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DEPARTMENT OF CHEMICAL ENGINEERING JAYPEE UNIVERSITY OF ENGINEERING & TECHNOLOGY, A-B ROAD, RAGHOGARH, DT. GUNA – 473226, M.P., INDIA
PRODUCTION OF PHENOL FROM CHLOROBENZENE
Shikhar Prakash (101446)Sumit Verma (101449)
1Production of Phenol from Chlorobenzene
Natural occurrences Natural occurrences:
During fractionation of coal tar, carbonic oil fraction is
separated containing 30-35wt% phenolic components and liquid
byproducts from gasification process.
Applications: Used as an disinfectant in household cleaners and in mouthwash,
used forsynthesis of dyes, aspirin (C9H8O4). Used for making picric acid , Used in the manufacturing of
Bisphenol - A Phenol is also used to produce Aniline
Product specifications & standards
Phenol is classified as a Class B poison.The US Pharmacopeia (USP) specifications for phenol
include:
a) Purity is to be no less than 98 wt%.
b) Clear solubility of 1 part of phenol in 15 parts of water.
c) A congealing temperature to be not lower than 39°C.
d) A content of non volatiles is no more than 0.05 wt%.
Phenol demand forecast in India
Graph 1: Production / Import of phenol in metric ton per year.
2011 2012 2013 2014 20150
50,000
100,000
150,000
200,000
250,000
300,000
DemandProductionImport
Year
Metric tonnes
Plant capacity on demand - supply basis (for 2014)
Demand: 240,000 TPA
Production: 80,000 TPA
Import: 160,000 TPA
Plant Capacity: 200,000 TPA (To meet the demand).
S. No.
Specification UnitsProcesses
Cumene Oxidation Toluene Benzoic Acid
Sulpho-nation
Chloro Benzene
Rasching
Feed Stocks1. Toluene T/T - 1.45 - - -2. Benzene T/T 0.67 - 0.95 1.01 0.9253. Chlorine T/T - - - 1.04 -4. Propylene T/T 0.38 - - - -
Utilities
(Consumption per tonne of phenol)
Steam Tonne 3.5 9.0 2.7 9.0 16.5Cooling water m3 35 65 80 250 50Process water m3 0.02 - 6.5 1.0 -Electricity KWh 350 650 100 3900 350Fuel Oil 106 KJ 4.5 3.5 15 5.5 14Inert gas(High Pressure)
SCF 80 40 - - -
Natural Gas BTU - - 2100 10000 4000
The most widely accepted technology for producing phenol is cumene oxidation process because of better economics due to by-product acetone. If one wants to avoid acetone, the choice will be toluene oxidation process.
Selected process
Phenol from chlorobenzeneThere aretwo reactions to convert chlorobenzene to phenol using chlorination route:
Causticization
C6H5 Cl+ NaOH → C6H5ONa
NaOH is in aqueous media (Operating conditions: 425°C and 350 atm, Exothermic reaction)
Hydrolysis C6H5ONa + HCl (aq) → C6H5 Cl + NaCl (aq)
(Operating conditions: 1 atm & 60 ° C)
Fig1. PFD for production of Phenol from Chlorobenzene
Material Balance
Phenol production with a purity of 99% = 2,00,000 TPA.
All calculations are done on per hour operation.
Working days in a year = 330 days.
Molecular weight of phenol = 94.
Per hour production = 25252.53 kg/hr.
= 268.644 kg mol/hr.
Various assumptions and values taken from literature:
Overall material balance
Component In (Kg/h) Out (Kg/h)
Chlorobenzene 32113.143 1605.668
Sodium hydroxide 14263.810 3423.303
Diphenyl oxide 2575.277 2575.277
Phenol -------- 25507.566
Sodium chloride -------- 15839.168
Total 48952.230 48950.982
Energy balance ΔH 298 = -114.567 KJ/mol
ΔH C6H5Cl = 285.297(230.0238) (373-303) = 17718836.42 J/mol
ΔH NaOH = 356.622 (86.0937) (573-303) = 3243363.955 J/mol
ΔHC6H5OH =271.033 (239.334)(353-303) = 3243363.955 J/mol
ΔH NaCl = 271.033(84.4090) (353-303) = 1143881.74 J/mol
Heat of reaction = Σ Heat of product – Σ Heat of reactant+ ΔH 298
Heat of reaction = -21735942.74 J/mol
Production of Phenol from Chlorobenzene 11
Heat balance across Heat balance across heat exchanger
heat exchanger inlet outlet reactor inlet
Tref = 303 K Tref = 303K,
Tin = 313 K T= 573K
QNaOH = 310595.5465 J Q NaOH = 8342126.471 J
QC6H5Cl = 5449157.38 J QC6H5Cl = 14019901.52 J
Q C12H10O = 45211.0613 J QC12H10O = 1358477.399 J
Heat balance reactor outlet Heat balance neutralizer in
Tref = 303 K, T = 698 K T ref = 303K, T= 333 K
QHCl = 19671615.81 J QHCl = 309069.2717 J
Q C6H5Cl = 1190158.848 J QNaOH = 223550.9719 J
QNaOH =2920034.506 J Q C12H10O = 136762.8128 J
Q C12H10O = 2147280.632 J Production of Phenol from Chlorobenzene 12
QC6H5OH = 3116121.024 J
QNaCl = 115353535.308 J
QC6H5Cl = 111834.3687 J
QNaOH = 372452.6559 J
Q C12H10O = 229770.867 J
Energy balance across distillation column
Assumptions:Temperature of distillate = 460 K
Boiling point of Diphenyl oxide = 531.46 K
Boiling point of phenol =455 K
Feed enters at =353 K
Production of Phenol from Chlorobenzene 13
Production of Phenol from Chlorobenzene 14
Utility required in reactor
Heat of reaction = -21735942.74 J/mol
Cp of water = -75.327 J/mol K
ΔH = n*Cp*dT
-21735942.74 = n*(-75.327)*(40)
n = 7213.861 moles
Weight of water required = 7213.861*18 = 129849.5126 g/hr
Process & mechanical design of neutralizing tank C6H5ONa + HCl C6H5Cl + NaCl EQUIPMENT - Cylindrical vessel with a drain valve and a turbine agitator
Total weight of the reacting mass = 48950.587 kg/h Average density at 60oC= 1.4006 kg/litre Total volume of reacting mass= Total weight of the reacting mixture
Average Density
Let residence time (T) = 2 hours
Vo= mav/dav =34.949 m3/hr
T = V / Vo
V = 69.898 m3
Where V = Volume of reactor
L/D = 1.25
D= 4.14 m, H=5.18 m
Mechanical design The maximum pressure in the tank is 14.70 psi (1
atm)
ts=[{(14.70 x 4.14)/(2 x 20000 x 0.8)}+0.005] x 2.54 =5.13 mm
Take shell thickness= 5mm
Design pressure is above 100 Kpa, ellipsoidal head would be an ideal choice
Major axis: Minor axis=2:1
Inside depth (B=A/2), A=D/2, B=D/4
B=1.035 cm
Volume V of the ellipsoidal head
V = (3.14 x 4.142 x 5.18/4) + (3.14 x 4.143/12) = 88.306 m3
Design of agitator
Let diameter of the agitator= 0.6 x D
Da= 0.6 x 4.14= 2.484 m
Speed of the agitator=75 rpm = 1.2 rps
Average Viscosity =3.6 cp
Average density of the slurry=1.1747 kg/lt
Calculating Reynolds Number Nre
Nre = 112584.00
Calculating Froude number Nfr
Nfr = n2 x Da/g = 1.252 x 2.484/9.81 = 0.3956
1 cm=1/30.8 ft
1 kg/lt= 62 lb/ft3
9.81 m/s2=32.17 ft/s2
Power=[(0.123)-0.0935 x 1.253 x (8.1710)5 x 1.4006 x 62]/32.17
Power=331.52 ft/lbf
Power=0.513 HP
Assuming frictional losses
Power= 1.5 HP
Torque in the shaft=2 x 550/2 π n
Torque in the shaft= 140 ft/lbf
Distillation Column: Process design Feed components:
Phenol – 271.0333 kmol/hrDiphenyl oxide – 15.13 kmol/hrTotal feed = 286.163 kmol/hr
Distillate components:
Phenol – 265.64 kmol/hrDiphenyl oxide – 2.683 kmol/hrTotal = 268.323 kmol/hr
Bottom components:
Phenol – 5.393 kmol/hrDiphenyl oxide – 12.447 kmol/hrTotal = 17.84 kmol/hr
Component Feed, xf Distillate, xd Bottom, xb
Phenol 0.947 0.99 0.302
Diphenyl oxide 0.053 0.009 0.698
Using Antoine Equation, we find vapor pressure:
P = A-(B/ (T+C)) T in Kelvin, Pressure in bar.
Component A B C
Phenol 4.24688 1509.677 -98.949
Diphenyl oxide 4.13678 1800.415 -95.324
Top temp at 123°C Bottom temp at 150°C
Phenol 0.14599 0.3948
Diphenyl oxide 0.01409 0.04487
Calculated Vapour Pressure in bar:
Heavy key component – Diphenyl oxideLight key component – Phenol
Relative volatility calculation :α top = 10.36α bottom = 8.798
α avg = (α top* α bottom)0.5
= (10.36*8.798)0.5
= 9.5475.
Fenske equation :
Nm = log [(XLK/ XHK)d*( XHK/ XLK)b] / log αavg
(XHK) d = 0.302
(XLK) d = 0.698
(XHK) b = 0.990
(XLK) b = 0.009
Nm = log [(0.698/ 0.302)*( 0.990/ 0.009)] / log 9.5475
= 2.52 Nm ≈ 3
Underwood’s Method:
∑ (αi*xif)/ (αi-θ) = 1-q
We get, θ =1.4960
∑ (αi*xif)/(αi-θ) = Rm+1
We get, Rm = 0.138
Gilliland’s correlation:
On solving, we get –N = 8.983 ≈ 9Assuming, tray efficiency = 0.5Therefore, actual no. of trays = 9/0.5 = 18
Tower diameter required at top:
Distillation: Vacuum distillation at 100mm Hg
Molar flow rate of vapor & liquid at top in enriching section –
L = R*D = 0.2074*268.323 = 55.650 kmol/hr
V = (R+1)*D = 1.2074*268.323 = 323.973 kmol/hr
L/V = 55.650/323.973 = 0.172
Mavg = ∑xiMi = 94.7621
Assuming tray spacing = 0.6 m
From Figure 11.27 of R.K Sinnott (Coulson & Richardsons) page-568
K1 = 0.08
uf = flooding velocity
uf = 3.6 m/sec
Now, Actual velocity = 0.85 * uf = 2.88 m/sec
Volumetric flow rate of vapor at the top, Qv = (V+Mavg) / ρv = 2.168 m3/s
An = net area required at the top
An = Qv/V = 0.753 m2
Down comer area, Ad = 0.12*Ac (Reference: Sinnott)
An = Ac – Ad
On solving, Ac = 0.856 m2
Di = 0.98 m
Tower diameter required at bottom:Similar procedure was followed to calculate
bottom diameter:Bottom diameter comes out to be 1.02 m
Height of Distillation Column:Height of column, Hc = no. of trays * tray
spacingActual no. of plates = 18Tray spacing = 0.6 mSo, height of column = 18 * 0.6 =10.8 m
Mechanical designCalculation of Thickness:Allowable design stress, f= 1.18MN/m2 Welding joint efficiency factor, J=0.85
t = [PDi/ (2*f*J-P)]
= [(13.33*103*1.02)/ (2*1.18x106*0.85)-(13.33*103)]
= 0.06 m
Economic Analysis
Costing of distillation columnThickness of shell = 0.06 m
Weight of vessel = = x 10.8 x 0.06 x 7850 = 16292.003 Kg Where r is the internal radius of distillation
column, L is the length of column, t is the thickness of shell.Density of carbon steel = 7850 Kg/m3
Weight of head, skirt = 10% weight of vessel.Total weight of column without tray = 1.1 x 16292.003 = 17921.23 Kg
Production of Phenol from Chlorobenzene 31
Production of Phenol from Chlorobenzene 32
Therefore, Purchased cost of distillation column without trays (1990) = $ 105
Production of Phenol from Chlorobenzene 33
Purchased cost of tray = $ 300 per/trayTotal cost of trays = 18 x $ 300 = $ 5400Quantity factor of each tray = 1.10Total cost of the trays = 1.10 x $ 5400 = $ 5940Total cost of distillation column in 1990 = $ (105 + 5940) =$
105940Cost index in 1990 (C1) = 356 (Chemical engineering plant
cost index refer Klaus D.Timmerhaus Page 163)
Cost index in 1990 (C2) = 588.6 P1 = Purchased cost of distillation column in 1990P2 = Purchased cost of distillation column in 2014 Present Cost = Original Cost P2 =105940 = $ 17518 = Rs 17518 59 = Rs 10,334,327
Production of Phenol from Chlorobenzene 34
Costing of various equipments1. Purchased cost of distillation column = Rs
10,334,3272. Purchased cost of heat exchanger = Rs.
82837363. Purchased cost of Neutralizer = Rs 3217984. Purchased cost of reactor = Rs 29966100
Production of Phenol from Chlorobenzene 36
S No Raw material Cost ($/kg)
Total Consumption
in Kg/Year
Rs/Year
01 Chlorobenzene 0.5 241619202 7127766459
02 Sodium Hydroxide 0.3 85856815.44 1519665633
03 Diphenyl ether 3 20396193.84 3610126310
Total 12257558402
Cost of raw materials
Component $/kg Total production (kg/yr) Rs/year
Phenol 1.6 202019923 19120683690
Diphenyl ether 3 20396193.84 3610126310
Total product cost 22730810000
Total product cost
Production of Phenol from Chlorobenzene 37
Cash flow statement
Cash flow statement Non-discounted parameters(a) CCP (cumulative cash position) = Rs 38.02 crores
(b) Payback PeriodLand + working capital = 1.12 + 3.67 = 4.8Payback period is the point at which cumulative cash flow is
equal to the sum of land and working capital.Payback period (PBP) = =3+((4.939-4.8)/(4.939-0.77))Therefore, PBP = 3.033 years
(c) Rate of return on investment (ROROI)
Where n is the project life. ROROI = 20.68 %
Production of Phenol from Chlorobenzene 38
Production of Phenol from Chlorobenzene 39
Plant layout
First Aid safety measuresEyes: Get medical aid immediately. Do NOT allow victim to rub or keep eyes closed. Extensive irrigation with water is required (at least 30 minutes).
Skin: Get medical aid immediately. Immediately flush skin with plenty of soap and water for at least 15 minutes while removing contaminated clothing and shoes. Wash clothing before reuse. Discard contaminated clothing in a manner which limits further exposure. SPEEDY ACTION IS CRITICAL! Destroy contaminated shoes.
Ingestion: Do NOT induce vomiting. If victim is conscious and alert, give 2-4 cupfuls of milk or water. Never give anything by mouth to an unconscious person. Get medical aid immediately.
Inhalation: Get medical aid immediately. Remove from exposure to fresh air immediately. If breathing is difficult, give oxygen. Do NOT use mouth-to-mouth resuscitation. If breathing has ceased apply artificial respiration using oxygen and a suitable mechanical device such as a bag and a mask.
Notes to Physician: Persons with liver or kidney disease should not be exposed to phenol for any length of time.
Antidote: Activated charcoal, followed by cathartic, may be preferred to ipecac induced emesis or lavage in decontamination of the GI tract and preventing systemic absorption of phenol.
Production of Phenol from Chlorobenzene 40
Conclusions
After studying the entire process of manufacture of phenol, there are a few recommendations: ◦ Phenol production has a very good scope
in India.◦ For most of the equipments, the fixed
capital investment is higher but the payback period is small.
Production of Phenol from Chlorobenzene 41
Thank You..
References [1] http://www.helium.com/items/2025739-medical-uses-for-phenol
[2] http://www.greener-industry.org.uk/pages/phenol/1PhenolAnnualProd.htm
[3] Kirk R. E., Othmer D. F., Encyclopedia of Chemical Technology, John Wiley and Sons, 1994, Volume 18 Page no: 291
[4]http://www.honeywell-pmt.com/sm/chemicalintermediates/phenol-n3/phenol-properties- spec.html?c=21
[5] http://www.icispricing.com/il_shared/Samples/SubPage186.asp
[6] http://en.wikipedia.org/wiki/Phenol#Properties
[7] http://en.wikipedia.org/wiki/Phenol
[8] http://hazard.com/msds/mf/baker/baker/files/p1949.htm
[9] Dryden C. E., Outlines of Chemical Technology, East-West Press, 2008
[10] Kirk R. E., Othmer D. F., Encyclopedia of Chemical Technology, John Wiley and Sons, 1999-2012
[11] Carl L.Yaws, Chemical Properties Handbook, Tata McGraw Hill publications, Third Edition.
[12] Max S.Peters, Klaus D.Timmerhaus, Plant design and economics fro chemical engineers, McGraw-Hill International editions, chemical and petroleum engineering series, fourth edition.
[13] http://www.matche.com/equipcost/
[14] http://avogadro.chem.iastate.edu/MSDS/phenol.htm
Production of Phenol from Chlorobenzene 43