Report BTP

47
A Report on Production of Phenol from 99.9% pure Cumene from Naptha cracker Production of 99.99% pure Bisphenol A from 99.99% pure Phenol Major Project Report submitted by Virender Pratap Singh Department of Chemical Engineering, IIT Roorkee On November 24, 2014

description

Report BTP

Transcript of Report BTP

  • A Report on

    Production of Phenol from 99.9%

    pure Cumene from Naptha cracker

    Production of 99.99% pure Bisphenol

    A from 99.99% pure Phenol

    Major Project Report submitted by

    Virender Pratap Singh

    Department of Chemical Engineering,

    IIT Roorkee

    On

    November 24, 2014

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    Table of content

    Phenol 1. Uses & present status of the product Page 2

    2. Market Prospects Page 5

    3. Available process for the production of product Page 7

    4. Techno-Economic appraisal of alternative processes Page 10

    5. Selection of Technology/Scheme

    5.1 Basis of Selection Page 11

    5.2 Details of selected process - Sunoco/UOP Process Page 11

    5.3 Process flow and recent technology advances Page 12

    6. Raw Material

    6.1. Sources of raw material Page 25

    6.2 Availability of Cumene Page 27

    6.3 Import Data Page 27

    6.4 Export Data Page 30

    6.5 Prevailing Prices Page 31

    6.6 Government Policies & Import duty Page 31

    BisPhenol A 1. Uses & present status of the product Page 32 2. Market Prospects Page 34 3. Available process for the production of product Page 35 4. Techno-Economic appraisal of alternative processes Page 36 5. Selection of Technology/Scheme Page 37

    References Page 46

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    Phenol

    1. Uses & present status of the product

    The main use of phenol is as a feedstock for phenolic resins, bisphenol A and

    caprolactam (an intermediate in the production of nylon-6). It is used in the

    manufacture of many products including insulation materials, adhesives, lacquers,

    paint, rubber, ink, dyes, illuminating gases, perfumes, soaps and toys. Also used in

    embalming and research laboratories. It is a product of the decomposition of organic

    materials, liquid manure, and the atmospheric degradation of benzene.

    It is found in some commercial disinfectants, antiseptics, lotions and ointments. Phenol

    is active against a wide range of microorganisms, and there are some medical and

    pharmaceutical applications including topical anaesthetic and ear drops, sclerosing

    agent.

    It is also used in the treatment of ingrown nails in the "nail matrix phenolization

    method".

    Another medical application of phenol is its use as a neurolytic agent, applied in order

    to relieve spasms and chronic pain. It is used in dermatology for chemical face peeling.

    Phenol is a toxic and corrosive compound often used in DNA extractions -- not exactly

    the kind of thing you want to eat. A variety of organic compounds, however, contain the

    same chemical group and structural features that distinguish phenol, and many of

    these other compounds are beneficial for your health. Compounds in this class are

    collectively called phenols.

    Cancer Prevention

    Some phenolic compounds are believed to be cancer chemopreventives, compounds

    that may decrease your risk of developing cancer. Epigallocatechin-3 gallate, for

    example, is a phenolic compound found in green tea and believed to be a cancer

    chemopreventive. A broad group of phenolic compounds called flavonoids are common

    in plants; according to a review in the "British Journal of Nutrition," there is evidence to

    suggest many flavonoids like anthocyanins may have anticancer effects.

    Antioxidants

    Many phenolic compounds found in plants may have antioxidant effects, meaning they

    react with and capture dangerously reactive compounds called free radicals before the

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    radicals can react with other biomolecules and cause serious damage. Flavnoids and

    tocopherols are two broad classes of phenolic compounds with antioxidant properties.

    Resveratrol, a phenolic compound found in grape skins and red wine, also has

    antioxidant effects.

    Other use are housing construction, fiber, detergents, gazing, coating, sheets and films

    etc.

    Apart from various uses phenol is toxic material should be handled carefully. In

    presence of light or higher temperature decomposition of phenol takes place so should

    be kept in dark container and away from sunlight.

    The most important chemical made from phenol is bisphenol A, which is used to make

    the polycarbonates. Phenol is also catalytically reduced to cyclohexanol, which is used in

    the manufacture of polyamides 6 and 6,6.

    Phenol is also used to make a range of thermosetting polymers (resins). It reacts with

    methanal in the presence of a catalyst to form phenol-methanal resins.

    Among the other uses of phenol is the production of phenylamine (aniline) needed, for

    example, for the manufacture of dyes. Antiseptics such as 2,4-and 2,6-dichlorophenols

    are also made from phenol.

    Phenolic resins are found in myriad industrial products. Phenolic laminates are made by

    impregnating one or more layers of a base material such as paper, fiberglass or cotton

    with phenolic resin and laminating the resin-saturated base material under heat and

    pressure. The resin fully polymerizes (cures) during this process. The base material

    choice depends on the intended application of the finished product. Paper phenolics

    are used in manufacturing electrical components such as punch-through boards and

    household laminates. Glass phenolics are particularly well suited for use in the high

    speed bearing market. Phenolic micro-balloons are used for density control. Snooker

    balls as well as balls from many table-based ball games are also made from phenol

    formaldehyde resin. The binding agent in normal (organic) brake pads, brake shoes and

    clutch disks are phenolic resin. Synthetic resin bonded paper, made from phenolic resin

    and paper, is used to make countertops.

    Phenolic resins are also used for making exterior plywood commonly known as WBP

    (Weather & boil proof) Plywood because Phenolic resins have no melting point but only

    a decomposing point in the temperature zone of 220 degree Celsius & above. Phenolic

    resin is used as a binder in loudspeaker driver suspension components which are made

    of cloth.

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    2. Market Prospects -

    1. Phenol Consumption 7166000 tonnes consumption in 2002

    2. Consumption Growth (%)

    1997-2002 2002-2007 2007-2012 2009-2014 2014-19

    5.2 4.4 1.7 5.1 2.5

    3. Capacity in 2002 - 7,843000 tonnes

    4. Production in 2010 8 million tonnes

    5. Capacity in 2010 10.4 million tonnes

    Demand: The outlook for the phenol market in 2014 is uncertain, particularly for major

    derivative Bisphenol A (BPA) which drives global demand. The global demand for phenol

    has been steadily increasing over the last 10 years. In 2000, global phenol demand

    stood at 6,072,774 tons, before increasing to 7,934,218 tons in 2010. A significant

    portion of the increase in demand for phenol was from the Asia-Pacific region, and this

    is expected to continue in the forecast period. The Asia-Pacific region is expected to

    account for 51.2% of global phenol demand in 2020. The global demand for phenol will

    increase to reach 11,576,620 tons by 2020.

    According to SRI consulting report 2010 global production and consumption of phenol

    were both around 8.0 million tonnes with global capacity utilization of 77%. Phenol

    consumption is expected to average growth of 5.1percent per year from 2009 to 2014

    and around 2.5% from 2014-19. Phenol is consumed mainly for production of bisphenol

    A and phenolic resins which accounted for 42% and 28% respectively of total phenol

    consumption in 2009.

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    Year Installed Capacity

    (in x10^3 MT)

    Production

    (in x10^3 MT)

    Consumption

    (in x10^3 MT)

    2006-07 ------------------- 71.27 137.43

    2007-08 ------------------- 74.94 175.73

    2008-09 ------------------- 75.75 165.47

    2009-10 ------------------- 71.59 171.94

    2010-11 ----------------- 79.81 202.01

    2011-12 77.13 65.93 211.54

    2012-13 77.13 59.92 232.24

    2013-14 77.13 46.39 258.35

    Fig. 2 Yearwise Installed Capacity, Production & Consumption of India

    Year Exports

    (quantity in MT)

    Exports

    (Value in lakhs)

    Imports

    (quantity in MT)

    Imports

    (Value in lakhs)

    2006-07 68754 40552 66158 37795

    2007-08 102871 66153 100793 63950

    2008-09 92918 46763 89723 43010

    2009-10 103071 51907 100351 48638

    2010-11 123490 93671 122197 91350

    2011-12 146762 111194 145616 109047

    2012-13 172758 139980 172323 138952

    2013-14 214098 172427 211956 169197

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    Fig. 3

    Producers Location Phenol Capacity (kT/year)

    Hindustan Organic

    Chemicals

    Kochi 42

    SI Group India Ltd Navi Mumbai 37

    3. Available process for the production of product -

    Significant improvements in the technology for the production of phenol have been

    made over the past decade. New catalysts and processes have been commercialized for

    the production of cumene via alkylation of benzene with propylene. Recent process

    design innovations have been commercialized for the cumene hydroperoxide route that

    remains the process of choice for the production of phenol. All of this effort has been

    directed at improving yield, process economics/costs, and process safety for the

    preparation of phenol as a key intermediate for the growing bis-phenol A and phenolic

    resins markets. A review of technology offerings by major licensors of these new

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    processes is provided as well as a discussion of key process differences and recent

    advances.

    Current state-of-the-art processes for the production of cumene as a feedstock for

    phenol involve technology offerings from UOP, Badger Licensing (formerly ExxonMobil

    and the Washington Group) and CDTech based on zeolitic catalysis. For cumene

    hydroperoxide processing to phenol technology, offerings by UOP/Sunoco (formerly

    Allied-UOP technology), GE/Lummus, and KBR (Kellogg-Brown & Root formerly BP-

    Hercules technology) represent the state-of the-art based on the autocatalytic cumene

    oxidation and dilute acid cleavage (cumene hydroperoxide decomposition) processing

    routes.

    Much of the improvement in these technologies falls along the lines of improved yield

    and stability for the zeolitic cumene technologies and improved yield, safety, and

    economy for the phenol technologies. A brief discussion regarding alternative methods

    of phenol production such as the toluene oxidation route and direct oxidation of

    benzene to phenol is also presented as shifting economic considerations in the future

    may make these processes more attractive.

    A. Sunoco/UOP Phenol process

    The Sunoco/UOP Phenol process produces high-purity phenol and acetone by the

    cumene peroxidation route, using oxygen from air. This process features low-pressure

    oxidation for improved yield and safety, advanced CHP cleavage for high product

    selectivity, an innovative direct product neutralization process that minimizes product

    waste, and an improved, low cost product recovery scheme. The result is a very low

    cumene feed consumption ratio of 1.31 wt. cumene/wt. phenol that is achieved without

    acetone recycle and without tar cracking. The process also produces an ultra-high

    product quality at relatively low capital and operating costs. Extensive commercial

    experience has helped to validate these claims.

    B. KBR 4th Generation Phenol process

    KBR 4th Generation Phenol process also claims improvements for the cumene

    peroxidation route for a process based on high-pressure oxidation technology. These

    include improved oxidation yield, an advanced cleavage system, elimination of tar

    cracking, and an efficient energy and waste management system.

    C. GE/Lummus Process

    It claims various improvements to the cumene peroxidation process. It is similar to KBR

    in that it is also based on high-pressure oxidation technology. Improvements include

    enhanced oxidation reaction rates, an advanced cleavage section using a co-catalyst,

    elimination of tar cracking, and an improved product recovery scheme.

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    Overall process description/chemistry

    The main reactions for phenol and acetone production via cumene peroxidation are

    shown in Fig. 4. Both reactions are highly exothermic. Oxidation of cumene to cumene

    hydroperoxide (CHP) proceeds via a free-radical mechanism that is essentially auto-

    catalyzed by CHP. The decomposition reaction is catalyzed by strong mineral acid and is

    highly selective to phenol and acetone. In practice, the many side reactions which take

    place simultaneously with the above reactions are minimized by optimization of process

    conditions. Dimethylphenylcarbinol is the main oxidation by-product, and the

    DMPC/AMS reactions play a significant role in the plant.

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    4. Techno-Economic appraisal of alternative processes

    GE/Lummus claims an improved flow scheme to clean up acids and other activity

    depressing components present in the recycle cumene stream. This results in enhanced

    cumene oxidation rates for their high-pressure oxidation technology. However, the

    process is more likely to have higher yields of these components as a result of the

    higher operating pressure. This requires greater measures to ensure adequate clean up

    compared to a more modern low-pressure system that provides higher oxidation yields.

    Also, the high pressure system is more complex and costly and requires higher air

    compression costs. With either low-pressure or high-pressure oxidation, the oxidation

    air strips light acids out of the oxidation products.

    With Sunoco/UOP low pressure oxidation, the air stripping combined with partitioning

    of the acids to the condensate in the spent air cumene recovery system and the weak-

    caustic scrubbing of the recycle cumene is so effective that no other method of acid

    removal is required. This does not appear to be the case for GE/Lummus high-pressure

    oxidation.

    KBR employs a similar high-pressure oxidation technology for the manufacture of

    phenol. KBR claim to have eliminated the sodium carbonate scrubbing system

    completely thereby reducing capital and operating costs. The aqueous effluent rate for

    the oxidation section is also said to be reduced by as much as 75% resulting in off-site

    treating savings. However, similar to GE/Lummus, higher reactor/compressor section

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    costs and lower yields are likely to more than offset these gains compared to low-

    pressure technology.

    GE/Lummus claims improvements in the CHP decomposition technology. The

    technology employs a cocatalyst CHP cleavage process using a very precise mix of NH3

    and H2SO4 to control acidity at the optimal level for maximum yield. However, use of

    such a pre-neutralized acid mix may greatly reduce reaction rate; resulting in much

    higher decomposer residence times.

    5. Selection of Technology/Scheme

    5.1 Basis of Selection

    Sunoco/UOP Process was chosen based on the benefits mentioned in the techno-

    economic appraisal above.

    5.2 Details of selected process - Sunoco/UOP Process

    The major processing steps include:

    (1) Liquid-phase oxidation of cumene to cumene hydroperoxide [CHP]

    (2) Concentration of CHP

    (3) Acid-catalyzed decomposition of concentrated CHP to phenol and acetone

    (4) Neutralization of acidic decomposition product

    (5) Fractionation of the neutralized decomposition product for recovery of acetone,

    phenol, AMS, and residue

    (6) Recovery of phenol and the effluent wastewater via an extraction process to prepare

    it for further downstream treatment required to meet effluent quality specifications

    (7) Hydrogenation of AMS back to cumene for recycling to synthesis; or, optionally,

    refining of AMS for sale as a product

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    The details of each of these main processing steps are discussed as follows highlighting

    recent technological advances made by various licensors of phenol technology.

    5.3 Process flow and recent technology advances

    5.3.1 Oxidation section process flow-

    Using the Sunoco/UOP process as an example, Fig. 7 shows a typical series flow two-

    oxidation reactor configuration for the low-pressure technology. As many as 56

    reactors or more reactors can be used in multiple reaction trains depending on the

    capacity of the unit, location, processing objectives, and to stage the investment over

    time as capacity increases are needed.

    The fresh cumene feed is pumped from the oxidation day tank to the combined feed

    surge drum. Recycle cumene streams from other sections of the plant are combined

    and flow through the feed pre-wash column, where organic acids are removed by

    scrubbing with weak caustic and water. The recycle cumene then joins with the fresh

    cumene feed in the combined feed surge drum. The combined feed is then pumped to

    oxidizer No. 1.

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    Cumene is also used for various utility-like purposes through the plant. Cumene is sent

    from the day tank to the phenol recovery section on a batch basis as make-up solvent. It

    is also used as pump seal flush in the various sections of the plant. The two oxidizers

    are in series with respect to liquid flow but in parallel with respect to air flow. The

    oxygen requirement for the oxidizers is supplied from atmospheric air. The air is first

    filtered and then compressed before going into the oxidizers through a sparger. The

    heat of reaction in the first oxidizer is balanced by adjusting the temperature of the cool

    cumene feed, so that no other cooling is required.

    For large phenol units, it is economical to recover the heat of reaction from the second

    oxidizer by heat integration with the concentration section. The hot oxidizer circulating

    liquid stream is used to supply heating to the pre-flash column upper vaporizer. The net

    oxidate from oxidizer No. 2 (effluent from oxidation section) flows directly to the

    concentration section. As shown in the flow diagram (Fig. 8) again for the Sunoco/ UOP

    process, the spent air streams from both oxidizers are combined and routed through a

    water-cooled condenser, a chilled condenser and an entrainment separator for the

    maximum removal of hydrocarbon and cumene. From the entrainment separator, the

    air flows to the charcoal absorbers.

    Two of the adsorbers are always on line in series flow, while the third one is being

    regenerated with steam. The cleaned air from the charcoal absorbers is vented to safe

    atmospheric disposal. A catalytic incinerator is usually not needed to meet emission

    limits, but one can be provided if regulations stipulate incineration as the emission

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    control method. The cumene collected by the charcoal adsorbers is recovered by

    desorption with low-pressure steam followed by condensing the steam and decanting

    the cumene and water phases. The cumene is then recycled to the

    feed pre-wash column.

    Recent advances in oxidation section technology

    For the Sunoco/UOP technology, recent improvements to the oxidation section include:

    (1) The use of high-efficiency charcoal adsorption to recover trace products from spent

    air

    (2) Use of an emergency water spray installation and elimination of oxidizer rupture

    disks

    (3) A reduction in oxygen content of vent gas thus reducing air compressor capacity

    (4) The elimination of the requirement for caustic scrubbing of fresh feed from zeolitic

    cumene unit

    (5) Use of a dilute caustic wash tower that replaces the feed wash mixer/settler system

    (6) The integration of the decanter with the concentration section vacuum system and

    elimination of the vent gas scrubber

    (7) The integration of the feed coalescer into the combined feed surge drum and

    (8) The use of common spares for oxidizer pumps and emergency coolers.

    All of these improvements serve to reduce capital and operating costs of the process

    making it one of the most effective phenol processes available

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    5.3.2 Concentration section process flow

    An example of the typical flow for the concentration section of the process where CHP

    in the oxidizer reactor effluent is concentrated to a level of 7585 wt.% prior to

    decomposition to phenol and acetone is shown for the Sunoco/UOP process in Fig. 9.

    The oxidate from the last oxidizer flows to the concentration section to recover

    unreacted cumene. For large phenol units, it is economical to use a two-column

    concentration system, in which the heat of reaction from oxidizer No. 2 and very low-

    pressure steam are used to vaporize cumene in the first (pre-flash) column, reducing

    the size of the main flash column. The pre-flash drum and flash column operate under

    vacuum to minimize the temperature necessary to concentrate the CHP. The vacuum is

    typically generated by an ejector system. Under vacuum in the pre-flash drum, cumene

    vaporizes in the upper vaporizer using heat from the second oxidizer cooler. Additional

    cumene vaporizes in the lower vaporizer with heat supplied by very low-pressure

    steam. Final CHP concentration is achieved in the flash column vaporizer and flash

    column, both of which operate under deeper vacuum than the pre-flash drum. The pre-

    flash drum bottoms stream flows through the flash column vaporizer, where additional

    cumene vaporizes using heat from low-pressure steam.

    The CHP content of the flash column overheads is minimized by rectification in the flash

    column, using either screen trays or packing, whichever is more economical. The flash

    column overheads, consisting of primarily cumene, is recycled to the oxidation section

    via the feed pre-wash column. The concentrated CHP collects in the integral

    receiver/cooler at the bottom of the flash column, where it is cooled to a safe

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    temperature. The CHP concentrate from the flash column bottoms reservoir is then

    pumped to the decomposition section.

    A cumene quench tank is also provided in this section for automatic emergency

    quenching of various strategic sections of the concentration section if necessary to

    maintain safe operating temperatures in the event of an incipient CHP decomposition

    excursion.

    Recent advances in Concentration section technology

    For the Sunoco/UOP process, recent improvements include:

    (1) Heat integration with oxidation section

    (2) A two-stage concentration section consisting of pre-flash and flash column

    (3) Elimination of overhead receivers

    (4) Use of a Packinox style exchanger in the flash column condenser

    (5) Use of power traps instead of level-controlled pumped condensate pots.

    All of these improvements are claimed to reduce capital costs for the process.

    5.3.3 Decomposition section flow

    The decomposition or cleavage section of the process involves the catalytic

    decomposition of concentrated CHP in the presence of ppm levels of acid to crude

    phenol and acetone. The most effective technology for this section is a unique two-step

    process described in U.S. Patent 4,358,618 by Sifniades/Allied Corporation patented in

    1982. The process involves the use of a back mixed reactor section at low

    temperature/higher contact time for the main CHP decomposition step followed by a

    plug flow dehydration section at higher temperature/short contact time for conversion

    of dicumylperoxide (DCP) to AMS. The process represents a breakthrough in AMS yield

    improvement and with the expiration of the patent in 1999, is currently being used by

    all licensors as the process of choice for modern high yield phenol technology. An

    example of the most advanced decomposer technology is the process offered by

    Sunoco/UOP shown in Fig. 10. It consists of a very simple but elegant drum and loop

    reactor design where concentrated CHP from the concentration section flows into the

    decomposer drum, along with a metered amount of water to maintain optimal reaction

    conditions in the decomposer recycle loop. Sulfuric acid is injected via injection pumps

    into the loop to provide the catalyst required for the decomposition of CHP to phenol

    and acetone. A circulation pump is provided to circulate the content of the decomposer.

    Sulfuric acid is injected into the circulating stream to such an extent that the

    decomposition of CHP and dehydration of dimethylphenylcarbinol (DMPC), a key by-

    product of oxidation reaction, are precisely controlled. The level of unreacted CHP is

    monitored via calorimeters, to which part of the acid catalyst flow is routed.

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    The effluent from the decomposer is pumped to the dehydrator in which the effluent is

    heated to a temperature where remaining DMPC is dehydrated and DCP converted to

    AMS at very high yield. This is a unique advantage of the Sunoco/UOP decomposition

    technology. The Sunoco/UOP process produces approximately 90% AMS yield from

    DMPC. This also results in higher phenol yield, thus lower cumene consumption and

    less residue (e.g., tar) formation.

    Recent advances in Decomposition section technology

    In addition to very high yields across the decomposer section, the Sunoco/UOP

    technology offers the following recent improvements:

    (1) The implementation of advanced process control (APC)

    (2) A reduction in required recycle rate from 100:1 to 25:1

    (3) The elimination of water injection tank and pumps

    (4) Use of acid totes to eliminate the acid tank dependent on unit size and client

    preference

    (5) Design of the unit for safe containment in most probable relief situations and

    elimination of the catch tank.

    The major advantage of these improvements is reduced capital costs and improved

    process yields and economics. AMS yields as high as 8590% across the decomposer

    section have been demonstrated making the Sunoco/UOP technology one of the most

    selective offerings in the industry today.

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    5.3.4 Neutralization section process flow

    The acid catalyst that is added in the decomposition section must be neutralized to

    prevent yield loss due to side reactions and protect against corrosion in the

    fractionation section. The Sunoco/UOP Phenol process uses a novel approach for

    neutralization: the acid catalyst is neutralized by injecting a stoichiometric amount of a

    diamine which does not need to be removed from the process, as shown in Fig. 11.

    The main advantages of direct diamine neutralization over conventional systems are:

    (1) A new/simplified design that is easy to operate and reduces capital cost

    (2) Process uses soluble salts that reduces reboiler fouling and lowers maintenance

    costs

    (3) Does not require water addition for neutralization which in turn lowers wastewater

    production and reduces distillation utilities.

    Recent advances in Neutralization section technology

    By replacing older ion exchange resin technology with the new direct neutralization

    process, Sunoco/UOP claim that phenolic wastewater production can be reduced by

    45% or more at lower capital cost.

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    5.3.5 Acetone refining section process flow

    Acetone is a major by-product of the CHP oxidation process for the production of

    phenol. The overall economics of the process are highly dependent on production of

    high quality acetone (e.g., 99.799.9% purity) for sales in the solvents market and bis-

    phenol A markets.

    Fig. 12 shows the typical flow scheme for the Sunoco/UOP process. Fractionation feed

    goes from the fractionation feed tank to the crude acetone column. Water is injected as

    necessary to the bottom of the crude acetone column to increase the volatility of the

    acetone and maintain the bottom temperature. The overhead of the column, consisting

    of acetone, water and some cumene flows to the finished acetone column (FAC).

    The key impurities removed in the FAC are aldehydes, which have been historically

    analyzed with the permanganate fading test, and water. More recently, as the product

    quality demands for acetone have increase, most phenol producers use gas

    chromatography (GC) as the definitive method for determining aldehyde content. The

    Permanganate Fading test is simply not effective for aldehydes unless the level is in the

    range of several hundred ppm or more. Caustic is injected into the FAC column to

    catalyze the condensation of trace aldehydes. The heavier condensation products are

    less volatile and leave with the FAC bottoms.

    High-purity acetone flows by gravity from the FAC side cut near the top of the column to

    the acetone product day tank. The net bottoms stream of the FAC flows to the FAC

    bottoms drum where cumene and water are separated. The water goes to the sewer

    while the cumene is recycled to the oxidation section.

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    Recent advances in Acetone refining section technology

    Recent improvements for the Sunoco/ UOP process include the use of stabbed-in

    condensers and elimination of overhead receivers, where appropriate, to save capital

    cost.

    5.3.6 Phenol fractionation and purification process flow

    Once the crude phenol has been produced, it must be further fractionated to prepare a

    finished product that is of sufficient purity to meet downstream user specs. An example

    of the phenol purification is shown in Fig. 13. It is based on Sunoco/UOP technology

    using AMS hydrogenation as a means of recycling the by-product AMS to maximize

    phenol production.

    The bottoms material from the crude acetone column flows to the cumene/AMS column

    where cumene and AMS are recovered overhead and sent to the cumene caustic wash

    in the phenol recovery section. A chemical agent is injected into the bottom half of the

    column for the removal of carbonyl impurities such as acetol (a-hydroxyacetone) and

    mesityl oxide from the phenol. The bottoms from the column are routed through a

    chemical treatment reactor which provides residence time for the chemical treatment

    reactions.

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    The effluent from the chemical treatment reactor flows to the crude phenol column

    where the heavy components distill to the bottoms and then flow into the residue

    stripper column for removal as the net residue by-product. This separate residue

    stripper column section allows the final stripping of phenol from the residue to be

    conducted at higher vacuum, which allows both the crude phenol column and residue

    stripper column to be reboiled with medium-pressure steam. Thus, no high-pressure

    steam is required for the phenol plant! The residue product has flow and combustion

    properties similar to No. 6 fuel oil, and is typically charged to a dedicated burner a

    boiler furnace.

    The crude phenol column has a top pasteurizing section to remove the small amount of

    light by-products generated during distillation. The main product from the column is

    taken off as a side cut and flows to IX resin treaters, in which the ion exchange resin

    catalyzes conversion of methylbenzofurans (MBF) and residual AMS to high-boiling

    components. MBF and AMS are otherwise difficult to remove by distillation. The effluent

    from the IX resin treaters goes to the phenol rectifier, where the heavy components

    along with some phenol are distilled to the bottoms and recycled back to the crude

    phenol column. The phenol rectifier also has a top pasteurizing section for removal of

    small amounts of light by-products generated during distillation. Phenol product flows

    by gravity from the rectifier side cut to storage.

    Recent advances in Phenol purification section technology

    For the Sunoco/UOP process, improvements in the phenol fractionation and purification

    section included:

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    (1) Replacement of the azeotropic phenol stripper with chemical/resin treating

    (2) Elimination of the acid neutralizer system

    (3) Use of stabbed-in condensers and elimination of overhead receivers where

    appropriate.

    The main benefit of these changes has been reduced capital/utilities cost while

    maintaining the already very high overall phenol product quality. Further, equipment

    sizes and wastewater have been significantly reduced by implementation of the

    advance Sunoco/UOP Phenol recovery technology shown in Fig. 14.

    5.3.7 AMS hydrogenation section flow

    The Sunoco/UOP Phenol process utilizes AMS hydrogenation technology developed by

    Huels. The Huels MSHPTM process is a mild hydrogenation process based on a Pd

    containing catalyst system that operates at moderate pressure. The process achieves

    nearly complete conversion of AMS with very high selectivity to cumene resulting in a

    very low overall process cumene/phenol consumption ratio of 1.31 w/w. The simple

    process shown in Fig. 15 has been demonstrated to operate without significant catalyst

    deactivation over multiple years of operation.

    In this section the AMS in the cumene/AMS stream from the phenol recovery section is

    selectively hydrogenated to cumene by the Huels MSHP process. The fresh

    cumene/AMS feed is mixed with reactor effluent recycle and hydrogen. The combined

    feed passes through Hydrogenation Reactor No. 1, where the bulk of the AMS is

    hydrogenated to cumene. The reaction is highly exothermic.

  • 23 | P a g e

    The reactor effluent recycle is cooled before joining with the fresh feed. The net flow

    goes to Hydrogenation Reactor No. 2 as a finishing reactor to complete conversion of

    AMS to cumene. Product from the second reactor goes through the product cooler and

    then to the product separator. Hydrogen flow is once through, with only a slight excess

    over stoichiometric. The flow rate of feed hydrogen is regulated based on the flow of

    excess hydrogen and light gases from the product separator. Dissolved gases which

    come out of solution when the liquid flashes to low pressure are disengaged in the flash

    drum. The cumene liquid product is then recycled to oxidation.

    Recent advances in AMS Hydrogenation section technology

    Advances in the Sunoco/UOP/Huels AMS hydrogenation technology include:

    (1) Elimination of the recycle hydrogen compressor

    (2) Elimination of the hydrogen flash drum and pumps. Both of these improvements

    save capital cost and utilities.

    5.3.8 Tar Cracking

    Both Sunoco/UOP and KBR claim that tar cracking of heavy ends produced in the

    phenol process is no longer required due to the improvement in process yield achieved

    over the last 10 years. KBR claims that phenolic tars have been reduced by as much as

    40%. By eliminating tar cracking, phenol product purity has improved so that total

    organic impurities (including cresols) have been reduced to 50 ppm, according to KBR.

    Sunoco/UOP, with additional refinements in cumene and phenol fractionation

    technology, have further reduced this level to about 30 ppm.

    5.3.9 Phenol process safety

  • 24 | P a g e

    Safety considerations in the production of phenol and acetone from cumene include

    design and operating criteria for processing the intermediate CHP. CHP decomposes

    rapidly to phenol and acetone when exposed to strong acids, even at low temperatures.

    This reaction is highly exothermic and is the second reaction step in the process.

    At high temperatures, the rate of CHP decomposition catalyzed by weak acids would

    also become significant. In addition, CHP reacts with cumene to form

    dimethylphenylcarbinol. This reaction occurs to some extent under normal conditions

    in the oxidation, concentration and decomposition sections, but the rate becomes

    significant at higher temperatures. At still higher temperatures, CHP also decomposes

    thermally to form acetophenone and methane. CHP decomposition catalyzed by weak

    acids and the thermal CHP reactions would only become significant from a safety

    standpoint in the event that heat cannot be removed. In such a case the increasing

    temperature from the heat of reaction would result in a higher reaction rate, creating

    the potential for an uncontrolled reaction.

    Thus, the availability of heat exchangers, cooling medium, and pumps for cooling CHP

    mixtures is critical from a safety standpoint. A significant advantage of the Sunoco/UOP

    low-pressure oxidation technology in addition to high yields is the very mild operating

    temperature (e.g., typically 8290 Degree Celcius) required for the process. The lower

    oxidizer operating temperature translates into a much longer allowable operator

    response time in the event intervention is required due to an upset to prevent oxidizer

    temperatures that are high enough to promote CHP thermal decomposition. The

    intervention response time may be as long as 24 h or more to avoid elevated

    temperatures and high rates of CHP decomposition in the oxidizers. For high-pressure

    processes such as KBR and GE/Lummus, the response time is much shorter, on the

    order of only a few hours, to prevent accelerated CHP thermal decomposition due to

    the higher initial process temperature (e.g., typically 95100 8C or more).

    The Sunoco-UOP Phenol process design and operating criteria are based on an industry

    accepted 10,000-year probability guideline. Safety provisions include emergency coolers

    and pumps, reliable power supplies, reliable cooling water supply, and further backup

    provisions including ability to use firewater as once through cooling water, and the

    capability to use cool cumene to reduce (quench) temperature. For all cooling services

    designated as critical, if cooling becomes unavailable, it must be possible to reestablish

    cooling within 20 h with 99.99% certainty.

    Analysis has shown that meeting this availability criterion typically requires a cooling

    water supply system with a minimum of three pumps, with two normally operating and

    the third in standby; and multiple independent power sources for the pumps and

    cooling tower fan. For all pumping services designated as critical, if pumping becomes

  • 25 | P a g e

    unavailable, it must be possible to re-establish pumping within 20 h with 99.99%

    certainty. Meeting this criterion typically requires multiple sources of power. Options for

    multiple independent power sources can include, but are not necessarily limited to, an

    emergency electric power generator, steam-driven turbine, a direct drive engine, or

    multiple independent external electric power supplies. While the first three options are

    less reliable than normal electrical power, the combination of multiple power sources

    provides a more robust system than a typical single external electrical power supply.

    For example, if a diesel powered emergency electric power generator is utilized, a

    probability of 97% is typical. Emergency generators are less reliable than normal

    electrical power because of the probabilities associated with failure to start, failure to

    run, and unavailability due to testing and maintenance. Quantitative risk assessment is

    typically performed to verify the reliability of such systems.

    6. Raw Material

    6.1. SOURCES OF RAW MATERIAL

    Cumene peroxidation process is a process involves the liquid phase air oxidation of

    cumene to cumene peroxide, which in turn is decomposed to phenol and acetone by

    the action of acid. During the cumene peroxidation process, there are two main raw

    materials used in this process which are cumene and oxygen. Oxygen is a gas form

    fluid. Oxygen is colourless gas that can be found in the air. In the air there is 21% of

    oxygen contains while another 79% is nitrogen gas. Oxygen acts as an oxidizer. Table

    shown the physical and chemical properties of oxygen as well as cumene.

    Most important cumene specifications:

    Purity 99.90 wt-%, min.

    Benzene 10 wt-ppm, max.

    Toluene 5 wt-ppm, max.

    Ethylbenzene 50 wt-ppm, max.

    n-Propylbenzene 300 wt-ppm, max.

    Butylbenzenes 100 wt-ppm, max.

    (for 99.5 wt-% AMS purity)

  • 26 | P a g e

    PHYSICAL AND CHEMICAL PROPERTIES of CUMENE (TYPICAL)

    PROPERTY DATA & INFORMATION

    Synonyms Isopropyl benzene

    Chemical Formula C6H5CH(CH3)2

    Physical State at room

    temperature

    Liquid

    Odor Aromatic

    Appearance Colorless liquid

    Boiling Point Critical

    Temperature

    152C -

    Melting Point -------------------------

    Specific Gravity 0.86 (Water = 1)

    Molar mass 120.00 g/mol

    Solubility in water Negligible solubility in cold water

    Vicosity

    (cSt @ 40C)

    0.7

    Vapor Pressure 1.1 kPa (8 mm Hg) (at 20C)

    Volatility 862 g/l VOC (w/v)

    Flash point Closed cup: 36C (96F). (Pensky-Martens.)

    Additional

    Properties

    Paraffin, Isoparaffin and Cycloparaffin Hydrocarbons

    Content = 99 Wt. % (ASTM D-

    1319);

    Average Density at 60F = 7.19 lbs./gal. (Calculated via

    ASTM D-287);

    Aniline Cloud Point Temperature = 52F (11C) (ASTM D-

    611);

    Kauri-Butanol (KB) Value = 96 (ASTM D-1133);

    Dry Point Temperature = 307F (153C) (ASTM D-86, D-850

    or D-1078);

    Evaporation Rate = 0.5 (n-Butyl acetate = 1.0);

    Heat Value = 18,670 Btu. per pound

  • 27 | P a g e

    STABILITY AND REACTIVITY

    Chemical

    Stability

    Stable.

    Hazardous

    Polymerization

    Not expected to occur.

    Conditions to

    Avoid

    Keep away from heat, sparks and flame. Forms explosive

    peroxides with prolonged storage

    Materials

    Incompatibility

    Strong acids, alkalies, and oxidizers

    Hazardous

    Decomposition

    Products

    No additional hazardous decomposition products were identified

    other than the combustion

    products identified in Section 5 of this MSDS.

    6.2 Availability of Cumene

    Ashland Chemical, Inc. and Chevron Chemical Co. offer cumene in tank car, tank truck,

    and barge quantities.

    Cumene is available from various Naptha crackers across India which includes - IOCL

    Panipat, Hazira of Reliance, IPCL Vadodara, Haldia of Haldia petrochemicals

    6.3 Import Data

    Major importers of cumene in India are -

    Macoma Hardwares

    Tuff Stone Marketing Pvt Ltd.

    Chemilab Corporation

    Schenectady Herdillia Limited

    Bayer Abs Limited

    7th Floor, Abs Towers Old Padra Road

    BARODA , Gujrat

    Btp India Private Limited

    Kences Towers, (Ii Floor) , No.1, Ramakrishna Street,t.nagar,

    CHENNAI, TAMIL NADU

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    6.4 Export Data

    Major Exporters in India are -

    Alok Industries Ltd.

    43-b;mittal Tower Nariman Point,

    MUMBAI. MAHARASHTRA

    M-tex Exports

    505,gagangiri Avenue, Samta Nagar,opp.raymonds,

    THANE , MAHARASHTRA

    Chemilab Corporation

    55, B. R. B. Basu Road, B- Block, 3rd Floor, Room No. 55,

    CALCUTTA , WEST BENGAL

  • 31 | P a g e

    6.5 Prevailing prices

    6.6 Govt Policies and Import Duty

    Import Duty on Cumene

    Description Duty (in

    INR)

    Basic Duty 5.00

    Education Cess 2.00

    Secondary Hiigher Education Cess 1.00

    Contravailing Duty (CVD) 12.00

    Additional Contravailing Duty 4.00

    Additional Cess 0.00

    National Calamity Contigent Duty (NCCD) 0.00

    Abatement 0.00

    Total Duty 22.85

  • 32 | P a g e

    Bisphenol

    1. Uses & Importance -

    Bisphenol is an important building block and its measure use is in the manufacture of

    polycarbonate plastic and epoxy resins. Other uses include in flame retardants,

    unsaturated polyester resin and polyacrylate, polyetherimide and polysulphone resin.

    Some common uses are mentioned below -

    Store Sales Receipts

    Some thermal paper receipts can contain BPA as a component of the heat sensitive

    coating that allows for inkless printing. This paper technology provides speedy, reliable

    and cost-effective printing.

    Packaging & Storage

    BPA is used to make polycarbonate plastic and polymeric coatings called epoxy resins

    for food packaging and storage that are essential to enhance the safety of our food

    supply and contribute to healthy, modern life styles.

    Medical

    Polycarbonate plastic is used to make critical components of many medical devices and

    their housings. Its optical clarity allows direct observation of blood or other fluids to

    monitor proper flow. Health care providers depend on medical devices and equipment

    made with BPA for a transparent view within the human body so they can check for the

    presence of air bubbles or other obstructions during medical procedures.

    Safety Equipment

    BPA is regularly used to strengthen products for human health and safety. Products like

    bike helmets, police shields, reading glasses and bullet-proof glass are all shatter

    resistant because of BPA.

    Electronics & Auto

    BPA is used to make parts of cars, circuit boards, flat screen televisions and smart

    phonesimproving safety and quality of many of the products.

    Industrial & Business

    From LED lights to adhesives, find out how BPA is used for industrial and architectural

    purposes.

  • 33 | P a g e

    Optical Media

    Compact Discs

    CD-ROMs

    Digital Versatile Discs

    HD-DVDs

    Blu-RayDiscs

    Holography Discs

    Innovative Data Storage Technology (e.g. Near Field Recording Discs)

    Forgery-proof holographic shadow pictures in ID cards

    Construction: Buildings

    Sheets for roofing, conservatory glazing

    Architectural glazing (e.g. sports arenas)

    Greenhouse glazing

    Rooflights

    Cover for solar panels

    Noise reduction walls for roads and train tracks

    Car port covers

    Glazing for bus stop shelters

    Roadsigns

    Internal safety shields for stadiums

    Transparent cabins for ski lifts

    Housings and fittings for halogen lighting systems

    Roadsigns

    Front panels for advertising posters, signboards(e.g. fuel stations)

    Large advertising displays

    Dust & water-proof luminaires for streetlights and lamp globes

    Diffusing reflectors for traffic lights

    Others: Safety

    Safetygoggles

    Protective visors for welding or handling of hazardous substances

    Protective visors for motor bikes, snowmobiles

    Motorbike and cycle helmets

    Fencing helmets

  • 34 | P a g e

    Safety shields for policemen

    Guards to protect workers from moving machine parts

    2. Market Prospects -

    Demand of bisphenol in India during 2010-11 was 30,000 tonnes per annum

    Global installed capacity: around 5.2 million tones

    Global demand around 4.2 million tones

    Global growth rate in demand 5 to 6percent

    Polycarbonate resin are the largest and fast growing BPA market, consuming

    60percent of the global production.

    Epoxy production

  • 35 | P a g e

    3. Production Methods -

    Various process technologies available for manufacture of bisphenol are:

    A) Synthesis of Bisphenol-A from phenol and acetone using Organic-Inorganic

    modified heteropoly acid catalyst

    BPA is conventionally produced through acid catalyzed condensation reaction between

    phenol and acetone by using ion-exchange resins promoted by mercapto compounds.

    Excellent performance is shown by ion-exchange resins in experiments. It has been

    tested that modified ion-exchange resins like Amberlyst show very good activity for BPA

    synthesis. Because of thermal instability of resin catalysts, they cannot be used at

    higher temperatures. The other problem being fouling of resin catalysts in the reactor.

    Use of inorganic acid catalysts have been tried and found effective.Bisphenol-A is

    synthesized using an effective design of heteropoly acid catalyst by organic-inorganic

    dual modification. Dual modification was made by partial Cs ion exchange for lowering

    acid strength and by immobilization of 2-diethylamino-ethanethiol (DEAT) adjacent to

    protonic acid sites. Yields near to 94% is achieved on designed catalyst which is

    equivalent to conventional ion-exchange catalyst (yield 96%). The aim of this study is to

    develop an effective strategy of catalyst design for BPA synthesis. Ion exchange resins

    are the preferred catalysts, but these have temperature limitations.

    B) Synthesis of bisphenols using ion-exchange catalysts

    Modification of an insoluble strong-acid cation-exchange resin in acid form by partial

    neutralization with a mercaptoamine yields an improved catalyst for the preparation of

    bisphenols by condensation of a phenol and a ketone.This invention relates to an

    improved resin catalyst for the preparation of bisphenols and particularly bisphenol A.

    More specifically, the improved catalyst is an insoluble strong-acid cation-exchange

    resin in acid form modified by partial neutralization with a mercapto amine. Sulfur

    compounds have long been recognized as effective promoters for the acid catalyzed

    condensation of phenols and ketones to form bisphenols. For example, in US. Patent

    2,359,242 Perkins and Bryner describe the use of H 5 in the condensation of phenol

    with acetone, methyl ethyl ketone, cyclohexanone, and other similar ketones. In US.

    Patent 2,917,550 Dietzler recommends as a promoter a soluble ionizable sulfur

    compound such as H S, methyl mercaptan, ethyl mercaptan, or n-octyl mercaptan.Such

    soluble promoters however introduce subsequent problems in the purification of the

    bisphenol. Particularly when the bisphenol is used in the synthesis of epoxy and

    polycarbonate resins, its purity is a critical factor. Extensive processing is often required.

    Thus the search for improved catalysts, greater process efliciency and enhanced

    product color, odor and purity continues.Recently Apel, Conte and Bender disclosed in

  • 36 | P a g e

    US. Patents 3,049,568 and 3,153,001 a resin catalyst prepared by partial esterification of

    a substantially anhydrous strong-acid cation-exchange resin with a lower alkyl

    mercaptoalcohol. By chemically bonding the mercaptan promoter to the insoluble resin

    by esterification, contamination of the product with the mercaptan is reducedIt has now

    been discovered that partial neutralization of a strong-acid cation-exchange resin with a

    C -C alkyl mercaptoamine provides another new and improved resin catalyst for the

    preparation of bisphenols. As illustrated by the following equation for partial

    neutralization of a sulfonated aromatic resin with 2-mercaptoethylamine.

    C) ZnCl2-modified ion exchange resin as an efficient catalyst for bisphenol-A

    production

    A ZnCl2-modified ion exchange resin as the catalyst for bisphenol-A synthesis was

    prepared by the ion exchange method. Scanning electron microscope (SEM),

    thermogravimetric analyzer (TGA) and pyridine adsorbed IR were employed to

    characterize the catalyst. As a result, the modified catalyst showed high acidity and good

    thermal stability. Zn2+ coordinated with a sulfonic acid group to form a stable active site,

    which effectively decreased the deactivation caused by the degradation of sulfonic acid.

    Thus the prepared catalyst exhibited excellent catalytic activity, selectivity and stability

    compared to the unmodified counterpart.To overcome the shortcomings of ion

    exchange resins, numerous efforts have been made, including loading thiol groups

    and/or amine groups by means of reduction, esterification, neutralization or ion

    exchange method. Takahim and Toshitaka successfully synthesized a modified catalyst

    with mercapto alkyl amine, which showed a great improvement in the condensation of

    phenol and acetone. Carvill et al. discovered that 4-(2-mercaptoethyl)-pyridine was a

    good modified reagent.Ion exchange resins have been used in other reactions, such as

    esterification, transesterification, oligomerization. Low acid strength is also one of their

    main drawbacks affecting the reaction efficiency. Some researchers attempted to solve

    this issue by introducing Lewis acids into the resins. Magnotta and Gates reported that

    the acidic property of the complex formed by AlCl3sulfonic acid can be similar to that of

    the superacid solution of SbF5 + FSO3H. Shi showed that the efficiency of acid-catalyzed

    transesterification and esterification reactions depend on the subtle balance between

    Lewis and Brnsted acidities.

    4. Techno-Economic appraisal of alternative processes

    The use of a novel catalyst based on heteropolyacid supported on clay, particularly

    dodecatungstophosphoric acid (DTP) supported on K-10 clay and its comparison with

    commercially available resins such as Amberlyst-15, Amberlyst-31 and Amberlyst-XE-

  • 37 | P a g e

    717p shows DTP/K-10 is an efficient and re-usable catalyst which could be employed at

    higher temperatures. The kinetics of the reaction with DTP/K-10 have shown interesting

    features among which the formation of intermediate isopropenyl phenol was found to

    be the rate determining step with the Eley-Rideal type of mechanism.of phenol to

    acetone are required for a facile progress of the reaction as well as to suppress the side

    reactions of acetone. Conventionally bisphenol-A is manufactured by the acid catalysed

    condensation of phenol and acetone. Ion exchange resins are the preferred catalysts,

    but these have temperature limitations. High molar proportions of phenol to acetone

    are required for a facile progress of the reaction as well as to suppress the side

    reactions of acetone. A large number of side-products are generated depending upon

    reaction conditions and the type of catalyst. An ideal catalyst for this reaction should be

    moderately acidic and shape selective, whereby lesser quantities of the by-products

    would be formed. Ion exchange resins have been used in other reactions, such as

    esterification, transesterification, oligomerization. Low acid strength is also one of their

    main drawbacks affecting the reaction efficiency. Some researchers attempted to solve

    this issue by introducing Lewis acids into the resins. It has been proved that the

    coordination of a Lewis acid with a Brnsted acid can increase its original

    acidity.Therefore, the design of dual acid catalysts based on resins can be advantageous

    in the BPA production. In this study, ZnCl2 acting as a Lewis acid was added into cationic

    ion exchange resins to fabricate a more efficient catalyst. To the best of our knowledge,

    this is the first resin catalyst for producing BPA that contains both a Brnsted acid and a

    Lewis acid.

    5. Details of selected process

    REACTION CHEMISTRY

    The acid catalysed condensation of phenol and acetone in homogeneous medium leads

    to several products; in particular with strong sulphuric and hydrochloric acids almost 28

    products have been identified. Strong acids such as 70% sulphuric acid, hydrochloric

    acid or sulphonated polystyrene divinylbenzene cation exchange

  • 38 | P a g e

    resins are industrially preferred. Fig. 1 shows the reaction scheme. In a strong

    acid medium, acetone is protonated to a stable carbenium ion as shown by

    reaction a in Fig. 1. Following steps occur:-

    Reaction b-The carbenium ion adds to the limiting quinonoid structure of

    phenol to yield a protonated carbinol.

    Reaction c-The carbinol rearranges to release water and yields protonated

    isopropenyl phenol.

    Reaction d- The isopropenylphenol adds to a second phenol molecule to yield

    bisphenol-A.

    Several by-products are formed during this reaction and are shown in next fig.

  • 39 | P a g e

  • 40 | P a g e

    The major one being the o,p 1 isomer formed by the reaction of p-isopropenyl-phenol

    with the phenol in the ortho position (reaction f). Other side products are the chroman

    derivatives formed by the reaction of phenol with mesityl oxide, which itself is a product

    of self-condensation of acetone followed by dehydration (reaction e, Fig. 2). Out of the

    28 products mentioned, those which are formed in relatively larger quantities are 2,2,4-

    trimethyl chromen, 1,1,3-trimethyl-5-indanol, 9,9- dimethylxanthane and dimethyl

    hydroxy biphenyl. The remaining by products constitute to less than 0.2% of the

    reaction mixture. It is obvious from Fig. 2 that the formation of byproducts can be

    suppressed if the self- condensation of acetone followed by dehydration leading to

    mesityl oxide is avoided. One of the ways would be to employ excess of phenol over

    acetone in batch experiments or semibatch mode of operation with continuous

    addition of acetone making the phenol to acetone ratio very high.

  • 41 | P a g e

    Chemicals and catalysts

    The preparation of alumina, zirconia, chromia exchanged clays and heteropoly

    acid supported on clays has been detailed elsewhere [3,11]. Amberlyst-15,

    Amberlyst-31 and Amberlyst XE-717p were procured from Rohm and Haas

    (USA). K-10 and Filtrol-24 were purchased from Fluka (Switzerland) and

    Engelhardt (Germany), respectively.

    Preparation of dodecatungstophosphoric acid (dtp) supported

    on clay (DTP/K-IO)

    Approximately 10 g of K-10 clay was dried in an oven at 120C for 1 h of which 8 g were

    weighed for subsequent experiment. 2 g of dry DTP was also weighed.The HPA was

    dissolved in 8 ml of dry methanol. This volume of solvent was approximately equal to

    the pore volume of the catalyst. The solution was added in aliquots of 1 ml each to the

    clay under constant stirring with a glass rod or kneading it properly. The solution was

    added at time intervals of 30 sec. Initially and up to the addition of 6 ml of the DTP

    solution, the clay was in the powdery form but upon subsequent addition the clay

    formed a paste. Further kneading of the paste for 10 min. yielded a dry free flowing

    powder. The preformed catalyst was dried in an oven at 120 C for 1 h and then

    calcined at 275C for 3 h.

    Reaction procedure

    All the experiments were carried out in a 100 ml Parr autoclave equipped with a

    four bladed turbine impeller. The temperature was maintained within i0.5C of

    the desired value. The vessel was also equipped with a speed regulator that could

    maintain the desired speed at + 1% of the set value. Predetermined quantities of

    reactants and the catalyst were charged into the autoclave and the temperature was

    raised to the desired value. Once the temperature was attained the initial sample was

    withdrawn at time=0 and the stirrer was started. Further samples were withdrawn at

    definite time intervals. A typical experiment consisted of 5.28 g (0.091 gmol) of acetone,

    42.77 g (0.451 gmol) of phenol, 1.25 g of catalyst (loading of catalyst, 0.0268 g/cm 3 of

    the liquid phase). The reaction temperature was maintained at 100C and 135C for the

    ion exchange resins and inorganic catalysts, respectively.

    Analysis

    The samples were analysed in a gas chromatograph (Perkin-Elmer Model 8500)

    equipped with a flame ionisation detector. A 2 0.003 m column packed with 10% OV-

  • 42 | P a g e

    17 supported on chromosorb WHP was used. Calibration curves were prepared by

    using standard samples and synthetic mixtures in order to quantify the data.

    Results and discussion

    1) Comparison of the activity of the catalysts

    A maximum of six products were detected in the reaction mixture. The products were

    identified as 1,1,3-trimethyl-5-indenol, 2,2,4-trimethyl chromen, 9,9- dimethyl xanthane,

    dimethyl hydroxy biphenyl, o,p-l-bisphenol and bisphenol- A. In the case of Amberlyst-

    31 and Ambedyst-XE-717p only o,p-l-bisphenol and bisphenol-A were formed, whereas

    in the case of Amberlyst-15, all the by products were formed in large quantities

    resulting in a lower selectivity to bisphenol-A.

    Since it was desired to test the efficacy of dodecatungstophosphoric acid supported on

    K-10, a few experiments were also conducted with the support clay K-10 as well as

    Filtrol-24 as shown in Table 1. Both K-10 and Filtrol-24 were rather ineffective. As was

    expected, Lewis acid type catalysts, such as alumina exchanged K-10, zirconia K-10,

    chromia exchanged K-10 and sulphated zirconia calcined at 650C did not show any

    conversion at 135C after 4 h of reaction The Bronsted acid type catalyst were more

    effective.

    Amberlyst-XE-717p is a promoted ion-exchanger where 17% of the acid sites are

    promoted with an undisclosed molecule [21]. The activity of the catalyst and selectivity

    for bisphenol-A were very high. The exchange with any sulphur compound reduces the

    acidity of the catalyst, whereby the yield of bisphenol- A is increased. The main side

    reactions were of acetone, particularly the formation of mesitylene and its subsequent

    reactions. The mesitylene reactions are promoted by strong acidic sites. The sulphur

    compounds selectively poison the strong acidic sites which are responsible for side

    reactions. The activity and selectivity of Amberlyst-15 are much lower than over DTP/K-

    10 and Amberlyst-31, both of which having similar activities; but the latter being more

    selective. Amberlyst XE- 717p is more active and selective than both DTP/K-10 and

    Amberlyst-31.However, Amberlyst-31 and Amberlyst-XE-717p, like any other ion

    exchanger have very poor thermal stability. They can be used at a maximum

    temperature of. By contrast, the clay modified catalysts can be used at temperatures as

    high as 300C. The lower selectivity of bisphenol-A with DTP/K-10 could be due to its

    high acidity giving rise to a variety of by-products. If the acidity of the catalyst is

    controlled by reducing the activity of some of the sites; for instance, by doping with

    sulphur compounds the formation of byproducts could be lowered. Further, some

    reactions can occur on the external surface of the catalysts without any shape

    selectivity.

  • 43 | P a g e

    2) Effect of speed of agitation

    Fig. shows the conversion of acetone at different time intervals. The conversions were

    found to remain practically the same at speeds beyond 1000 rpm thereby indicating

    absence of solid-liquid mass transfer resistance. Further reactions were conducted at a

    speed of 1000 rpm. Since acetone was taken as a limiting reactant it could be concluded

    that any external resistance to its transfer from the bulk liquid phase to the external

    surface of the catalyst was absent.

    Effect of catalyst loading

    Fig. shows the plot of initial rate of reaction of acetone (roi , gmol/cm3/s) against

    catalyst loading (w, g/cm3). It indicates that the rate of reaction increases linearly up to a

    loading of 2.6z 10 -2 g/cm 3 and thereafter remains constant even though the loading is

    almost doubled. Since the number of acidic sites available in the reaction medium is

    proportional to the available intra-particle surface, the initial rate of reaction of acetone

    should be directly proportional to catalyst loading (mass/volume) if there are no intra-

    particle diffusion limitations.

    This indicates the following:

    An intra-particle diffusion limitation was set in for the transfer of acetone from the

    exterior surface of catalyst beyond a solid loading of 2.6x l0 2 g/cm 3, acetone being the

    limiting reactant (CAo

  • 44 | P a g e

    The side reactions were also significant due to extra available active sites.

    It clearly demonstrated that mass transfer limitations were set in and not all internal

    surface area was utilised for the reaction. In fact, the acetone concentration would

    become zero at a certain distance from the centre of the particle and the reaction would

    become intra-particle mass transfer controlled. Further experiments were therefore

    done at catalyst a loading of 2.6 x l0 -2 g/cm 3 in the absence of intra particle resistance.

    Effect of temperature

    Fig. shows plots of conversion of acetone with time at temperatures of 120, 135 and

    150C. The rate of reaction increases as the temperature increases. The conversions at

    120C are linear with respect to time showing zero-order dependence on acetone

    concentration. The other two lines indicate non-zero order dependence which will be

    discussed later in the kinetic interpretation.

  • 45 | P a g e

    Conclusion

    The reaction of phenol and acetone was studied over different catalysts. DTP/K- 10,

    Amberlyst-31 and Amberlyst XE-717p were found to be better catalysts. DTP/K-10 is

    reusable and better as regards its use at higher temperatures. The kinetics was studied

    with DTP/K-10 as catalyst where the rate determining step is the formation of p-

    isopropenylphenol from chemisorbed acetone and phenol from the liquid phase within

    pores according to Eley-Rideal mechanism. The catalyst was characterised fully. By

    taking higher mole ratio of phenol to acetone, a number of byproducts are avoided. The

    kinetic model was found to fit the data satisfactorily.

  • 46 | P a g e

    References -

    http://nptel.ac.in/courses/103107082/module7/lecture8/lecture8.pdf

    http://ac.els-cdn.com/S0926860X04007562/1-s2.0-S0926860X04007562-

    main.pdf?_tid=c5bf66dc-7338-11e4-b6fa-

    00000aacb35e&acdnat=1416765020_591b5a96e1d46785e235961d2b374f14

    https://www.citgo.com/CITGOforYourBusiness/MSDS.jsp

    http://www.infodriveindia.com/indian-importers/cumene-importers.aspx

    http://www.sify.com/news/naphtha-cracker-project-at-indian-oil-s-panipat-

    complex-dedicated-to-nation-news-national-lcpukciehfbsi.html

    http://mcgroup.co.uk/researches/cumene

    http://www.icis.com/globalassets/global/icis/pdfs/sample-reports/chemicals-

    cumene.pdf

    http://www.pib.nic.in/newsite/erelease.aspx?relid=69826

    https://www.zauba.com/customs-import-duty/CUMENE/india.html

    https://www.zauba.com/importanalysis-CUMENE/hs-code-29096000-report.html

    http://www.seair.co.in/product-import-data/cumene-import-data.aspx

    www.sciencedirect.com

    www.wikipedia.com