Cumene Manufactring

Manufacturing of Cumene
Chapter 1 INTRODUCTION
Cumene is the common name for isopropyl benzene, an organic compound that is an aromatic hydrocarbon. It is a constituent of crude oil and refined fuels. It is a flammable colorless liquid that has a boiling point of 152 C. Nearly all the cumene that is produced as a pure compound on an industrial scale is converted to cumene hydro-peroxide, which is an intermediate in the synthesis of other industrially important chemicals such as phenol and acetone. Cumene (isopropyl benzene) is produced by reacting propylene and benzene over an acid catalyst. Cumene may be used to increase the octane in gasoline, but its primary use is as a feedstock for manufacturing phenol and acetone. The preparation of cumene was first described in 1841 when Gerhardt and Cahours obtained it by distilling cumic acid with lime. The use of aluminium chloride to alkylate benzene was reported by Radziewanowski in 1892. Before the development of the cumene route to phenol and acetone, cumene had been used extensively during World War II as a fuel additive to improve the performance of aircraft piston engines. Like phenol and acetone, -methylstyrene, diisopropylbenzene, or acetophenone, although these cumene derivative compounds are of considerable commercial importance. Currently, over 80% of all cumene is produced by using zeolite based processes. Early processes using zeolite based catalyst system were developed in the late 1980s.[9]
Gharda institute of technology, lavel
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Chapter 2 PROPERTIES
Cumene is colorless liquid soluble in alcohol, carbon tetra chloride, ether and benzene. It is insoluble in water.
2.1 PHYSICAL PROPERTIES OF CUMENE[8]

PROPERTY Molecular weight Boiling Point, C Freezing point, C Density, gm/cm3 0C 20C 40C Thermal conductivity, w/m.k 25C Viscosity, mPa.s (cp) 0C 20C 40C Surface tension, mN/m 20C Flash point, C Autoignition temperature, C 0.791 44 523 1.076 0.791 0.612 0.124 0.8786 0.8169 0.8450 VALUE 120.19 152.39 -96.03
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Antoine Constants A B C 13.99 3400 207.78
2.2 THERMODYNAMIC PROPERTIES OF CUMENE[8]

PROPERTY Relative molar mass Critical temperature, C Critical pressure, Kpa Critical density, g/cm3 Heat of vapourisation at bp, J/g Heat of vapourisation at 25C, J/g VALUE 120.2 351.4 3220 0.280 312 367
2.3 CHEMICAL PROPERTIES:[8]

1. Cumene undergoes oxidation t o give cumene hydroperoxide by means of air or Oxygen C6H5CH(CH3)2 + O2 C6H5C(CH3)2OOH Cumene Oxygen Cumene Hydroperoxide 2. By the catalytic action of dilute sulphuric acid, cumene hydroperoxide is split into Phenol and acetone C6H5C(CH3)2OOH C6H5OH + CH3COCH3 Cumene Hydroperoxide Phenol Acetone
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Chapter 3 USES
Cumene is used[2] 1. As feedback for the production of Phenol and its co-product acetone 2. The cumene oxidation process for phenol synthesis has been growing in popularity Since the 1960s and is prominent today. The first step of this process is the formation of cumene hydroperoxide. The hydroperoxide is then selectively cleaved to Phenol and acetone. 3. Phenol in its various for maldehyde resins to bond construction materials like plywood and composition board (40% o f the phenol produced) for the bisphenol. A employed in making epoxy resins and polycarbonate (30%) and for caprolactum, the starting material for nylon-6 (20%). Minor amounts are used for alkylphenols and pharmaceuticals. 4. The largest use for acetone is in solvents although increasing amounts are used to make bisphenol A and methylacrylate. 5. Methylstyrene is produced in controlled quantities from the cleavage of cumene Hydroperoxide or it can be made directly by the dehydrogenation o f cumene. 6. Cumene in minor amounts is used as a thinner for paints, enamels and lacquers and to produce acetophenone, the chemical intermediate dicumylperoxide and diisopropyl benzene. 7. Cumene is also used as a solvent for fats and raisins.
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Chapter 4 MANUFACTURING PROCESSES OF CUMENE.

There are four types of manufacturing process of cumene. 1. Liquid phase alkylation using Phosphoric acid. 2. Liquid phase alkylation using Aluminium chloride. 3. Q-Max process. 4. CD-Cumene process. 4.1 LIQUID PHASE ALKYLATION USING PHOSPHORIC ACID [2]
4.1.1 INTRODUCTION
SPA (Solid phosphoric acid) remains a viable catalyst for cumene syenthesis. In recent years , producers have been given increasing incentives for better cumene product quality of the phenol, acetone, and especially alpha-methyl styrene produced from the downstream phenol units. 4.1.2 CHEMICAL REACTION Main Reaction C6H6 + CH3.CH=CH2 Side Reaction C6 H6 + nCH3CH=CH2 C6 H6-n.(CH)n C6H5. C3H7 ;
4.1.3 PROCESS DESCRIPTION Propylene-propane feedstock from refinery off gases from a naphtha steam cracking plant and recycle benzene is mixed with benzene are charged upflow into fixed bed reactor, which operates at 3-4 MPa and at 200-260 C and pumped at 25 atms. Into the top of a reactor packed stage wise with H3PO4 impregnated catalyst. The SPA catalyst provides an essentially complete conversion of propylene on a one pass basis. The temperature is maintained at approximately 250 C by adding cold propane at each stage to absorb heat of reaction. The reactor effluent is depropanized and the propane split into quench or product streams. The propanized bottoms are separated into benzene, cumene,and polycumenes in the remaining
Gharda institute of technology, lavel Page 5
two stills. A typical reactor effluent stream contain 94.8 wt% cumene and 3.1 wt% diisopropylbenzene (DIPB). The remaining 2.1% is primarily heavy aromatics. This high yield of cumene is achieved without transalkylation of DIPB is the key advantage of SPA catalyst process. The cumene product is 99.9 wt% pure. The heave aromatics which have research octane no (RON) of about 109 can be either used as high octane gasoline blending components or combined with additional benzene and sent to transalkylation section of the plant where DIPB is converted to cumene. The overall yield of cumene for this process based on benzene and propylene is typically 97-98 wt% if transalkylation is included or 94-96 wt% without transalkylation
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4.1.4 PROCESS FLOW DIAGRAM
Figure 4.1.4.a Liquid phase alkylation using phosphoric acid
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4.2 LIQUID PHASE ALKYLATION USING AlCl3 [2]

4.2.1 INTRODUCTION Aluminium chloride is a preferred alkylating agent for the production of cumene. Basically the design is same to that described for other processes, having pretreatment section if required, a reactor section and a distillation section. The reaction conditions, including arrangement for the feeding catalyst and recycle of polyalkylbenzenes for dealkylation are however quite different. 4.2.2 PROCESS DESCRIPTIONIf feed treatment is required depending on the quality of feedstock, propylene is dried in a regenerative absorptive drier and fed to de-ethanizer where c2 compounds are distilled. The bottoms pass to a propylene column where c4s and heavier are removed in the base stream. Liquid propylene in the overheads is vaporized and fed to the reactor. Fresh benzene contains too much water for immediate addition to the reactors, is mixed with recycle benzene and fed to column. After condensation, benzene and water separate in a decanter. Benzene from the base contains less than 10ppm water. The reaction section usually consists of two or more brick lined vessels partitioned into reaction and settling zones with downstream separators and wash drums. All the reactants and recycle streams are introduced into the reaction zone. Since agitation is required, propylene vapours are admitted at the base where catalyst complex, which is insoluble in a hydrocarbon, tends to settle. The complex is hereby lifted and mixed intimately with the reactants. Aluminium chloride is added to the top of the reactor and the promoter usually HCl or isopropyl enters with the reactant. The promoter is essential for stabilizing the catalyst complex, for only a stable complex will catalyze the reaction. In addition to the gaseous feed to distribute the catalyst complex, there may be provided a pump to recirculate settled complex to the top of the reaction zone and a compressor to recycle propane. The distillation section consist of ethylbenzene unit have been constructed where the catalyst complex is prepared in a separate vessel. Care has to be taken with the reactor off gases which in addition to benzene and other light hydrocarbons contains HCl. The benzene is recovered in an absorber containing recycling PAB and the HCl is scrubbed out of the off- gas in two towers, one containing water and the other containing caustic
soda solution. The residual gas can be compressed and used as fuel. The material heavier than cumene is not disposed of as fuel, is returned to the reactors for transalkylation after removing the heaviest polyalkylbenzenes. The later operation is conducted in a small column under high vacuum. 4.2.3 PROCESS FLOW DIAGRAM
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Fig 4.2.3.a Liqid phase alkylation using Aluminium Chloride Gharda institute of technology, lavel Page 10
4.3 Q-MAX PROCESS[1,5,6]

4.3.1 INTRODUCTION The Q- Max process is based on liquid phase process. The Q-Max process produces nearly equilibrium levels of cumene between 85 to 95 mole% and DIPB between 5 and 15 mole%. The Q-Max process had selected most promising catalyst based on beta zeolite for cumene production. 4.3.2 PROCESS DESCRIPTION A Q-max unit consists of an alkylation reactor, a distillation section, and a transalkylation reactor. Both reactors are fixed bed. The alkylation reactor is divided into four catalyst beds contained in a single reactor vessel. Propylene and a mixture of fresh and recycle benzene are charged to the alkylation reactor, where the propylene reacts to completion to form mainly cumene. Effluent from the alkylation reactor is sent to the depropanized column, which removes the propane that entered the unit with the propylene feed, along with any excess water which may have accompanied the feeds. The Depropanizer column bottoms is sent to the benzene column where benzene is collected overhead and recycled. Benzene column bottom is sent to the cumene column where cumene product is recovered overhead. The bottom from the cumene column, containing mostly diisopropylbenzene is sent to the DIPB column where DIPB is recovered and recycled to the transalkylation reactor. The bottoms from the DIPB column consist of a small stream of heavy aromatic by-product which are normally used as high octane gasoline blending component. The catalyst in both the alkylation and transalkylation reactors is regenerable. The typical design cycle length between regenerations is 2years, but the unit can be designed for somewhat longer cycles if desired. Ultimate catalyst life is at least three cycle. Mild operating conditions and a corrosion free process environment permit the use of carbon steel construction and conventional process equipment.
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Recycle Benzene Benzene Propylene Propane DIPB Cumene
Alkylation Reactor
Heavies Transalkylation Reactor Benzene Column Cumene Column DIPB Column
Depropanizer
Figure4.3.3.a : Q-Max process
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4.4 CD CUMENE PROCESS[1]

4.4.1 INTRODUCTION The CD- Cumene process produces ultra high purity cumene using a proprietary zeolite catalyst that is non corrosive and environmentally friendly. 4.4.2 PROCESS DESCRIPTION Cumene is formed by the catalytic alkylation of benzene with propylene. CD-cumene process uses a proprietary zeolite catalyst. The catalyst is non corrosive and environmentally friendly. This modern process features higher product yields, with a much lower capital investment, than the environmentally outdated acid- based processes. The unique catalytic distillation column combines reaction and fractionation in a single unit operation. The alkylation reaction takes place isothermally and at low temperature. Reaction products are continuously removed from the reaction zones by distillation. These factors limit the formation of by-product impurities, enhance product purity and yields, and result in expected reactor run lengths in excess of two years. Low operating temperatures result in lower equipment design and operating pressures, which help to decrease capital investment, improve safety of operations, and minimizing fugitive emissions. All waste heat, including the heat of reaction, is recovered for improved energy efficiency. The CD-cumene technology can process chemical or refinery grade propylene. It can also use dilute propylene streams with purity as low as 10mol percent, provided the content of other olefins and related impurities are within specification. ZEOLITE CATALYST. Except for the CDTech process, which combines catalytic reaction and distillation in a single column, all zeolite-based processes consist of essentially the same flowsheet configuration. The alkylation reaction is carried out in fixed-bed reactors at temperatures below those used in SPA-based processes. When refinerygrade propylene is used as a feedstock, the effluent from alkylation is sent to a depropanizer column that removes propane overhead. A separate transalkylation reactor converts recycled PIPB and benzene to additional cumene. The
bottoms of the depropanizer are then mixed with the transalkylation reactor effluent and fed to a series of three distillation columns. Benzene, product cumene, and PIPB are respectively separated in the overhead of each column, with PIPB and benzene recycled to the reaction system. A small stream of heavy aromatics is separated in the bottoms of the PIPB column. Like the AlCl3 catalyst, zeolites are sufficiently active to transalkylate PIPB back to cumene. Overall selectivity of benzene to cumene is quite high, varying from 99.7% to almost stoichiometric, depending on the nature of the zeolite employed. Product purities as high as 99.97% can be obtained, with B/P feed ratios between 3 and 5. A particular advantage of the zeolite catalysts is that they are regenerable and can be used for several cycles. Therefore, the waste disposal problems associated with SPA and AlCl3 catalysts are greatly reduced. In addition, carbon steel can be used as the material of construction throughout the plant because of the mild operating conditions and the absence of highly corrosive compounds. One limitation of the zeolite technology is potential poisoning of the catalyst by contaminants in the feed. Depending on feedstock quality, guard beds or additional feed pretreatment may thus be required. If refinerygrade propylene is used, for example, its sulfur content must be closely controlled.
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Benzene Propane Cumene
Propylene
Cumene Column
Transalkylator
PIPB Column
PIPB Recycle
Heavies
Figure : CD- Cumene process
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Chapter 5 SELECTION OF PROCESS

5.1 ADVANTAGES 5.1.1 LIQUID PHASE ALKYLATION USING PHOSPHORIC ACID[2] a) The SPA catalyst provides an essentially complete conversion of propylene on a one pass basis. b) Cumene product 99.9 wt% pure. c) By product removal is relatively simple. 5.1.2 LIQUID PHASE ALKYLATION USING AlCl3[2] a) Propane in propylene feed is recovered as liquid petroleum gas(LPG) b) By product removal is relatively simple. c) PAB may be recycled to the reactor as aluminium chloride has ability to transalkylated PAB in presence of benzene. 5.1.3 Q-MAX PROCESS[1] a) The catalyst in the both alkylation and Transalkylation reactor are regenerable. b) The expected catalyst cycle is 2-4 years and the catalyst should not need replacement for at least 3 cycles. c) The Q-Max requires minimum pretreatment of feeds, which further minimizes the capital costs. 5.1.4 CD- CUMENE PROCESS[1] a) High selectivity and lower by product formation. High product yield; reduced plot area. b) Lower maintenance cost. c) Decrease capital investment; improve safety and operability; applicable to conversion of existing cumene plants. d) Reduces utilities and operating cost; recover all waste heat and heat of reactions.
e) Improves economics plant can be custom designed to process specific feed stocks including the less expensive feedstock. f) Continuous process. g) Meets evolving environmental requirements. h) Catalytic reaction and distillation is done in single column.
5.2 DISADVANTAGES 5.2.1 LIQUID PHASE ALKYLATION USING PHOSPHORIC ACID[2]: a) Cumene yield is limited to 95% because of the oligomerization of propylene and the formation of heavy alykalate by-products. b) The process requires a relatively high benzene propylene molar feed ratio on the order of 7/1 to maintain cumene yield. c) The catalyst is not regenerable and must be disposed at the end of each short catalyst cycle. 5.2.2 LIQUID PHASE ALKYLATION USING ALUMINIUM CHLORIDE[2]: a) Feed pretreatment is required. b) The presence of HCL in and around the reaction area can be troublesome; its treatment is the major disadvantage of this process. Q-Max Process and CD-Cumene process doesnt have any disadvantage. But from this two processes CD-Cumene process is more effective than Q-max process because, a) Extends reactor run length over one year without regeneration, sustain high conversion and selectivity. b) Decrease capital investment, improves safety and operability. c) Reduces utilities and operating costs, recovers all waste heat and heat of reaction. d) Improves economics- plans can be custom designed to process specific feedstocks including less expensive feedstock. So that we are selecting CD-cumene process of manufacturing of CUMENE.
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Chapter 6
THERMODYNAMIC FEASIBILITY Table 6.a : Thermodynamic data Component Cumene Propylene Benzene Chemical reaction C3H6 + C6H6 C9H12 Reaction temperature = 170 6.1 Calculation of heat of reaction at 443K Hr = Hf298 + }..[10] Cp values are,[4] Cp(cumene) = 124.62 + 6.39210-1T 1.733110-3T2 + 2.214610-6T3 Cp(propylene) = 54.718 + 3.451210-1T 1.631510-3T2 + 3.875510-6T3 Cp(benzene) = 31.662 + 1.3043T 3.607810-3T2 + 3.824310-6T3 For Cumene ( ) { ( ) + ( ) Cp (J/mol k) 217.96 115.3 137.87 Entropy @298(J/mol k) 388.57 266.6 269.20 Hf @298(KJ/mol) 3.93 20.42 82.93 Gf @298(KJ/mol) 136.96 62.72 129.66
298
443 (124.62+6.3293*10-1T-1.7331*10-3T2+2.2146*10-6T3)dT
= 18069.9 + 34002.58 34936.24 + 16956.92 = 34.093 KJ/mol
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For Propylene
443 298 (54.718
+ 3.4512*10-1T - 1.6315*10-3T2 + 3.8755*10-6T3)dT
= 7934.11 + 18540.71 32888.16 + 29674.23 = 23.260 KJ/mol For Benzene

298
353(-31.662 + 1.3043T 3.6078*10-3T2 + 3.8243*10-6T3)dT +30.75 = 4590.99 + 70070.25 72726.89 + 29282.21 + 30.75 = 22.065KJ/mol
Heat of formation at 298K Hf298 = Hf(product) Hf(reactant)[10] = Hf(cumene) [Hf(propylene) +Hf(benzene) ] = 3.93 (20.42 + 82.93) = 99.42KJ/mol Heat of reaction at 443K Hr443 = 99.42 + 34.093 23.260 22.065 = 110.652KJ/mol Heat of reaction is negative, so the reaction is exothermic.
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6.2 Calculation of Entropy S443 = S298 + ( ) ..[11]
= S298 + ln(T2/T1) + (T2 T1) { [1/(T2)2] [1/(T1)2] } For Cumene S443 = 388.57 + 124.621 ln(443/298) + 6.3293(443298) +1.733110-3 [ (1/4432) (1/2982) ] = 388.57 +49.401 + 917.74 1.06810-8 = 1355.711J/mol For propylene S443 = 266.6 +54.718 ln(443/298) + 3.451210-1(443298) + 1.631510-3 [ (1/4432) (1/2982) ] = 266.6 +21.694 +50.04 110-8 = 338.334J/mol For Benzene S443 = 269.20 31.662 ln(443/298) + 1.304310^-1(443298) + 3.607810-3 [ (1/4432) (1/2982) ] = 269.20 12.55 +18.912 2.2210-8 = 275.56J/mol
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Entropy of reaction at 443k S443 = S(product) S(reactant) [11] = 1355.711 (338.334 +275.56) =741.817J/mol = 741.81710-3 KJ/mol 6.3 calculation of Gibbs free energy G = H TS [11] = 110.652 [443(741.81710-3)] = 439.27KJ/mol Gibbs free energy is negative, so the reaction is feasible. 6.4 Calculation of equilibrium constant G = RT ln(Kp) ...... [10] Kp = = = 1.12
( )
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Chapter 7 MATERIAL BALANCE

Plant capacity 300,000 ton / year. Assuming 300 working days. Basis- 1000 ton/ day cumene production = 41666.67 kg/hr = 346.67 kmol/hr ReactionMain reaction: C3H6 + C6H6 C9H12 Side reaction: C9H12 + C3H6 C6H4( CH (CH3)2)2 Assuming 95% conversion is possible in reactor-1. Hence 90% of cumene get converted into cumene and 5% propylene get reacted with cumene to form PIPB. Propylene fed = 346.67 kmol/hr Benzene to propylene feed ratio is 4:1. Benzene fed = 1400 kmol/hr Propylene reacted = 0.95 * 346.67 = 329.33 kmol/hr Unreacted propylene = 346.67 329.33 = 17.34 kmol/hr Benzene reacted = 0.9 * 346.67 = 312 kmol/hr
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Since the reaction is exothermic. Hence heat evolved in CD-column is = 0.95 * propylene feed * heat of reaction = 0.95 * 346.67 * 96.428 = 31757.26 kJ Benzene evaporated = (total heat evolved) / (latent heat of benzene) = (31757.26) / (30.75) = 1032.75 kmol Benzene fed into CD-column = benzene evaporated in CD-column + benzene reacted = 1032.75 + 312 = 1344.75 kmol/hr Unreacted benzene = 1344.75 312 = 1032.75 kmol/hr Cumene produced = 312kmol/hr But 5% of propylene reacts with the cumene and produce PIPB (it contains DIPB and little amount of TIPB) Cumene produced = 312 0.05 * 346.67 = 294.67 kmol/hr Cumene produced in finishing reactor = 0.05 * 346.67 = 17.33 kmol/hr From given, Selectivity of propylene to cumene = 81.7 Benzene reacted with DIPB to produce cumene = 0.05 * 346.67 = 17.33 kmol/hr DIPB produced = 0.98 * 17.33
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= 16.98 kmol/hr Net amount cumene produced = 312 + 17.33 + 16.98 = 346.31kmol/hr PIPB produced = 0.02 * 17.33 = 0.3466 kmol/hr Material balance of cumene column: cumene 346.31 Kmol/hr
Cumene + DIPB 346.31 Kmol/hr + 17.33 Kmol/hr
DIPB 17.33 Kmol/hr Material balance of DIPB column: DIPB 16.9834 Kmol/hr
DIPB 17.33 Kmol/hr
Heavy ends 0.3466 Kmol/hr

Material balance of transalkylation reactor: Cumene 16.9834Kmol/hr
Benzene + PIPB 16.9834 Kmol/hr +16.9834Kmol/hr
Material balance for finishing reactor:
Benzene = 17.33 kmol/hr cumene = 17.33 kmol/hr propylene = 17.33 kmol/hr
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Chapter 8 ENERGY BALANCE

Plant capacity is 300,000 ton / year. Assuming 300 working day . Basis = 1000 ton of cumene per day = 346.67 kmol/hr Cp values data: Component Cumene Propylene Benzene A 10.149 31.298 -31.368 B 5.1138E-1 7.2449E-1 4.7460E-1 C -1.7703E-5 1.9481E-4 -3.1137E-4 D -2.2612E-7 -2.1582E-7 8.5237E-8
Energy balance on CD-column Benzene propylene unreacted benzene + propylene cumene + PIPB
Cumene synthesis is exothermic reaction. The heat given out when 1mol propylene reacted is the heat of reaction = 96.428 kJ Hence total heat given out = 33393.98 kJ/hr This amount of heat is taken out of reaction zone by evaporation of benzene. This vapour phase benzene is then cooled and bring to liquid phase. Hence heat taken out in condenser is, Condenser load = 33393.98 kJ/hr
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Energy balance on cumene column : Cumene
Cumene + DIPB
DIPB The cumene with PIPB comes out from CD-column at 152 C. This mixture is heated to near about 170 C to distill out cumene from the PIPB column. Heat load on reboiler = mCpT = [346.67 * 217.96 * (170-152)] + [17.33 * 382.42 * (170-152)] = 1477.96 * 103 kJ/hr The cumene is cooled to liquid phase, Load on condenser = mCp(35-170) = 346.67 * 217.96 * (35-170) = 10200.63 * 103 kJ/hr
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Energy balance on PIPB column-
DIPB
DIPB
Heavy ends PIPB comes out from cumene column is separated in DIPB and heavier ends, for this separation mixture is heated to 200 c. Reboiler load = 17.33 * 382.42 * (200-170) = 1988.35 * 102 kJ/hr Energy balance on transalkylation reactorCumene
Benzene + PIPB
In this unit producing cumene from DIPB and benzene. Since reaction is exothermic. The net heat given out from the reaction = 96.428 * 17.33 = 1671.09 kJ/hr Condenser load = 1671.09 kJ/hr
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Chapter 9 DESIGN OF MULTICOMPONENT DISTILLATION COLUMN

Assume 99% benzene is separated as a overhead & 99.5% cumene is separated as bottom product In our case 1. 2. 3. 4. Propylene lighter than light key Benzene light key Cumene heavy key PIPB heavier than heavy key
Material balance Component Feed Moles 17.34 1032.75 346.31 17.33 1413.73 Distllate Mol 17.34 1022.42 1.732 Bottom Mol 10.33 344.58 17.33 372.24
Propylene Benzene Cumene DIPB Total
Mol. Fraction 0.0123 0.721 0.245 0.0122
Mol fraction 0.0166 0.98 0..166 -
Mol fraction 0.0277 0.926 0.0465
Vapor pressure data Log p = A- B/(T+C) Calculation of top temperature Component Propylene Benzene Cumene yi 0.0166 0.98 0.00166 pi 31627.13 927.68 96.31 ki 17.15 1 0.09 xi = yi/ki 0.000968 0.98 0.018 0.999
Top temperature = 870C
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Calculation of bottom temperature Component Propylene Benzene Cumene Xi 0.0277 0.926 0.0465 Pi 4521.18 733.30 185.11 ki 5.43 0.9 0.188 yi = kixi 0.150411 0.8334 0.008742 0.993
Bottom temp = 152 0 C Nmin = =

( ( ) ( )
)(
= 3.67 Minimum reflux ratio Lower pinch temperature = column top temp. + (temp. of bottom- temp of top) = 87 + (152-87) = 130.33 Upper pinch temperature = column top temp. + = 87 + (152-87) = 108.67 Component Vapour pressure at 108.67 45881.14 1684.86 209.34 38.91 i Vapour pressure at 130.33 64840.97 2865.66 409.01 89.26 i avg (temp. of bottom- temp of top)
Propylene Benzene Cumene DIPB
219.17 8.05 1.0 0.186
158.53 7.0 1.0 0.218
186.4 7.51 1.0 0.2
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The minimum reflux ratio can be calculated by underwoods method RRmin + 1 = =1q The feed line is a saturated liquid at its boiling point, so q = 1. By trial and error method, lies between, B < < A A = 7.51 B = 1 1 < < 7.51 Trial and error method 7 5 1.2 2 1.5 R Rmin = 0.238 Assume, = 1.5 R = 1.5 * 0.238 = 0.367 = (0.238/1.238) = 0.2 = (0.36/1.36) = 0.264 L.H.S 10.58 2.1 -0.354 0.749 0.423 R.H.S 0.000358 0.000508 0.00244 0.001355 0.00187 = L.H.S R.H.S 10.579642 2.099492 -0.356 0.74 0.421 for all component.
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From, fig.9.4, Erbar Maddox correlation ( = 0.38 N= = 9.66 = 10 Assuming 50 % efficiency of stages Theoretical no of stages = = 20
vs
The Principal factor that determine 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
vfl = (
)0.5
Where Vfl = flooding velocity of gas ( vapour ) K = constant l , v = density of liquid & vapour respectively here , = 2.7 Kg/ m3 = 862 Kg/ m3 Assuming plate spacing 0.45m from fig 9.1 K = 0.08 vfl = 1.42 m/s. Assuming 85% flooding condition Vfl = 0.85 1.42 = 1.21 m/s.
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Maximum flow rate Vmax = = 8.36 m/s Net area required = An = = = 5.88 m2. An = At Ad = At 0.12At = 0.88At At = = 6.68 m2 Column diameter Dt =
= = 2.91 m
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LIQUID FLOW PATTERN: Liquid flow pattern is determined by two parameters 1. Maximum liquid flowrate 2. Column diameter Here , Lmax = = 0.0238 m3/s Hole area, Ah = 10% of active area Aa = At 2Ad = 6.68 2 0.80 = 5.08 m2 Ah = 0.10 5.08 = 0.508 m2 Weir length = 0.77 Dt = 0.77 2.91 = 2.24 m Lets take Hole diameter = 7 mm Plate thickness= 5 mm
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PLATE DESIGN: Column diameter = 2.91 m Column cross section , At = 6.68 m2 Weir Height : Since column operating at pressure above atmospheric pressure, hw = 50 mm Plate thickness = 5 mm CROSS CHECK:( FOR PLATE DIMENSIONS) Maximum Liquid rate = 23.12 kg/s Assuming turndown ratio at 70% of maximum liquid flowrate , so that minimum liquid flowrate = *23.12 =16.184 kg/s.
The height of liquid crest over the segmental weir:
(how)max = 0.70 (
)(2/3)
= 36 mm of clear liquid
(how)min = 0.75 (
)(2/3)
= 30 mm of clear liquid At minimum flowrate, dh hw + how = 50+30=80 mm
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from fig 9.2, Kw = 30.2 therefore minimum vapour velocity, vmin =
( (
( (
)) ))
vmin =
= 7.20 m/s But actual vapour velocity = = = 9.92 m/s.
Thus the minimum operating velocity (9.92 m/s) lies well above the weep point (i.e. when vapour velocity = 7.20 m/s) Therefore our design is safe from operating point of view Plate pressure drop : The total plate pressure drop is given by, ht = hd + hl + hr dry plate drop hd = K1+ K2 (vgh)2 ( ) for sieve plate , K1=0, K2=
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Discharge coefficient Cv is determined as follows,
From fig.9.3, Cv= 0.765 Velocity through holes Vgh = hd = 50.85*10-3 ( ) ( )
= 3.42 mm of clear liquid Pressure drop due to staric liquid head, hl = hw + how = 50+36 = 86 mm of clear liquid Residual head, hr = = = 14 mm of clear liquid
The total pressure drop ht = hd + hl + hr = 3.42 + 86 + 14 = 103.42 mm of clear liquid
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Downcomer area backup : Backup in downcomer is given by, Hdc = ht + hw + how + hda Head loss in the downcomer due to liquid flow under the downcomer apron : hda = 0.166*( now, Aap = hap*lw Hap= height of lower edge of the apron above the tray = hw 10 = 50 10 =40 mm Lw = 2.24 m Aap = Area under the downcomer apron = 0.04 * 2.24 = 0.0896 m2 Since Aap < Ad we take Ad as Am hda = 0.166 (
)2
= 1.12 mm of clear liquid Hdc = 103.42+ 50 +36 + 1.12 = 190.54 mm of clear liquid
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Check : To avoid flooding : Hdc < Now , ( ( ) ) ( )
Since hdc < 0.250m ,so there will be no flooding at specified operating condition that means tray spacing is acceptable. Residence time : r = = = 5.68 s. Total height of tower = [no of plates * tray spacing] + clearance at top + clearance at bottom = [20 * 0.5] + 0.5 + 0.5 = 10 m So the design is satisfactory.
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SHELL THICKNESS : For thickness of shell of distillation column we required following data, 1. Design Pressure, P = 1.1 * operating pressure = 1.1 * 2.757 = 3.0327 N/mm2 2. Permissible tensile stress, f = 95 N/mm2 ( MOC= CARBON STEEL) 3. Joint efficiency facor , J = 0.85 4. Inner diameter, Di =2.91 m 5. Corrosion allowance, C = 1.5 mm Shell thickness is given by, ts= ts = ts = 57.19 mm Head thickness : for safety we use hemispherical head at top & bottom of distillation column. The head thickness is given by , th = th = th = 23 mm
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Chapter 10
COST ESTIMATION
Cost of cumene plant of capacity 400 TPD in 1990 is Rs.23.4107 Therefore cost of 1000 TPD in 1990 is: C1 = C2 (Q1/Q2)0.6 = 23.4 x 107(1000/400)0.6 = Rs.4.055 x 108 Chemical Engineering Plant Cost Index: Cost index in 1990 = 357.6 Cost index in 2010 = 539.1 Thus, Present cost of Plant = (original cost) (present cost index)/(past cost index) = (4.055 x 108) (539.1/357.6) = Rs. 6.113108 Fixed Capital Cost (FCI) = Rs. 6.113108 Estimation of Capital Investment Cost: I. Direct Costs: material and labour involved in actual installation of complete facility (70-85% of fixed-capital investment) a) Equipment + installation + instrumentation + piping + electrical + insulation + painting (5060% of Fixed-capital investment) 1. Purchased equipment cost (PEC): (15-40% of Fixed-capital investment) Consider purchased equipment cost = 25% of Fixed-capital investment PEC = 25% of 6.113108 = 0.25 6.113108 = Rs. 1.528108 2. Installation, including insulation and painting: (25-55% of purchased equipment cost.) Consider the Installation cost
= 40% of Purchased equipment cost

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= 40% of 1.528108 = 0.40 1.528108 = Rs.0.6112108 3. Instrumentation and controls, installed: (6-30% of Purchased equipment cost.) Consider the installation cost = 20% of Purchased equipment cost = 20% of 1.528x108 = 0.20 1.528108 = Rs. 0.3056108 4. Piping installed: (10-80% of Purchased equipment cost) Consider the piping cost = 40% Purchased equipment cost = 0.40 1.528108 = Rs. 0.6112108 5. Electrical, installed: (10-40% of Purchased equipment cost) Consider Electrical cost = 25% of Purchased equipment cost = 25% of 1.528 108 = 0.25 1.528108 = Rs.0.382108 B. Buildings, process and Auxiliary: (10-70% of Purchased equipment cost Consider Buildings, process and auxiliary cost, = 40% of PEC = 40% of 1.528 108 = 0.40 1.528108 = Rs. 0.6112108
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C. Service facilities and yard improvements: (40-100% of Purchased equipment cost) Consider the cost of service facilities and yard improvement, = 60% of PEC = 60% of 1.528 108 = 0.60 1.528108 = Rs. 0.9168108 D. Land: (1-2% of fixed capital investment or 4-8% of Purchased equipment cost) Consider the cost of land = 6% PEC = 6% of 1.528 108 = 0.06 1.528108 = Rs. 0.09168108 Thus, Direct cost = Rs. 5.058108 ----- (82.74% of FCI) II. Indirect costs: expenses which are not directly involved with material and labour of actual installation of complete facility (15-30% of Fixed-capital investment) A. Engineering and Supervision: (5-30% of direct costs) Consider the cost of engineering and supervision, = 10% of Direct costs = 10% of 5.058 108 = 0.1 5.058 108 = Rs.0.5058108 B. Construction Expense and Contractors fee: (6-30% of direct costs) Consider the construction expense and contractors fee, = 10% of Direct costs = 10% of 5.058108 = 0.1 5.058 108
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= 0.5058108 C. Contingency: (5-15% of Fixed-capital investment) Consider the contingency cost = 10% of Fixed-capital investment = 12% of 6.113108 = 0.12 6.113108 = Rs. 0.7336108 Thus, Indirect Costs = Rs. 1.7452108 --- (28.55% of FCI) III. Fixed Capital Investment: Fixed capital investment = Direct costs + Indirect costs = (5.058108) + (1.7452108) = Rs. 6.803108 IV. Working Capital: (10-20% of Fixed-capital investment) Consider the Working Capital = 15% of Fixed-capital investment. = 15% of 6.803108 = 0.15 6.803108 = Rs. 1.0205108 V. Total Capital Investment (TCI): Total capital investment = Fixed capital investment + Working capital = (6.803108) + (1.0205108) = Rs. 7.8235108 Estimation of Total Product cost: I. Manufacturing Cost = Direct production cost + Fixed charges + Plant overhead cost. A. Fixed Charges: (10-20% total product cost) i. Depreciation: (13% of FCI for machinery and equipment and 2-3% for Building Value for) Consider depreciation = 13% of FCI
Depreciation = (0.136.803108) + (0.030.6112108) = Rs. 0.9027108 ii. Local Taxes: (1-4% of fixed capital investment) Consider the local taxes = 3% of fixed capital investment = 0.036.803108 = Rs. 0.2041108 iii. Insurances: (0.4-1% of fixed capital investment) Consider the Insurance = 0.7% of fixed capital investment = 0.0076.803108 = Rs. 0.0476108 iv. Rent: (8-12% of value of rented land and buildings) Consider rent = 10% of value of rented land and buildings = 10% of ((0.09168108) + (0.6112108)) = Rs. 0.0703x108 Thus, Fixed Charges = Rs. 1.2247108 B. Direct Production Cost: (about 60% of total product cost) Now we have Fixed charges = 10-20% of total product charges (given) Consider the Fixed charges = 15% of total product cost Total product charge = fixed charges/15% = 1.2247108/15% = 1.2247108/0.15 = Rs. 8.1647108 i. Raw Materials: (10-50% of total product cost) Consider the cost of raw materials, = 25% of total product cost
Raw material cost = 25% of 8.1647108 = 0.258.1647108 = Rs. 2.0412108
ii. Operating Labour (OL): (10-20% of total product cost) Consider the cost of operating labour, = 12% of total product cost = 12% of 8.1647108 = 0.128.1647108 = Rs. 0.9797108 iii. Direct Supervisory and Clerical Labour (DS & CL): (10-25% of OL) Consider the cost for Direct supervisory and clerical labour, = 12% of OL = 12% of 0.9797108 = 0.120.9797108 = Rs. 0.1176108 iv. Utilities: (10-20% of total product cost) Consider the cost of Utilities, = 12% of total product cost = 12% of 8.1647108 = 0.128.1647108 = Rs. 0.9797108 v. Maintenance and repairs (M & R): (2-10% of fixed capital investment) Consider the maintenance and repair cost, = 5% of fixed capital investment
= 0.056.803108 = Rs. 0.3402108 vi. Operating Supplies: (10-20% of M & R or 0.5-1% of FCI) Consider the cost of Operating supplies, = 15% of M & R = 15% of 0.3402108 = 0.15 0.3402108 = Rs. 0.05103108 vii. Laboratory Charges: (10-20% of OL) Consider the Laboratory charges, = 15% of OL = 15% of 0.9797108 = 0.150.9797108 = Rs. 0.1469108 viii. Patent and Royalties: (0-6% of total product cost) Consider the cost of Patent and royalties, = 4% of total product cost = 4% of 8.1647108 = 0.048.1647108 = Rs. 0.3266108 Direct Production Cost = Rs. 4.983108 ----- (61% of TPC) C. Plant overhead Costs (50-70% of Operating labour, supervision, and maintenance or 5-15% of total product cost); includes for the following: general plant upkeep and overhead, payroll overhead, packaging, medical services, safety and protection, restaurants, recreation, salvage, laboratories, and storage facilities.
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Consider the plant overhead cost, = 60% of OL, DS & CL, and M & R = 60% of ((0.9797108) + (0.1176108) + (0.3402108)) = Rs. 0.8625108 Thus,Manufacture cost = Direct production cost + Fixed charges + Plant overhead costs. Manufacture cost = (4.983108) + (6.803108) + (0.8625108) Manufacture cost = Rs. 12.6485108 II. General Expenses = Administrative costs + distribution and selling costs + research and development costs A. Administrative costs:(2-6% of total product cost) Consider the Administrative costs , = 5% of total product cost = 0.05 8.1647108 = Rs. 0.4082108 B. Distribution and Selling costs: (2-20% of total product cost); includes costs for sales offices, salesmen, shipping, and advertising. Consider the Distribution and selling costs, = 15% of total product cost = 15% of 8.1647108 = 0.15 8.1647108 = Rs. 1.2247108
C. Research and Development costs: (about 5% of total product cost) Consider the Research and development costs, = 5% of total product cost = 5% of 8.1647108
= 0.05 8.1647108 = Rs. 0.4082108 D. Financing (interest): (0-10% of total capital investment) Consider interest = 5% of total capital investment = 5% of 7.8235108 = 0.057.8235108 = Rs. 0.3912108 = Rs. 2.4323108 IV. Total Product cost = Manufacture cost + General Expenses = (12.6485108) + (2.4323108) = Rs. 15.0808108 V. Gross Earnings/Income: Wholesale Selling Price of cumene per kg = Rs.53 Total Income = Selling price Quantity of product manufactured = 53 x 30000000 = Rs. 15.9108 Gross income = Total Income Total capital investment = (15.9108) (8.1647108) = Rs. 7.7353108 Let the Tax rate be 45% (common) Net Profit = Gross income - Taxes = Gross income (1- Tax rate) = 7.7353 x 108(1-0.45) = Rs. 4.2544108
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Pay back period = FCI/(net profit) = 6.803*108/4.2544*108 = 1.6. Rate of return = net profit* 100/(total capital investment) = 4.2544*108*100 / 7.8235*108 = 54.38 %
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Chapter 12
ENVIRONMENTAL AND HAZOP STUDY

Environmental Considerations: Vigilance is required in both the design and operation of process plant to ensure that legal standards are met and that no harm is done to the environment. Considerations must be given to: (1) All emissions to land, air, water. (2) Waste management. (3) Smells. (4) Noise. (5) The visual impact. (6) Any other nuisances. (7) The environmental friendliness of the products. Waste Management: Waste arises mainly as by products or unused reactants from the process, or as off- specification product produced through mis-operation. Gaseous Waste: Gaseous effluents which contain toxic or noxious substances will need treatment before discharge into the atmosphere. Gaseous pollutants can be removed by absorbtion or adsorbtion. Finely dispersed solids can be removed by scrubbing, or using electrostatic precipitators. Flammable gases can be burnt. Liquid Waste: The waste liquids from a chemical process, other than aqueous effluents will usually be flammable and can be disposed of by burning in suitable designed incinerators. The gases leaving an incinerator may be scrubbed, & acid gases neutralized. Aqueous Waste: The principal factors which determine the nature of an aqueous industrial effluent and on which strict controls will be placed by the responsible authority are: (1) pH. (2) Suspended solid. (3) Toxicity. (4) Biological oxygen demand.
The pH can be adjusted by the addition of acid or alkali. Lime is frequently used to neutralize acidic effluents. Suspended solids can be removed by settling, using clarifiers. For some effluents it will be possible to reduce the toxicity to acceptable level by dilution. Other effluents will need chemical treatment. The oxygen concentration on water course must be maintained at a level sufficient to support aquatic life. It is measured by a standard BOD test. Toxicological data: The toxicological data for a cumene plant is usually supposed to have the following values on the various environmental parameters as given below: Threshold limit value 50 ppm, Skin effects primary irritant, Absorption through skin slowly absorbed, Narcotic properties yes, Depressant properties yes. Medical examination for workers required in some countries Other precautions as for all aromatics. Noise: It can cause a serious nuisance in the neighbourhood of a process plant. Noisy equipment should, as far as practicable, be sited well away from the site boundary. Earth banks and screens of trees can be used to reduce the noise level perceived outside the site. Visual Impact: Large equipments such as storage tanks, can be painted to blend in with, or even contrast with, the surroundings. Landscaping and screening by belts of trees can also help improve the overall appearance of the site. 11.1 MATERIAL SAFETY DATA SHEET 11.1.1 HAZARDS IDENTIFICATION Inhalation Breathing high concentrations may be harmful. Mist or vapor can irritate the throat and lungs. Breathing this material may cause central nervous system depression with symptoms including nausea, headache, dizziness, fatigue, drowsiness, or unconsciousness. Eye Contact This material can cause eye irritation with tearing, redness, or a stinging or burning feeling. Further, it can cause swelling of the eyes with blurred vision. Effects may become more serious with repeated or prolonged contact. Skin Contact -
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May cause mild skin irritation with redness and/or an itching or burning feeling. Effects may become more serious with repeated or prolonged contact. It is likely that some components of this material are able to pass into the body through the skin and may cause similar effects as from breathing or swallowing it. Ingestion Swallowing this material may be harmful. Swallowing this material may cause stomach or intestinal upset with pain, nausea, and/or diarrhea. This material can get into the lungs during swallowing or vomiting. Small amounts in the lungs can cause lung damage, possibly leading to chronic lung dysfunction or death. Swallowing this material may cause effects. Chronic Health Effects Summary Secondary effects of ingestion and subsequent aspiration into the lungs may cause pneumatocele (lung cavity) formation and chronic lung dysfunction. Conditions Aggravated by Exposure Disorders of the following organs or organ systems that may be aggravated by significant exposure to this material or its components include: Skin, Respiratory System, Central Nervous System (CNS). Target Organs May cause damage to the following organs: kidneys, liver, mucous membranes, spleen, upper respiratory tract, skin, adrenal, central nervous system (CNS), eye, lens or cornea. Carcinogenic Potential This product is not known to contain any components at concentrations above 0.1% which are considered carcinogenic by OSHA, IARC or NTP. 11.1.2 FIRST AID MEASURES Take proper precautions to ensure your own health and safety before attempting rescue or providing first aid. Inhalation Move victim to fresh air. If victim is not breathing, immediately begin rescue breathing. If breathing is difficult, 100 percent humidified oxygen should be administered by a qualified individual. Seek medical attention immediately. Keep the affected individual warm and at rest.
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Eye Contact Check for and remove contact lenses. Flush eyes with cool, clean, low-pressure water for at least 15 minutes while occasionally lifting and lowering eyelids. Do not use eye ointment unless directed to by a physician. Seek medical attention if excessive tearing, irritation, or pain persists. Skin Contact Remove contaminated shoes and clothing. Flush affected area with large amounts of water. If skin surface is damaged, apply a clean dressing and seek medical attention. Do not use ointments. If skin surface is not damaged, clean affected area thoroughly with mild soap and water. Seek medical attention if tissue appears damaged or if pain or irritation persists. Ingestion Do not induce vomiting. If spontaneous vomiting is about to occur, place victims head below knees. If victim is drowsy or unconscious, place on the left side with head down. Never give anything by mouth to a person who is not fully conscious. Do not leave victim unattended. Seek medical attention immediately. 11.1.3 FIRE FIGHTING MEASURES NFPA Flammability Classification - NFPA Class-IC flammable liquid. Flash Point - Closed cup: 36C (96F). (Pensky-Martens.) Lower Flammable Limit - AP 0.9 % Upper Flammable Limit - AP 6.5 % Autoignition Temperature - 424C (795F) Hazardous Combustion Products - Carbon dioxide, carbon monoxide, smoke, fumes, and/or unburned hydrocarbons. Special Properties This material releases vapors at or below ambient temperatures. When mixed with air in certain proportions and exposed to an ignition source, its vapor can cause a flash fire. Use only with adequate ventilation. Vapors are heavier than air and may travel long distances along the ground to an ignition source and flash back. A vapor and air mixture can create an explosion hazard in confined spaces such as sewers. If container is not properly cooled, it can rupture in the heat of a fire.
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Extinguishing Media SMALL FIRE: Use dry chemicals, carbon dioxide, foam, water fog, or inert gas (nitrogen). LARGE FIRE: Use foam, water fog, or water spray. Water fog and spray are effective in cooling containers and adjacent structures. However, water can cause frothing and/or may not extinguish the fire. Water can be used to cool the external walls of vessels to prevent excessive pressure, autoignition or explosion. Do not use a solid stream of water directly on the fire as the water may spread the fire to a larger area. Protection of Fire fighters Firefighters must use full bunker gear including NIOSH-approved positive pressure selfcontained breathing apparatus to protect against potential hazardous combustion or decomposition products and oxygen deficiencies. Evacuate area and fight the fire from a
maximum distance or use unmanned hose holders or monitor nozzles. Cover pooling liquid with foam. Containers can build pressure if exposed to radiant heat; cool adjacent containers with flooding quantities of water until well after the fire is out. Withdraw immediately from the area if there is a rising sound from a venting safety device or discoloration of vessels, tanks, or pipelines. Be aware that burning liquid will float on water. Notify appropriate authorities of potential fire and explosion hazard if liquid enter sewers or waterways. 11.1.4 ACCIDENTAL RELEASE MEASURES Flammable Liquid! Release causes an immediate fire or explosion hazard. Evacuate all nonessential personnel from immediate area and establish a "regulated zone" with site control and security. A vapor-suppressing foam may be used to reduce vapors. Eliminate all ignition sources. All equipment used when handling this material must be grounded. Stop the leak if it can done without risk. Do not touch or walk through spilled material. Remove spillage immediately from hard, smooth walking areas.Prevent spilled material from entering waterways, sewers, basements, or confined areas. Absorb or cover with dry earth, sand, or other non-combustible material and transfer to appropriate waste containers. Use clean, non-sparking tools to collect absorbed material. For large spills, secure the area and control access. Prevent spilled material from entering sewers, storm drains, other drainage systems, and natural waterways. Dike far ahead of a liquid spill to ensure complete collection. Water mist or spray may be used to reduce or disperse vapors; but, it may not prevent ignition in closed spaces. This material will float on water and its run-off may create an explosion or fire hazard. Verify that responders are properly
HAZWOPER-trained and wearing appropriate respiratory equipment and fire-resistant protective clothing during cleanup operations. In an urban area, cleanup spill as soon as possible; in natural environments, cleanup on advice from specialists. Pick up freeliquid for recycle and/or disposal if it can be accomplished safely with explosion-proof equipment. Collect any excess material with absorbant pads, sand, or other inert non-combustible absorbent materials. Place into
appropriate waste containers for later disposal. Comply with all applicable local, state and federal laws and regulations. 11.1.5 HANDLING AND STORAGE Handling A spill or leak can cause an immediate fire or explosion hazard. Keep containers closed and do not handle or store near heat, sparks, or any other potential ignition sources. Avoid contact with oxidizing agents. Do not breathe vapor. Use only with adequate ventilation and personal protection. Never siphon by mouth. Avoid contact with eyes, skin, and clothing. Prevent contact with food and tobacco products. Do not take internally. When performing repairs and maintenance on contaminated equipment, keep unnecessary persons away from the area. Eliminate all potential ignition sources. Drain and purge equipment, as necessary, to remove material residues. Follow proper entry procedures, including compliance with 29 CFR 1910.146 prior to entering confined spaces such as tanks or pits. Use gloves constructed of impervious materials and protective clothing if direct contact is anticipated. Use appropriate respiratory
protection when concentrations exceed any established occupational exposure level Promptly remove contaminated clothing. Wash exposed skin thoroughly with soap and water after handling. Non-equilibrium conditions may increase the fire hazard associated with this product. A static electrical charge can accumulate when this material is flowing through pipes, nozzles or filters and when it is agitated. A static spark discharge can ignite accumulated vapors
particularly during dry weather conditions. Always bond receiving containers to the fill pipe before and during loading. Always confirm that receiving container is properly grounded. Bonding and grounding alone may be inadequate to eliminate fire and explosion hazards associated with electrostatic charges. Carefully review operations that may increase the risks associated with static electricity such as tank and container filling, tank cleaning, sampling, gauging, loading, filtering, mixing, agitation, etc. In addition to bonding and grounding, efforts to mitigate the hazards of an electrostatic discharge may include, but are not limited to,
ventilation, inerting and/or reduction of transfer velocities. Dissipation of electrostatic charges may be improved with the use of conductivity additives when used with other mitigation efforts, including bonding and grounding. Always keep nozzle in contact with the container throughout the loading process. Do not fill any portable container in or on a vehicle. Do not use compressed air for filling, discharging or other handling operations. Product container is not designed for elevated pressure. Do not pressurize, cut, weld, braze solder, drill, or grind on containers. Do not expose product containers to flames, sparks, heat or other potential ignition sources. Empty containers may contain material residues which can ignite with explosive force. Observe label precautions. Storage Keep container tightly closed. Store in a cool, dry, well-ventilated area. Store only in approved containers. Do not store with oxidizing agents. Do not store at elevated temperatures or in direct sunlight. Protect containers against physical damage. Head spaces in tanks and other containers may contain a mixture of air and vapor in the flammable range. Vapor may be ignited by static discharge. Storage area must meet OSHA requirements and applicable fire codes. Additional information regarding the design and control of hazards associated with the handling and storage of flammable and combustible liquids may be found in professional and industrial documents including, but not limited to, the National Fire Protection Association (NFPA) publications NFPA 30 ("Flammable and Combustible Liquid Code"), NFPA 77 ("Recommended Practice on Static Electricity") and the American Petroleum Institute (API) Recommended Practice 2003, (Protection Against Ignitions Arising Out of Static, Lightning, and Stray Currents"). Consult appropriate federal, state and local authorities before reusing, reconditioning, reclaiming, recycling or disposing of empty containers or waste residues of this product. 11.1.6 EXPOSURE CONTROLS AND PERSONAL PROTECTION Engineering Controls Provide ventilation or other engineering controls to keep the airborne concentrations of vapor or mists below the applicable workplace exposure limits indicated below. All electrical equipment should comply with the National Electrical Code. An emergency eye wash station and safety shower should be located near the work-station.
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Personal Protective Equipment Personal protective equipment should be selected based upon the conditions under which this material is used. A hazard assessment of the work area for PPE requirements should be
conducted by a qualified professional pursuant to OSHA regulations. The following pictograms represent the minimum requirements for personal protective equipment. For certain operations, additional PPE may be required. Eye Protection Safety glasses equipped with side shields are recommended as minimum protection in industrial settings. Chemical goggles should be worn during transfer operations or when there is a likelihood of misting, splashing, or spraying of this material. water and safety shower should be located near the work station. Hand Protection Avoid skin contact. Use heavy duty gloves constructed of chemical resistant materials such as Viton or heavy nitrile rubber. Wash hands with plenty of mild soap and water before eating, drinking, smoking, use of toilet facilities or leaving work. Do not use gasoline, kerosene, solvents or harsh abrasives as skin cleaners. Body Protection Avoid skin contact. Wear long-sleeved fire-retardant garments (e.g., Nomex) while working with flammable and combustible liquids. Additional chemical-resistant protective gear may be required if splashing or spraying conditions exist. This may include an apron, boots and additional facial protection. If product comes in contact with clothing, immediately remove soaked clothing and shower. Promptly remove and discard contaminated leather goods. Respiratory Protection For known vapor concentrations above the occupational exposure guidelines (see below), use a NIOSH-approved organic vapor respirator if adequate protection is provided. Protection factors vary depending upon the type of respirator used. Respirators should be used in accordance with OSHA requirements (29 CFR 1910.134). General Comments Use of this material in spaces without adequate ventilation may result in generation of hazardous levels of combustion products and/or inadequate oxygen levels forbreathing. inadequate warning for hazardous conditions.
A suitable emergency eye wash
Odor is an
10.1.7 STABILITY AND REACTIVITY Chemical Stability - Normally stable but may form peroxides when stored for prolonged time periods in contact with air. Conditions to Avoid - Keep away from heat, sparks and flame. prolonged storage. Materials Incompatibility -Strong acids, alkalies, and oxidizers.. 10.1.8 TOXICOLOGICAL INFORMATION Toxicity Data Effects from Acute Exposure: Overexposure to cumene may cause upper respiratory tract irritation and severe CNS depression. Effects from Prolonged or Repeated Exposure: High-level exposure to cumene vapors significantly increases renal tubule adenoma in male rats. Furthermore this exposure is associated with increased alveolar/broncheolar adenoma and carcinoma in mice and with increased hepatocellular carcinoma in female mice. At this time the relevance of these finds to human health are not clear. 10.1.9 ECOLOGICAL INFORMATION Ecotoxicity - LC50 (fish): 1- 10 mg/l. This product is potentially toxic to freshwater and saltwater ecosystems. Environmental Fate - This product will normally float on water. Components will evaporate rapidly. Aquatic toxicity values are expected to be in the range of 1 - 10 mg/l based upon data from components and similar products. This material may be harmful to aquatic organisms and may cause long term adverse effects in the aquatic environment. The log Kow value for this product is 3.66. 10.1.10 DISPOSAL CONSIDERATIONS Hazard characteristic and regulatory waste stream classification can change with product use. Accordingly, it is the responsibility of the user to determine the proper storage, transportation, treatment and/or disposal methodologies for spent materials and residues at the time of disposition. If discarded, Cumene is regulated by US EPA as a listed hazardous waste (U055). Transportation, treatment, storage and disposal of waste material must be conducted in accordance with RCRA regulations (see 40 CFR 260 through 40 CFR 271). State and/or local Forms peroxides with
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regulations may be more restrictive. Contact the RCRA/Superfund Hotline at (800) 424-9346 or your regional US EPA office for guidance concerning case specific disposal issues.
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Chapter 11 PLANT LOCATION AND LAYOUT Plant location and site selection: The location of the plant can have a crucial effect on the profitability of a project and the scope for future expansion. Many factors must be considered when selecting a suitable site. The factors to be considered are: 1. Location with respect to the marketing area 2. Raw material supply. 3. Transport facilities. 4. Availability of labour. 5. Availability of utilities: water,fuel,power. 6. Availability of suitable land. 7. Environmental impact, and effluent disposal. 8. Local community considerations. 9. Climate. 10. Political and strategic considerations. Marketing Area: For materials that are produced in bulk quantities such as cement, mineral acids and fertilizers where the cost of the product per ton is relatively low and the cost of transport a significant fraction of the sales price, the plant should be located close to the primary market. This consideration will be less important for low volume production, high-priced products, such as pharmaceuticals. Raw Materials: The availability and price of suitable raw materials will often determine the plant location. Plant producing bulk chemicals are best located close to the source of the major raw material: where this is also close to the marketing area. Transport: The transport of materials & products to & from the plant will be an overriding consideration in site selection. If practicable, site should be selected that is close to at least two major forms of transport road, rail, waterway (canal or river) or a sea port. Road transport is being increasingly used, and is suitable for long-distance transport of bulk chemicals. Air transport is convenient &
efficient for the movement of personnel &essential equipment & supplies & the proximity of the site airport should be considered. Availibility of labour: Labour will be needed for construction of the plant & its operation. Skilled construction workers will usually be brought in from outside the site area, but there should be an adequate pool of unskilled labour available locally ; & labour suitable for training to operate the plant. Skilled tradesmen will be needed for plant maintenance. Local trade union customs & restrictive practices will have to be considered when assessing the availability & suitability of the local labour for recruitment & training. Utilities(Services) Chemical processes invariably require large quantities of water for cooling & general process use , & the plant must be located near a source of water of suitable quantity. Process water may be drawn from a river, from wells, or purchased from a local authority. At some sites the cooling water required can be taken from a river or lake , or from the sea; at other locations cooling tower will be needed. Electrical power will be needed at all sites. Electrochemical processes that require large quantities of power; for example, aluminium smelters need to be located close to a cheap source of power. A competitive priced fuel must be available on site for steam & power generation. Environment impact,& disposal: All industrial processes produce waste products & full consideration must be given to the difficulties & cost of their disposal. The disposal of toxic & harmful effluents will be coverd by local regulations & the appropriate authorities must be consulted during the initial site survey to determine the standards that must be met. An environmental impact assessment should be made for each new project or major modification or addition to an existing process. Local community considerations: The proposed plant must fit in with & be acceptable to the local community. Full consideration must be given to the safe location of the plant so that it does not impose a significant additional risk to the community. On a new site, the local community must be able to provide adequate facilities for the plant personnel: school, banks, housing & recreational & cultural facilities.
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Land (site selection) Sufficient suitable land must be available for the proposed plant & for future expansion. The land should ideally be flat, well drained & have suitable load bearing characteristics. A full site evaluation should be made to determine the need of piling or other special formations. Climate: Adverse climate conditions at a site will increase cost. Abnormally low temperatures will require the provisition of additional insulation & special heating for equipment & pipe runs. Stronger structures will be needed at locations subject to high winds (cyclone hurricane areas) or earthquakes. Political & Stratergic Considerations: Capital grants tax concessions & other inducements are often given by the government to direct renew investments to preferred locations, such as areas of high unemployment. The availability of such grants can be the overriding consideration in site selection. Site Layout: The process units & ancillary buildings should be laid out to give the most economical Flow of materials & personnel around the site. Hazardous processes must be located at a safe distance from other buildings. Consideration must also be given to the future expansion of the site. The ancillary buildings & services required on a site, in addition to the main processing units will include. 1. Storages for raw materials & products: tank farms & warehouses. 2. Maintenance workshops. 3. Stores for maintenance & operating supplies. 4. Laboratories for process control 5. Fire stations & other emergency services. 6. Utilities: steam boilers, compressed air, power generation , refrigeration, transformer stations. 7. Effluent disposal plant . 8. Offices for general administration. 9. Canteens & other amenity buildings, such as medical centers. 10. Car parks When roughing out the preliminary site layout, the process units will normally be sited first & arranged to give a smooth flow of materials through the various processing steps, from raw
material to final product storage. Process units are normally spaced at least 30m apart; greater spacing may be needed for hazardous processes. The location of the principal ancillary buildings should then be decided. They should be arranged so as to minimize the time spent by personnel in travelling between buildings. Administration offices & laboratories, in which a relatively large number of people will be working, should be located well away from potentially hazardous processes. Control rooms will normally be located be located adjacent to the processing units, but with potentially hazardous processes may have to be sited at a safer distance. The sitting of the main process units will determine the layout of the plant roads, pipe alleys & drains. Access roads will be needed to each building for construction & for operation & maintenance. Utility buildings should be sited to give the most economical run of pipes to & from the process units. Cooling towers should be sited so that under the prevailing wind the plume of condensate spray drifts away from the plant area & adjacent properties. The main storage area should be placed between the loading & unloading facilities & the process units they serve. Storage tanks containing hazardous materials should be sited at least 70m from the site boundary. Plant Layout: The economic construction & efficient operation of a process unit will depend on how well he plant & equipment specified on the process flow-sheet is laid out. The principal factors to be considered are: 1. Economic consideration: construction & operating cost 2. The process requirements 3. Convenience of operation 4. Convenience of maintenance 5. Safety 6. Future expansion 7. Modular construction Costs: The cost of construction can be minimised by adopting a layout that gives the shortest run of connecting pipe between equipment & the least amount of structural steel work. However this will not necessarily be the best arrangement for operation & maintainance.
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Process Requirements: An example of the need to take into account process considerations is the need to clevate the base of columns to provide the necessary net positive suction head to a pump or the operating head for a thermosyphon reboiler. Operator: Equipment that needs to have frequent operator attention should be located convenient to the control room. Valves,sample points, and instruments should be located at convienient positions and heights.Sufficient working space and head room must be provided to allow easy access to equipments. Maintainance: Heat exchangers need to be cited so that the tube bundles can be easily withdrawn for cleaning and tube replacement. Vessels that require frequent replacement of catalyst or packing should be located on the outside of buildings. Equipment that requires dismantling for maintainnace, such as compressors and large pumps, should be placed under cover. Safety: Blast walls maybe needed to isolate potentially hazardous equipment, and confine the effects of an explosion. At least two escape routes for operators must be provided from each level in the process buildings. Plant Expansion: Equipments should be located so that it can be conveniently tied in with any future expansion of the process. Space should be left on pipe alleys for future needs, and services pipes over-sized to allow for future requirements. Modular Constructions: In resent years there has been a move to assemble sections of plant at the plant manufacturers site. These modules will include the equipment, structural steel, piping and instrumentation. The modules are then transported to the plant site, by road or sea. The advantage of modular construction are : (1) Improved quality control (2) Reduced construction cost (3) Less need for skilled labour on site. (4) Less need for a skilled personal on overseas sites.
Some of the disadvantages are: (1) Higher design costs. (2) More structural steel work. (3) More flanged connections. (4) Possible problems with assembly on site. Utilities: The word utilities is not generally used for the ancillary services needed in the operation of any production process. These services will normally be supplied from a central site facility, and will include: (1) Electricity. (2) Steam for process heating. (3) Cooling water. (4) Water for general use. (5) Demineralised water. (6) Compressed air. (7) Inert gas supplies. (8) Refrigeration. (9) Effluent disposal facilities. Electricity: .The power required for electrochemical processes, motor drives, lighting, and general use maybe generated on site, but will more usually be purchased from the local supply company. The voltage at which the supply is taken or generated will depend on the demand. For a large site the supply will be taken at a very high voltage, typically 11,000 or 33,000 V. Transformers will be used to step down the supply voltage to the voltages used on the site. In the United Kingdom a three phase 415V system is used for general industrial purposes, and 240V single phase for lighting and other low power requirements. If a number of large motors is used, a supply at an intermediate high voltage will also be provided, typically 6000 or 11,000V Steam: The steam for heating is usually generated in water tube boilers using the most economical fuel level available. The process temperatures required can usually be obtained with low temperature steam typically 2.5 bar and steam distributed at a relatively low pressure, typically around 8 bar
(100 psig). Higher steam pressures, or proprietary heat transfer fluids, such as dowtherm will be needed for high process temperatures. Combined Heat and Power (Co-generation): The energy costs on a large site can be reduced if the electrical power required is generated on the site and the exhaust steam from the turbines used for process heating. The overall thermal efficiency of such systems can be in the range 70-80 %, compared with the 30-40 % obtained from a conventional power station, where the heat in the exhaust steam is wasted in the condenser. Whether a combined heat and power system scheme is worth considering for a particular site will depend on the size of the site, the cost of fuel, the balance between the power and heating demands, and particularly on the availability of and cost of, stand by supplies and the price paid for any surplus power electricity generated. Cooling Water: Natural and forced draft cooling towers are generally used to provide the cooling water required in a site; unless water can be drawn from a convinient river or lake in sufficient quantity. Water for General Use: The water required for general purposes on a site will usually be taken from the local mains supply, unless a cheaper source of suitable quantity water is available from a river, lake or well. Demineralised Water: Demineralised water from which all the minerals have been removed by ion exchange, is used where pure water is needed for process use, and as boiler feed water. Mixed and multiple bed ion exchange units are used, one resin converting the cations to hydrogen and the other removing the acid radicals. Water with less than one ppm of dissolved solids can be produced. Refrigeration: It will be needed for processes that require temperatures below those that can be economically obtained with cooling water. For temperatures down to around 10 o C chilled water can be used. For lower temperatures, down to -30oC, salt brines are used to distribute the refrigeration round the site from a central refrigeration machine. Compressed Air: It will be needed for general use, and for the pneumatic controllers that are usually used for chemical process plant control.
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Inert Gases: Where large quantities of inert gas are required for the inert blanketing of tanks and for purging is usually supplied from a central facility. Nitrogen is normally used and is manufactured on site in an air liquefaction plant, or purchased as liquid in tankers. Effluent Disposal: Facilities will be required at all sites for the disposal of waste materials without creating a public nuisance.
SITE LAYOUT
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Product Dispatch Gate 2 E.T.P. Section Tank Farm Wind Space for future Main Control expansion Room Power Station Plant Utilities Main unit
Workshop
R & D centre
Canteen Medical Admin. Building Gate 1 Green Belt Centre Security Office Parking Area
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Chapter 13 REFERENCE 1. Navid Naderpour , Petrochemical Production Process SBS Publisher t
Distributors Pvt.Ltd. 2. Petroleum Technology - Wiley Critical Content, Vol.-2, pp 3. Sun G Gyu Lee, Encyclopedia of Chemical Processing- Taylor & Francis Publisher,Vol.-1 4. PERRY & CHILTON, Chemical Engineers Handbook 5. Austin,G.T.Shreves Chemical Process Industries5th Ed.,McGraw Hill International Edition. 6. Drydens outline of chemical technology for 21st Century. 7. Kirk Othmer Encyclopedia Of Chemical Technology(2005), Fifth edition, Volume 10. 8. Ullmmans Encyclopedia Of Industrial Chemistry(1985), Volume 12. 9. Y.V.C.Rao, Chemical Engineering Thermodynamics(2005), Universities Press(India) Private Limited. 10. B I Bhatt, S M Vora, Stoichiometry, 4th Ed., McGraw Hill, USA, 2005. 11. Himmelblau D. V., Basic principles and calculations in chemical engineering, 5th Ed., Prentice-Hall, USA, 1989. 12. 639120 - Brayford, D.J., Cumene, in Encyclopedia of Chemical Processing and Design, 14 (1982), 33-52
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Manufacturing of Cumene

Gharda institute of technology, lavel

2.1 PHYSICAL PROPERTIES OF CUMENE[8]

Gharda institute of technology, lavel

Antoine Constants A B C 13.99 3400 207.78

2.2 THERMODYNAMIC PROPERTIES OF CUMENE[8]

2.3 CHEMICAL PROPERTIES:[8]

Gharda institute of technology, lavel

Gharda institute of technology, lavel

Chapter 4 MANUFACTURING PROCESSES OF CUMENE.

Gharda institute of technology, lavel

4.1.4 PROCESS FLOW DIAGRAM

Figure 4.1.4.a Liquid phase alkylation using phosphoric acid

Gharda institute of technology, lavel

4.2 LIQUID PHASE ALKYLATION USING AlCl3 [2]

Gharda institute of technology, lavel

4.3 Q-MAX PROCESS[1,5,6]

Gharda institute of technology, lavel

4.3.3 PROCESS FLOW DIAGRAM

Heavies Transalkylation Reactor Benzene Column Cumene Column DIPB Column

Figure4.3.3.a : Q-Max process

Gharda institute of technology, lavel

4.4 CD CUMENE PROCESS[1]

Gharda institute of technology, lavel

4.4.3 PROCESS FLOW DIAGRAM

Benzene Propane Cumene

Figure : CD- Cumene process

Gharda institute of technology, lavel

Chapter 5 SELECTION OF PROCESS

Gharda institute of technology, lavel

Gharda institute of technology, lavel

+ 3.4512*10-1T - 1.6315*10-3T2 + 3.8755*10-6T3)dT

= 7934.11 + 18540.71 32888.16 + 29674.23 = 23.260 KJ/mol For Benzene

Gharda institute of technology, lavel

6.2 Calculation of Entropy S443 = S298 + ( ) ..[11]

Gharda institute of technology, lavel

Gharda institute of technology, lavel

Chapter 7 MATERIAL BALANCE

Gharda institute of technology, lavel

Gharda institute of technology, lavel

Cumene + DIPB 346.31 Kmol/hr + 17.33 Kmol/hr

DIPB 17.33 Kmol/hr

Heavy ends 0.3466 Kmol/hr

Material balance of transalkylation reactor: Cumene 16.9834Kmol/hr

Benzene + PIPB 16.9834 Kmol/hr +16.9834Kmol/hr

Material balance for finishing reactor:

Benzene = 17.33 kmol/hr cumene = 17.33 kmol/hr propylene = 17.33 kmol/hr

Gharda institute of technology, lavel

Chapter 8 ENERGY BALANCE

Gharda institute of technology, lavel

Energy balance on cumene column : Cumene

Gharda institute of technology, lavel

Energy balance on PIPB column-

Gharda institute of technology, lavel

Chapter 9 DESIGN OF MULTICOMPONENT DISTILLATION COLUMN

Propylene Benzene Cumene DIPB Total

Mol. Fraction 0.0123 0.721 0.245 0.0122

Mol fraction 0.0166 0.98 0..166 -

Mol fraction 0.0277 0.926 0.0465

Top temperature = 870C

Gharda institute of technology, lavel

Bottom temp = 152 0 C Nmin = =

Propylene Benzene Cumene DIPB

+ 3.451210-1T - 1.631510-3T2 + 3.8755*10-6T3)dT