occurs and bottom stream exits containing
ethylbenzene, PEB and other products.
PEB and ethylbenzene proceed to benzene stripping section which operates in the
temperature range of 295-325 0C depending upon the pressure. Fired heater (or hot oil)
provides heat for thermal duty. The stripping heat input also decreases the alkylation
temperature thus improving the alkylation rate of reaction and minimizes the use of catalyst
required
CHAPTER 5
THERMODYNAMICS
5.1.1 Alkylation:
Ethylbenzene Ethylene
5.1.2 Transalkylation:
The main reaction is the alkylation of benzene to give ethylbenzene (Rx.-1). The
above reaction is carried out at 1900 C in the presence of Zeolite Catalyst.
Since the inlet temperature of reactants and outlet temperature of product are at
different temperature we use the following formula for calculating Heat of Reaction at
T=463K
353
298 CP (Benzene) dT - v (Benzene).......[Ref.7]
Where,
463
298 Cp(Product) dT = Sensible Heat of Ethylbenzene
353
298 CP(Benzene) dT = Sensible Heat of Benzene up to its boiling point
+ 6.7508x10-4xT2 ) - 32.75x103
Where,
T2 = Reaction Temperature
T1 = Inlet Temperature
= 97.7686 J/mol.K
= 23.8507 J/mol.K
= 27.479 J/mol.K
= -119.0342x103 - 463x46.4389
CHAPTER 6
MATERIAL BALANCE
MATERIAL BALANCE:
Material balance is the basis of process design. A material balance taken on complete
process determines the quantities of material required and the products produced. Balance
over individual process unit sets the process stream flows and compositions.
Material balances are also useful tool for study of plant operation and trouble
shooting. They can be used to check the performance against design to check instrument
calibration and to locate the source of material loss
= 9433.962 Kmol/Day
Chemical Reaction:
x + 2y = 9433.962
Selectivity =
83 =
x = 83 y
83y +2y=9433.962
85y = 9433.962
y = 110.987 Kmol/day
ENERGY BALANCE
ENERGY BALANCE:
In the process design energy balances are made to determine the energy requirements
of the processs: the heating, cooling and power required in the plant operation an energy audit
on plant will show the pattern of energy usage and suggest the areas for energy conservation
& solving.
The process is considered as perfectly steady state and accumulation of both mass and
energy will be zero.
Q = HP HR + Hr ....( Ref. 7)
Hi =
463
= ni 298 (a + bT +cT2 + dT3) dT
= ni (a (463 - 298) + b/2 (4632 2982 ) + c/3 ( 4633 2983 )+d/4 (4634 2984))
+ 9.5169*109* 1.7551*10-8 )
= 81.070*106 KJ
= 1.1060*109 KJ
= 34735.848*103*25.0405*103
= 8.6980*108 KJ
= 9211.992*103*33390.98087
= 3.0759*108 KJ
= 110.987*103*43691.1745
= 4.8491*106 KJ
HR = HE + HB,IN
= 81.070*106 + 1.1060*109
= 1.18707*109 KJ
FOR EFFLUENT:
= 1.1822*109 KJ
HR = -119.0342 KJ
Therefore Q = HP HR + HR
= - 4.8701*106 KJ
FOR REACTANTS:
HDEB = 6.3763*106 KJ
HB= 1.1636*109 KJ
HR = 1.16997*109 KJ
FOR EFFLUENT:
HEB =9.7662*106 KJ
HB = 1.1599*109 KJ
HP = 1.16966*109 KJ
353
298 CP (Benzene) dT - v (Benzene)......(Ref.7)
= -25.1701 KJ/mol
Q = HP HR + Hr
= -310.025*103 KJ
F = 44391.779 Kmol
D = 34846.83 Kmol
W = 9544.949 Kmol
(ASSUMPTION)
L = 1.5*D
V=L+D
Fhf = 966.707*106 KJ
Whw= 135.442*106 KJ
Dhd = 220.311*106 KJ
Qc = V*B
= 87117.075* 30.75*103
= 2.6786*109 KJ
= 2.0676*109 KJ
F = 9544.949 Kmol
D = 9433.962 Kmol
W = 110.987 Kmol
(ASSUMPTION)
L = 1.5*D
V=L+D
Fhf = 316.957*106 KJ
Whw= 4.8818*106 KJ
Dhd = 219.285*106 KJ
Qc = V*EB
= 23.584*106* 35.56
= 8.3864*108 KJ
= 7.4584*108 KJ
CHAPTER 8
NUMBER OF TRAYS :
In design of distillation column, first we calculate the no. of stages required for
desired separation of component of feed mixture.
We get 99.5% benzene as overhead product & 0.5% as bottom product. (ASSUMPTION)
. = 3.44
y=
Here q= 0.33
tan = - 0.5
= - 26.56
Intercept on Y-axis =
From graph;
x = 0.65 , y = 0.86
Minimum reflux ratio for feed partially vapour ised is given by,
Rm = = 0.6428
= 0.9642
= 0.51
It is pass from (0.005, 0.005) on the diagonal & the point of intersection of feed line &
operating line of rectification section i.e. (0.68, 0.84)
= = 17
The Principal factor that determines the tower diameter is the gas (vapour) velocity. It
is the flooding condition that fixes the upper limit of gas (vapour) velocity. The flooding
velocity is given by
0.5
vfl = ....(Ref. 10)
K = constant
K=1
An = 1.555 m2
An = (100-12) % of At
At =
Dt = ....(Ref. 10)
Dt = 1.5 m
= 0.1977 m3/s
From fig. 8.2 we can say that the liquid flow pattern is single pass plate
= 0.10*0.8837
= 0.08837 m2
= 0.77*1.5
= 1.155m
Weir Height:
hw = 50 mm
Plate thickness = 5 mm
Assuming turndown ratio at 70% of maximum liquid flow rate, so that minimum
(2/3)
(how)max = 0.75
= 38 mm of clear liquid
(2/3)
(how)min = 0.75
vmin =
vmin =
= 6.3326 m/s
= 7.3982 m/s
Thus the minimum operating velocity (7.3982 m/s) lies well above the weep point (i.e. when
vapour velocity = 6.3326 m/s)
ht = hd + hl + hr
hd = K1+ K2 (Vgh)2
Fig. 8.4 Discharge coefficient for gas flow through sieve plates
Vgh =
hd = 50.85*10-3
hl = hw + (how)max
= 50+38
= 88 mm of clear liquid
Residual head,
ht = hd + hl + hr
= 34.73 + 88 + 14.41
Head loss in the downcomer due to liquid flow under the downcomer apron :
hda = 0.166*
Now,
Aap = hap*lw
= hw 10 = 50 10 =40 mm
lw = 1.1 m
= 0.04 * 1.1
= 0.044 m2
2
hda = 0.166
= 15 mm of clear liquid
Check:
To avoid flooding:
hdc <
Now,
Since hdc < 0.275 m, so there will be no flooding at specified operating condition that means
tray spacing is acceptable
Residence Time:
r =
= = 7 sec
SHELL THICKNESS:
ts=
ts =
ts = 24 mm
HEAD THICKNESS:
For safety we use hemispherical head at top & bottom of distillation column. The
head thickness is given by,
th = ....(Ref. 11)
th = ....(Ref. 11)
th = 10 mm
HEIGHT OF COLUMN:
= 10.51 m
CHAPTER 9
COST ESTIMATION
= 5.5*106*(539.1/76.2)
x= Rs. 1.8371*1010
Gross annual earnings = Total Annual Sales Total Annual Product Cost
= 1.95*1010 1.8371*1010
= Rs. 1,12,90,00,000
= 1,12,90,00,000 (0.4*1,12,90,00,000)
= Rs. 67,74,00,000
CHAPTER 10
HEALYH AND SAFETY aspects of the personnel & equipment are important in the
plant. The plant has a variety of compounds that are hazardous to personnel as well as
environment . fire accidents , exposure to chemicals, explosions are some of the major
hazards in the operation the plant . hence safety and environment is given a careful attention.
1. Fire fighting equipments such as CO2 extinguishers and foam extinguishers should be
provided.
2. Electrical equipment in flammable area should be flame proof
3. Lighting conductors should be insulated
4. Welding should be prohibited in the operating plant area . hot work permits should be
demanded for welding purposes
5. Smoking should be prohibited in plant area
6. All leaks in pipelines and elsewhere should be immediately reported and rectified
7. Plant should be kept free of accumulations of waste combustibles ,cotton waste,
paper etc.
Generally, the prime responsibility for plant safety is to be assigned to the line
management. By doing so, overlapping of accountability is prevented. Safety department
fits in a role of staff function by contributing its experience, knowledge and judgment to
influence managements decision on matters concerning safety.
1. Special care is needed when working with chemicals that are known to have
hazardous properties. It is important to understand the hazard in each case and to take
proper precaution.
2. With newly developed chemicals, there may be no toxicity or other hazard data
available. It is safest policy to treat all substances as hazardous until they have been
provided to be otherwise.
3. Work in a well-ventilated fume cupboard ;use safety screens;always wear protective
clothing; use the appropriate type of gloves; wear eye protection
4. Known or suspected carcinogenic substances should only be used after consulation
with senior laboratory management
5. Containers of hazardous substances normally carry warning signs on their labels
The major hazard is from exposure to toxic chemicals. The chemicals in the plant that
are hazardous to the health are carbon black feedstock, its vapours, hydrogen and carbon
monoxide. Thus proper care of personal safety should be taken.
1. Respiratory Protection:
For normal operations, chemical goggles should be worn, along with hard hats. For
situations in which the potential for exposure is greater, a face shield is also recommended.
Safety showers and eyebaths should be provided. They should be located in the
immediate work area and readily accessible to personnel. Both should be tested routinely and
frequently to ensure proper operation
Waste Removal :
The waste gases are sent to vacuum cleanup and incinerated. Thus, waste are
removed.
3. Hazard Identification :
Potential Acute Health Effects:
Hazardous in case of eye contact (irritant), of ingestion, of inhalation. Slightly
hazardous in case of skin contact (irritant, permeator)
Potential Chronic Health Effects :
Slightly hazardous in case of skin contact (irritant, sensitizer).
CARCINOGENIC EFFECTS:
Classified 2B (Possible for human) by IARC.
MUTAGENIC EFFECTS:
Mutagenic for mammalian somatic cells. Mutagenic for bacteria and/or yeast.
TERATOGENIC EFFECTS: Not available.
DEVLOPMENTAL TOXICITY: Not available.
The substance may be toxic to central nervous system (CNS)
Repeated or prolonged exposure to the substance can produce target organs damage.
Other Toxic Effects on Humans :
Hazard in case of ingestion of inhalation.
Slightly hazardous in case of skin contact ( irritant )
Special Remarks on Toxicity to Animals :
Lethal Dose/Conc.50% Kill :
LD50[Rabbit]- Route: Skin: Dose : 17800ui/Kg
Lowest Published Lethal Dose/Conc.:
LDL[Rat]-Rout : Inhalation ( vapour ); Dose: 4000ppm/4H
Special Remarks on Chronic Effects on Humans :
May cause adverse reproductive effects and birth defects (teratogenic) based
on animal test data.
May cause cancer based on animals data. IARC evidence for carcinogenetic in
animals is sufficient. IARC evidence of carcinogenicity in humans inadequate.
May affect genetic material (mutagenic).
Special Remarks on other Toxic Effects on Humans:
Acute Potential Health Effects :
Skin:
Can cause mild skin irritation. It can be absorbed through intact skin.
Eyes:
Contact with vapour or liquid can cause severs eye irritation depending on
concentration. It may also cause conjunctivitis. At a vapour exposure level of 85
200 ppm, it is mildly and transiently irritating to the eyes; 1000 ppm cause further
irritation and tearing; 2000 ppm results in immediate and severe irritation and tearing;
5000 ppm is intolerable (ACGIH, 1991; Clayton and Clayton, 1994). Standardize test
for eye irritation using 500 mg resulted in severe irritation ( RTECS )
Inhalation:
Exposure to high concentrations can cause nasal, mucous membrane and
respiratory tract irritation and can also result in chest constriction and trouble
breathing, respiratory failure and even death. It can also affect behaviour/Central
Nervous System. The effective dose for CNS depression in experimental animals was
10,000 ppm (ACGIH, 1991). Symptoms of CNS depression include headache, nausea,
weakness, dizziness, vertigo, irritability, fatigue, light headedness, sleepiness, tremor,
loss of coordination, judgement and consciousness, coma and death. It can also cause
pulmonary enema. Inhalation of 85 ppm can produce fatigue, insomnia, headache and
mild irritation of the respiratory tract (Haley & Bemdt, 1987).
Ingestion:
Do not drink, pipette or siphon by mouth. May cause gastrointestinal/digestive
tract irritation with Abdominal pain, nausea, omitting. Ethylbenzene is a pulmonary
aspiration hazard. Pulmonary aspiration of even small amounts of the liquid may
cause fatal pneumonities.
8. Transport information
DOT classification: CLASS 3: Flammable liquid
Identification: Ethylbenzene UNNA: 1175 PG: II
Special Provisions for transport: Not available.
CHAPTER 11
Expansion :
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
CHAPTER 12
CONCLUSION
The selection of process for the manufacturing of Ethylbenzene by Mixed liquid
vapour phase zeolite catalyst process is studied and concluded that is economic one. It is a
simple Process.
Though the process is very simple care should be taken to avoid formation of
polyethylbenzene.
CHAPTER 13
REFERENCES