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Cumene Manufacturing Procedure

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  • Manufacturing of Cumene

    Gharda institute of technology, lavel Page 1

    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]

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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 VALUE

    Molecular weight 120.19

    Boiling Point, C 152.39

    Freezing point, C -96.03

    Density, gm/cm3

    0C

    20C

    40C

    0.8786

    0.8169

    0.8450

    Thermal conductivity, w/m.k

    25C

    0.124

    Viscosity, mPa.s (cp)

    0C

    20C

    40C

    1.076

    0.791

    0.612

    Surface tension, mN/m

    20C

    0.791

    Flash point, C 44

    Autoignition temperature, C 523

  • Manufacturing of Cumene

    Gharda institute of technology, lavel Page 3

    Antoine Constants

    A

    B

    C

    13.99

    3400

    207.78

    2.2 THERMODYNAMIC PROPERTIES OF CUMENE[8]

    PROPERTY VALUE

    Relative molar mass 120.2

    Critical temperature, C 351.4

    Critical pressure, Kpa 3220

    Critical density, g/cm3 0.280

    Heat of vapourisation at bp, J/g 312

    Heat of vapourisation at 25C, J/g 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.

  • Manufacturing of Cumene

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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 C6H5. C3H7 ;

    Side Reaction

    C6 H6 + nCH3CH=CH2 C6 H6-n.(CH)n

    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

    Jie_ShengHighlight

  • Manufacturing of Cumene

    Gharda institute of technology, lavel Page 6

    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

  • Manufacturing of Cumene

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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 DESCRIPTION-

    If 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

  • Manufacturing of Cumene

    Gharda institute of technology, lavel Page 9

    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

  • Manufacturing of Cumene

    Gharda institute of technology, lavel Page 10

    Fig 4.2.3.a Liqid phase alkylation using Aluminium Chloride

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    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.

  • Manufacturing of Cumene

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    4.3.3 PROCESS FLOW DIAGRAM

    Recycle Benzene

    Benzene

    Propylene

    Cumene

    DIPB

    Heavies

    DIPB

    Column

    Cumene

    Column

    Benzene

    Column

    Transalkylation

    Reactor Depropanizer

    Alkylation

    Reactor

    Propane

    Figure4.3.3.a : Q-Max process

  • Manufacturing of Cumene

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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

  • Manufacturing of Cumene

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    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.

  • Manufacturing of Cumene

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    4.4.3 PROCESS FLOW DIAGRAM

    PIPB Recycle

    Cumene

    Cumene Column

    PIPB

    Column

    Heavies

    Propane

    Benzene

    Propylene

    Figure : CD- Cumene process

    Transalkylator

  • Manufacturing of Cumene

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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.

  • Manufacturing of Cumene

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    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.

  • Manufacturing of Cumene

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    Chapter 6

    THERMODYNAMIC FEASIBILITY

    Table 6.a : Thermodynamic data

    Component Cp (J/mol k) Entropy

    @298(J/mol k)

    Hf @298(KJ/mol)

    Gf @298(KJ/mol)

    Cumene 217.96 388.57 3.93 136.96

    Propylene 115.3 266.6 20.42 62.72

    Benzene 137.87 269.20 82.93 129.66

    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 + 6.39210-1

    T 1.733110-3T2 + 2.214610-6T3

    Cp(propylene) = 54.718 + 3.451210-1

    T 1.631510-3T2 + 3.875510-6T3

    Cp(benzene) = 31.662 + 1.3043T 3.607810-3

    T2 + 3.824310

    -6T

    3

    For Cumene

    298443 (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

    298443

    (54.718 + 3.4512*10-1

    T - 1.6315*10-3

    T2

    + 3.8755*10-6

    T3)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

    Reaction-

    Main 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

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    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 A B C D

    Cumene 10.149 5.1138E-1 -1.7703E-5 -2.2612E-7

    Propylene 31.298 7.2449E-1 1.9481E-4 -2.1582E-7

    Benzene -31.368 4.7460E-1 -3.1137E-4 8.5237E-8

    Energy balance on CD-column

    Benzene unreacted benzene + propylene

    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 reactor-

    Cumene

    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. Propylene lighter than light key

    2. Benzene light key

    3. Cumene heavy key

    4. PIPB heavier than heavy key

    Material balance

    Component Feed Distllate Bottom

    Moles Mol.

    Fraction

    Mol Mol

    fraction

    Mol Mol

    fraction

    Propylene 17.34 0.0123 17.34 0.0166 - -

    Benzene 1032.75 0.721 1022.42 0.98 10.33 0.0277

    Cumene 346.31 0.245 1.732 0..166 344.58 0.926

    DIPB 17.33 0.0122 - - 17.33 0.0465

    Total 1413.73 372.24

    Vapor pressure data

    Log p = A- B/(T+C)

    Calculation of top temperature

    Component yi pi ki xi = yi/ki

    Propylene 0.0166 31627.13 17.15 0.000968

    Benzene 0.98 927.68 1 0.98

    Cumene 0.00166 96.31 0.09 0.018

    0.999

    Top temperature = 870C

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    Calculation of bottom temperature

    Component Xi Pi ki yi = kixi

    Propylene 0.0277 4521.18 5.43 0.150411

    Benzene 0.926 733.30 0.9 0.8334

    Cumene 0.0465 185.11 0.188 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. +

    (temp. of bottom- temp of top)

    = 87 +

    (152-87)

    = 108.67

    Component Vapour

    pressure at

    108.67

    i Vapour pressure at

    130.33

    i avg

    Propylene 45881.14 219.17 64840.97 158.53 186.4

    Benzene 1684.86 8.05 2865.66 7.0 7.51

    Cumene 209.34 1.0 409.01 1.0 1.0

    DIPB 38.91 0.186 89.26 0.218 0.2

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    The minimum reflux ratio can be calculated by underwoods method

    RRmin + 1 =

    for all component.

    = 1 q

    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

    L.H.S R.H.S = L.H.S R.H.S

    7 10.58 0.000358 10.579642

    5 2.1 0.000508 2.099492

    1.2 -0.354 0.00244 -0.356

    2 0.749 0.001355 0.74

    1.5 0.423 0.00187 0.421

    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

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    From, fig.9.4, Erbar Maddox correlation (

    vs

    )

    = 0.38

    N =

    = 9.66

    = 10

    Assuming 50 % efficiency of stages

    Theoretical no of stages =

    = 20

    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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  • Manufacturing of Cumene

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  • Manufacturing of Cumene

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  • Manufacturing of Cumene

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  • Manufacturing of Cumene

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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 (50-

    60% 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

  • Manufacturing of Cumene

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    = 40% of 1.528108

    = 0.40 1.528108

    = Rs.0.611210

    8

    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 1.52810

    8

    = Rs. 0.916810

    8

    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. 0.0916810

    8

    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

  • Manufacturing of Cumene

    Gharda institute of technology, lavel Page 48

    = 0.505810

    8

    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) + (1.745210

    8)

    = 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. 1.020510

    8

    V. Total Capital Investment (TCI):

    Total capital investment = Fixed capital investment + Working capital

    = (6.803108) + (1.020510

    8)

    = 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

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    Depreciation = (0.136.803108) + (0.030.611210

    8)

    = 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) + (0.611210

    8))

    = 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

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    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

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    = 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) + (0.117610

    8) + (0.340210

    8))

    = Rs. 0.8625108

    Thus,Manufacture cost = Direct production cost + Fixed charges + Plant overhead costs.

    Manufacture cost = (4.983108) + (6.80310

    8) + (0.862510

    8)

    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

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    = 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) + (2.432310

    8)

    = 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*10

    8

    = 1.6.

    Rate of return = net profit* 100/(total capital investment)

    = 4.2544*108*100

    / 7.8235*10

    8

    = 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.

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    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 self-

    contained 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 non-

    essential 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

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    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,

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    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. A suitable emergency eye wash

    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. Odor is an

    inadequate warning for hazardous conditions.

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