PRODUCTION OF BISPHENOL-A

RAHUL AGRAWAL (08431G)AAKASH SUMAN (08401G)

13 Th Sept.2011 Project Review-1

DEPARTMENT OF CHEMICAL ENGINEERINGJAYPEE UNIVERSITY OF ENGINEERING AND TECHNOLOGY,

A.B. ROAD, RAGHOGARH, DIST. GUNA -473226, M.P., INDIA

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ACKNOWLEDGEMENT

We wish to express deep sense of gratitude and sincere thanks to our project supervisor Dr. Ashish S. ChaurasiaAssistant Professor, Department of Chemical Engineering & Chemical Technology for his valuable guidance,encouragement, suggestions, and moral support throughout the period of this project work.

We express our thanks to Professor N. J. Rao – Vice Chancellor of Jaypee University for his valuablesuggestions. We would like to thank Professor K. K. Tiwari, who is associated with JUET after his retirement fromICT Mumbai for his guidance and suggestions during this project work. We would like to thank Dr. G. K. Agrawalfor his suggestions during this work. Our special thank to Dr. Hari Mahalingam – Head of Chemical EngineeringDepartment for providing all the necessary facilities to complete this work. We would like to thank all other facultymembers of Chemical Engineering Department for their support during this work.

Signature of the student--------------------------------------Name of student -----------------------------------------------Designation -----------------------------------------------------Date ------------------------------------------------------------

Signature of the student--------------------------------------Name of student -----------------------------------------------Designation -----------------------------------------------------Date --------------------------------------------------------------

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PREFACE

I am glad to present the project entitled, “ PRODUCTION OF BISPHENOL A” to this university “ JAYPEE UNIVERSITY OF ENGINEERING AND TECHNOLOGY “,GUNA. The project contents have been planned in such a way that the general requirements can be fulfilled.

During our efforts which has been given to make this wonderful project ,we have observed that the basic information and and the fundamental concepts which has been incurred to make this project are sufficient.

We are thankful to our project guide Dr. Ashish Chaurasia, and other faculty members of this institution who has given us the adequate information and also encouraged us to do this project. We are also thankful to this institution for providing this golden opportunity to this project successfully.

We are feeling great to do this project which has been provided by Dr. G. K Agrawal .

RAHUL AGRAWAL 08431GAAKASH SUMAN 08401G

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CONTENT

CHAPTER 1: HISTORICAL PROFILENATURAL OCCURRENCE 5TRADITIONAL APPLICATIONS/USES 5MANUFACTURERS 6HISTORY OF PRODUCT IN INDIA 7

CHAPTER 2: APPLICATIONSCURRENT APPLICATION 8VARIOUS GRADES/ SPECIFICATIONS/STANDARDS 9

CHAPTER 3: ECONOMIC SCENARIOGLOBAL SUPPLY SCENARIO 10GLOBAL DEMAND AND SUPPLY 10GLOBAL DEMAND SCENARIO 11PRODUCT WISE MARKET 11PRICE AND PRICE VARIATION 12GROWTH ASPECTS 12COMPANY WISE CAPACITIES 12

CHAPTER 4: PROPERTIESPHYSIO-CHEMICAL PROPERTIES 14-PHYSICAL PROPERTIES-CHEMICAL PROPERTIESBIO-ENVIRONMENTAL CHARACTERISTICS 15-ENVIRONMENTAL FATE AND IMPACTS-METABOLISM FATE AND IMPACTSHANDLING CONSIDERATIONS 15STORAGE CONSIDERATIONS 16SAFETY CONSIDERATIONS 16

CHAPTER 5: MANUFACTURING PROCESSESBADGER BPA TECHNOLOGY 17SINOPEC/ LUMMUS TECHNOLOGY 19MITSUBISHI CHEMICAL BPA TECHNOLOGY 20CHEMWIK PROCESS TECHNOLOGY 21

References 25

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Chapter-1: Historical profile

Natural occurrence:-

Bisphenol A (abbreviated BPA) does not occur as such in nature. It is a man-made molecule and was invented in 1891. It is a relatively small synthetic, organic compound with a molecular weight of 228. It is a white powder and is an estrogen mimicker, and can cause hormone disrupting effects. Bisphenol A is mainly used as a bifunctional monomer in the manufacture of polycarbonate plastic and epoxy resins and as an antioxidant in PVC.

Traditional applications:-

BPA is a monomer used to make polycarbonate resins for applications such as construction, electronics and food containers. Some 63% of BPA is used to make polycarbonates. A further 27% goes into epoxy resin production, and the remaining 10% is used for other products including speciality resins and flame retardants. Bisphenol A is used primarily to make plastics, and products containing bisphenol A-based plastics have been in commerce use since 1957. At least 8 billion pounds of BPA are used by manufacturers yearly. It is a key monomer in production of epoxy resins and in the most common form of polycarbonate plastic. The overall reaction to give polycarbonate can be written:Polycarbonate plastic, which is clear and nearly shatter-proof, is used to make a variety of common products including baby and water bottles, sports equipment, medical and dental devices, dental fillings and sealants, eyeglass lenses, CDs and DVDs, and household electronics. BPA is also used in the synthesis of polysulfones and polyether ketones, as an antioxidant in some plasticizers, and as a polymerization inhibitor in PVC. Epoxy resins containing bisphenol A are used as coatings on the inside of almost all food and beverage cans, however, due to BPA health concerns, in Japan epoxy coating was mostly replaced by PET film.  Bisphenol A is also a precursor to the flame retardant tetrabromobisphenol A, and was formerly used as a fungicide. Bisphenol A is a preferred color developer in carbonless copy paper and thermal paper,  with the most common public exposure coming from some  thermal point of sale receipt paper. BPA-based products are also used in foundry castings and for lining water pipes

Uses:-

Plastics and resins made using BPA are found in many of the products you use every day to make your life more convenient - products like canned foods to eyeglasses to vital medical equipment and food and beverage containers.Some other Uses of Bisphenol A are:-

baby bottles and nursing products dental sealants and orthodontic products water bottles and other food and beverage containers the liners of food cans CDs and DVDs eyeglasses water pipes sports safety equipment medical equipment and tubing consumer electronics PVC

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Manufacturers:-

Jingjiang Concord Plastics Technology Co., Ltd china Shanghai Righton Co., Ltd. China Bayer Polymers Baytown, Texas Dow Chemical Freeport, Texas Sabic Innovative Plastics Burkeville, Alabama Sabic Innovative Plastics Mount Vernon, Indiana Hexion Specialty Chemicals Deer Park, Texas Sunoco Chemicals Haverhill, Ohio Kesar Loteparhuram, India Mitsubishi chemicals ltd. Idemitsu chemicals pvt.ltd. Kesar petroproducts pvt. Ltd. India Mitsubishi chemicals Ltd.

Earlier Industrial applications:-

The main market for bisphenol-A (BPA) is in the production of polycarbonate (PC) with the second largest outlet being epoxy resins. Other uses include flame retardants (mainly tetrabromobisphenol-A), unsaturated polyester resins and polyacrylate, polyetherimide, polysulphone resins, other polysters, the halogenated form is used as flame retardants, the alkylated form is used as stblizer and antioxidants for rubber and other plastics.In India, Bisphenol A is primarily used in manufacturing of epoxy resins, phenolic resins and processing of polyvinyl chloride. Epoxy resins are thermosetting resins chiefly used for coating and adhesives. The glass fibre reinforced laminates of epoxy resins are light in weight and have the highest tensile strength for any reinforced plastics. High quality higher grade polycarbonates is needed to produce consumer goods such as glazing, electrical parts, compact disc and automotive parts.

History of Bisphenol A in India:-

Bisphenol A was first developed in 1891 but saw little use until the 1930s when it was used as a synthetic estrogen product. The first reported synthesis of BPA was from Thomas Zincke of the University of Marburg, Germany. The Uses came into notice in 1930s when it was used as a synthetic estrogen product. Use of Bisphenol A slowed with the discovery of DES, a more potent artificial estrogen, later found to cause reproductive cancer in the children of mothers who took it. In the 1940s and 1950s, scientists discovered that Bisphenol A, when combined with the gas phosgene, helped create a clear, hard plastic called polycarbonate. This material was used in eyeglasses, baby bottles, shatter-resistant lights and many other applications. The commercial production of bisphenol a started in india in 1970’s.

Bisphenol A on Timeline

1891: Bisphenol A, or BPA, is developed.

1930s: The chemical is used as a synthetic estrogen.

1960s: Food manufacturers begin to use BPA to make hard, clear plastic for items such as baby bottles and the lining of metal food cans, including liquid baby formula.

1968: The first Phenol producing plant was installed in india in 1968 with the commissioning of unit of Herdillia Chemicals Ltd at Thane, Maharashtra with an installed capacity of 10,000 tonne per annum.

1998: Patricia Hunt, a geneticist at Washington State University, notices that control mice had many more defective eggs when stored in polycarbonate cages.

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2000-present: More than 1,000 studies are published showing harm to lab animals from BPA, including cancer, obesity, diabetes, reproductive failures and neurological disorders.

2008: Annual sales of BPA exceed $6 billion.

April 2008: Canadian health officials begin steps to declare BPA a toxin and to have it banned from use in baby bottles and tableware for children. Several manufacturers - including Nalgene, Wal-Mart, Toys "R" Us and CVS pharmacies - announce plans to phase out use of the chemical in children's products.

August 2008: The Food and Drug Administration declares BPA to be safe.

September 2008: The National Toxicology Program, an advisory board to the FDA and Environmental Protection Agency, releases its report expressing some concern for how BPA affects the prostate and neural development of fetuses, infants and children. It also expressed concern about the chemical's effect on breast tissue and early puberty.  A study published in the Journal of the American Medical Association in September tied BPA to heart disease in humans. Lawmakers start to call for a ban of the chemical in children's products.

October 2008: The FDA's Science Board finds that the FDA ignored hundreds of studies on BPA and advises the agency to reopen its investigation of the chemical. A study finds that even low levels of BPA can interfere with chemotherapy for breast cancer patients.

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Chapter-2:Applications

Current Applications:-

Some of the common applications of Bisphenol A-polycarbonate plastic include:

CDs, DVDs, Blu-Ray and other discs Roof lights Covers for solar panels Security glazing, e.g. transparent cabins for ski

lifts Roof modules in cars Safety goggles and protective visors Helmets Sunglasses Reusable water bottles Roofs of sport stadiums Safety hats

Medical equipment (blood oxygenators, respirators, dialysers, single-use operating instruments)

Housings for electronic equipment (cell phones, cameras, hairdryers, computers, TVs, coffee makers)

Electrical kettles Plug connectors Electrical equipment, such as plug connections

or switches Headlamps and bumpers in cars Conservatory or green house glazing

Some of the common applications of Bisphenol A-epoxy resins include coatings for:

Underwater ship hulls Cargo tank linings Steel bridges Storage tanks(metal and concrete) Electric motors, engines, machinery Construction panels(cladding, metal roofing,

ceilings, garage doors) Gardening tools and equipment Automotive parts and coatings Steel furniture

Flooring (industrial/public buildings, food/catering industry, chemical plants, pharmaceutical industry, hospitals)

Food and drink cans/can ends General lined cans(oil, hairspray) Collapsible tubes Coil coatings for household appliances Composites used for rackets, surfboards,

helmets, pipes, windmill blades, aviation Adhesives

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Printed circuit boards Printing inksVarious Grades of Bisphenol A

Bisphenol A has following grades: ВЧ,АП,А,Б,В. Grade ВЧ, АП are intended for production of optical polycarbonate; Grade A is used for production of molding and extrusion polycarbonates, as well as extra grade polysulfones and epoxy resins; Grade Б is employed in processes of production of epoxy resins and lacquers; Grade В 1 sort – for production of epoxy resins, lacquers, adhesives and other products; Grade B 2 sort – for production of epoxy resins, adhesives and other products.

Specifications for Bisphenol Aameter Value

Molecular Formula C15H16O2Mol Wt 228.29CAS # [80-05-7]Description White powder or flakesAssay 99.6 % minCrystallization Point in deg cel 156 minFree phenol in ppm 300 maxIsomers (%) 0.1 maxMoisture (%) 0.1 max

Standards for Bisphenol A

BISPHENOL A-STANDARD PRODUCT Value UnitSPECIFICATIONS PARAMETER

PURITY(asp,p-isomer,dry state),min. 99.93 wt %

MELTING point,min. 156.8 Celcius

o,p-isomer,max. 300 ppm Phenol,by GC,max 30 . ppm

Iron,max. 0.1 ppm

Ash,max. 1 ppm

Color25g/35cm3 MeOH,max. 5 APHA

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Chapter 3: Economic Scenario

Global supply scenarioGlobal BPA capacity in 2008 was around at 5.16-mtpa, and demand about 4.38-mt. Asia is the largest producing region, with 45% of total capacity, followed by Europe (28%) and America (24%) Within Asia, 68% of total capacity is in three countries – Japan, Korea and Taiwan. Taiwan alone accounts for 27% of total Asian capacity, followed closely by Japan (26%) and Korea (15%). China has only 11% of Asian capacity for BPA, but accounts for 28% of total Asian demand. Japan ranks second in terms of demand in Asia, with an 18% share, followed by Korea and Taiwan (15% each). While BPA was in oversupply in 2005 and 2006, the market became relatively tight from mid-2007 due to a shortage of its raw material, phenol, and increased demand from PC and epoxy resins. However, much new phenol capacity has started coming on stream from 2008, while new BPA capacity has also been added in Asia, pushing the market back into over supply.Indian scenario:- is totally opposite and shows a tight supply of the product

Global/ Indian supply and demand for BPA [2009](KPA)

Region Capacity Demand

America 1,226 972Europe 1,438 1,040

AsiaChina 261 651Japan 615 565Korea 345 436Taiwan 645 691Other Asian(including India) 480 650Total Asia 2,346 2,793Others 150 174Total 5,160 5,179

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Global/Indian demand scenarioThe main market for BPA, globally, is in production of PC resins, followed by use for manufacture of epoxy resins.Other uses include flame retardants (mainly tetrabromobisphenol-A), unsaturated polyester resins and polyacrylate,polyetherimide and polysulphone resins.

PC MarketsThe market for BPA had been growing strongly at an average rate of 10% per year over the last few years, driven primarily by increasing demand for PC resins. Optical media, including audio compact discs (CDs), CD-ROMs, recordable CDs and digital versatile disks (DVDs), had been driving growth in BPA demand via PC. However, the growth in this application is slowing significantly, due to the downloading of music and films from the Internet and other competing technologies becoming more popular. PC resins are also used in the place of traditional materials, such as metal and glass, in automotive components while glazing and sheet products can be used in architectural, security and transportation applications. Automotive glazing offers potentially strong growth opportunities for BPA/PC producers. While PC is being used in rear body parts, roof modules and fixed side windows, there has been strong resistance from automobile manufacturers in the more general replacement of glass. The higher cost, compared to glass, could be a limiting factor, although PC does offer weight savings, broader design options and easier handling that could bring efficiencies on the automotive production line. Over the next few years, applications are expected to widen into back lights and rear windows in truck cabins, moveable side windows and vehicle top applications.

Epoxy resinsThe second largest end use of BPA is epoxy resins. There are several types of epoxy resins, but those based on BPA and epichlorohydrin account for the majority. High performance coatings are one of the primary applications, followed by electrical/electronic laminates, adhesives, flooring and paving applications, mainly in the automotive, construction and aerospace industries. BPA will grow at an average annual rate of 5.5% during 2009–2014, as the industry tries to recover volume lost during the recessionary years. Bisphenol A consumption for epoxy resins production will experience the fastest growth in Asia.

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Price and Price variations:-Bayer Shanghai chemicals ltd- USD 2661.11 per ton/Rs.122916/ tonShanghai Sinopec Mitsui Chemicals co. ltd- USD 2629.81 per ton/ Rs.121470.92/ tonThere is no significant price change seen in past 2-3 years.

Growth prospectsGlobal BPA consumption has increased at an average rate of almost 10% per year from 2007 to 2010, driven by PCdemand and improved epoxy resin markets. However, growth has slowed considerably. In Europe, growth is expected to be flat, while the strongest growth will be in Asia, mainly China. Up to 2010, growth in the Chinese market was mainly due to epoxy resins. However, with the start-up of PC capacity in China by Teijin and Bayer and several projects planned, BPA demand in China will be driven in the future by PC. Another driver behind BPA demand is the strong growth in Asia, as a whole. In 2005-207, Asian BPA markets grew at an average of 13% per year with PC pushing it at 19% year. Future growth will be much lower, as the global economic downturn hits markets. The US market is expected to grow at 4.2% per year up to 2012, with PC and epoxy resins growing at 4.5% per year and 3.5% per year respectively. US demand is expected to increase from 1.06- mt in 2006 to reach 1.25-mt tons in 2011. In 2007, BPA imports were 4,810-tons, while exports were 34,500-tons. In short, PC will continue to be the main driver for BPA, with global growth forecast at 5-6% per year.

GLOBAL BISPHENOL A CAPACITY, '000 TONNE/YEARCompany Location Capacity

West EuropeBayer Antwerp, Belgium 140

Krefeld-Uerdingen,Germany 160

Dow Stade, Germany 100GE Plastics Bergen op Zoom,

Netherlands 110Cartagena, Spain 210

Shell Pernis, Netherlands 110

East EuropePetro Borzesti Borzesti, Romania 10ZC Blachownia, Poland 10

North AmericaAristech Haverhill, Ohio 110Bayer Baytown, Texas 120

160

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Dow Freeport, Texas 45166

GE Plastics Burkville, Alabama 68Mount Vernon, In 260

Shell Deer Park, Texas 102113

AsiaWuxi Resin Wuxi, China 10Kesar Lote parshuram, India 7.5Idemitsu Chiba, Japan 70Mitsubishi Kashima, Japan 80Mitsui Nagoya, Japan 80

Osaka, Japan 60Shin Nihon* Kyushu, Japan 95Mitsui Pulau Sakra,

Singapore 70Kumho P&B Yeochon, S Korea 30Nan Ya Mailiao, Taiwan 72Chang Chun Mailiao, Taiwan 20Taiwan Prosperity Linyuan, Taiwan 25

In India there is a demand of 40000 MTPA of Bisphenol A (2009) and the installed capacity within India is 28000 MTPA rest of the product is been imported from the outside market.The manufacturers presumed to increase their manufacturing capacities with level of demand they see in future. As the global market is already over supplied, most of them don’t see any further growth in manufacturing capacities except some of the Asian countries like India and China, because the market in the asian countries is very tight and the consumption and demand gap is still not covered by the Domestic production units.

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Chapter-4: Properties

Physio-chemical Properties:-Bisphenol are colorless, odourless substances and most of them are solid at room temperature. The melting point of most of the important Bisphenols are between 100-200C. Bisphenols are virtually insoluble in water. Their solubility in organic solvent is determined by their substituents. Whereas bisphenol A is the only readily soluble in polar media such as ethers and alcohols, bisphenols with large aliphatic groups in the molecule are soluble in araliphatic and aliphatic hydrocarbons. The alkali salts of bisphenol are water soluble. However their solubility decreases drastically with increasing substitution. The boiling points of bisphenols are very high because of the size of the molecules and its polarity. For this reason and because of the decomposition frequently observed during boiling. Bisphenols are rarely distilled. Some important physical properties of bisphenols are summarized below.

Physical properties of industrially important Bisphenol A are:-

Density at 20oC 1.04g/cm3

160oC 1.065g/cm3

Bulk density 0.492g/cm3

Bp at 101.3kPa 360oC 1.4 kPa 240oC 0.4 kPa 222oCHeat of vaporization at 101.3 kPa 404J/gFlash point 227oCIgnition temperature 510oCSolubility of water at 83oC 0.344 wt%Solubility in acetone, alcohols goodSolubility in methylene chloride ca 1 wt%

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Chemical properties of Bisphenol A:-The chemical properties of Bisphenols are determines by Phenolic OH groups, the aromatic rings and the alkyl bridge. They therefore undergo the same reactions as the corresponding substituted monophenols. They are also

suitable as building block for higher molecular mass linears polyesters are polyethers because of their bifuctionality.Bisphenols which are alkylated ortho to the OH group readily trap radicals and are therefore suitable as stabilizers.Under hydrogenation condition of Bisphenol a is cleaved to give 4-isopropylphenol, alkali catalyzed cleavage gives 4-isopropylphenol in good yields. Both compounds are good to obtain by other methods. The alkali catalyzed cleavage of various Bisphenols has been investigated . the cleavage can also be catalyzed by acid to form indans and spirobisindans.The purely thermal cleavage is generally less straight forward.

Bioenvironmental Characteristics’:-Enviromental Fate of bisphenol A:-• The vast majority of BPA produced, greater than 99.9%, is consumed at manufacturing sites to make products such as polycarbonate plastic or epoxy resins .Low levels may be released to the environment in the effluent water from biological wastewater treatment plants. Bisphenol A dust (particulates) is controlled by workplace practices and engineering design and is not a significant contributor to environmental exposures. The relatively small amount of vapor released to the atmosphere is rapidly degraded by sunlight.• The distribution of BPA in the environment can be predicted by its physical properties (Staples et al, 1998). Bisphenol A is a solid with low volatility at ambient temperature conditions, water solubility of 120-300 milligrams per liter and a greater solubility at alkaline pH values. Based on these properties, a simple equilibrium model predicts that about 50% of BPA in the environment has the potential to bind to sediments or soils with the rest remaining in the water column.• Biodegradation plays a major role in the removal of BPA from the environment. Rapid and extensive breakdown of BPA has been demonstrated in a variety of laboratory biodegradation tests. Recent studies demonstrate that BPA degrades

Impact:-The trace amounts of BPA remaining in treated wastewater will continue to biodegrade in receiving waters and downstream of treatment plants. Studies using real world surface water samples taken from various geographies demonstrate rapid degradation with a half- life in the range of 1 to 4 days (i.e., time for 50% degradation). Numerous publications have reported measured concentrations of BPA in streams and rivers in Japan,

Europe and the United States. The median reported water concentrations from 21 European and 13 United States studies are 0.016 and 0.5 micrograms/L respectively.

Aquatic tests performed on a fresh water and salt water algae, invertebrates and fish , suggest that bisphenol A is only moderately toxic to aquatic animals.

Bio-concentration and metabolism studies have shown that bisphenol A has no significant bioaccumulation potential.

Human Metabolism Fate:-Following the four-step procedure recommended by the United States National Academy of Sciences (NRC, 1983), a safety assessment of BPA concludes that the potential human exposure to BPA from food contact with polycarbonate plastic and epoxy resin is minimal and poses no known risk to human health. This conclusion is based on the following key points:BPA is not carcinogenic and does not selectively affect reproduction or development. The No-Observed-Adverse- Effect-Level (NOAEL) for BPA, confirmed in multiple laboratory animal tests, is 50 mg/kg body weight per day;The estimated dietary intake of BPA from food contact with polycarbonate plastic and epoxy resin, based on the results of multiple migration studies with consistent results, is less than 0.000118 mg/kg body weight/day; andThis potential human exposure to BPA is more than 400 times lower than the maximum acceptable or "reference" dose for BPA of 0.05 mg/kg body weight per day established by the U.S. Environmental Protection Agency, which is derived from the No-Observed-Adverse- Effect-Level.

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An independent analysis by the European Commission's Scientific Committee on Food (SCF), using a similar methodology, has confirmed the safety of polycarbonate plastic and epoxy resin food contact applications. The SCF estimated total dietary intake of BPA from all food contact sources to be in the range of 0.00048 to 0.0016 mg/kg body weight per day, which is below the Tolerable Daily Intake set by the SCF of 0.01 mg/kg body weight per day.The use of polycarbonate plastic and epoxy resins for food contact applications has been and continues to be recognized as safe by the U.S. Food and Drug Administration, the European Commission's Scientific Committee on Food, the United Kingdom Food Standards Agency, the Japanese Ministry for Health, Labor and Welfare, and other regulatory authorities worldwide.

Health effects on human being and other organisms:-

Bisphenol A is an endocrine disruptor, which can mimic the body's own hormones and may lead to negative health effects. Early development appears to be the period of greatest sensitivity to its effects, and some studies have linked prenatal exposure to later neurological difficulties. Regulatory bodies have determined safety levels for humans, but those safety levels are currently being questioned or under review as a result of new scientific studies.  A 2011 study that investigated the number of chemicals to which pregnant women in the U.S. are exposed found BPA in 96% of women. In 2007, a consensus statement by 38 experts on bisphenol A concluded that average levels in people are above those that cause harm to many animals in laboratory experiments. However, they noted that while BPA is not persistent in the environment or in humans, biomonitoring surveys indicate that exposure is continuous, which is problematic because acute animal exposure studies are used to estimate daily human exposure to BPA, and no studies that had examined BPA pharmacokinetics in animal models had followed continuous low level exposures. They added that measurement of BPA levels in serum and other body fluids suggests that either BPA intake is much higher than accounted for, or that BPA can bioaccumulate in some conditions such as pregnancy, or both.  A 2011 study.A 2008 report by the U.S. National Toxicology Program (NTP) later agreed with the panel, expressing "some concern for effects on the brain, behavior, and prostate gland in fetuses, infants, and children at current human exposures to bisphenol A," and "minimal concern for effects on the mammary gland and an earlier age for puberty for females in fetuses, infants, and children at current human exposures to bisphenol A." The NTP had "negligible concern that exposure of pregnant women to bisphenol A will result in fetal or neonatal mortality, birth defects, or reduced birth weight and growth in their offspring."

ObesityA 2008 review has concluded that obesity may be increased as a function of BPA exposure, which "merits concern among scientists and public health officials".A 2009 review of available studies has concluded that "perinatal BPA exposure acts to exert persistent effects on body weight and adiposity". Another 2009 review has concluded that "Eliminating exposures to (BPA) and improving nutrition during development offer the potential for reducing obesity and associated diseases". Other reviews have come with similar conclusions. A later study on rats has suggested that perinatal exposure to drinking water containing 1 mg/L of BPA increased adipogenesis in females at weaning. 

Breast cancerA 2008 review has concluded that "perinatal exposure to low doses of BPA, alters breast development and increases breast cancer risk". Another 2008 review concluded that "animal experiments and epidemiological data strengthen the hypothesis that fetal exposure to xeno estrogens may be an underlying cause of the increased incidence of breast cancer observed over the last 50 years". BPA may be similar to diethylstilbestrol caused birth defects and cancers in young women whose mothers were given the drug during pregnancy. A 2011 study using the rhesus monkey, a species that is very similar to humans in regard to pregnancy and fetal development, found that prenatal exposure to BPA causes changes in female primates' uterus development. A 2011 rodent study found that male rats exposed to BPA had lower sperm counts and testosterone levels than those of unexposed males. A 2011 mice study found that male mice exposed to BPA became demasculinized and behaved more like females in their spatial navigational abilities. They were also less desirable to female mice.

Handling:-Minimize exposure to product dust resulting to open transfer operations ,mechanical handling and fabrication.Good housekeeping and controlling of dust is necessary to minimize dust ignition hazard.

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Packaging consideration:-Following are the controls for sacks, bulk sacks, hopper trucks and cars that may help increase plant safety.Sacks25 kg Sacks are commonly used for Bisphenol A packaging.Sacks should be stored in a clean, well ventilated area.Before a sack is lifted , it should be inspected for snags and punctures.

Bulk Sacks500-1000kgs Bulk sacks are commonly used for Bisphenol A packaging.Lifting straps are attached to the bulk sack to allow the sack to be lifted by a tow motor or hoist.Bulk sacks are typically made of Ultraviolet (UV) resistant woven ,Polypropylene or similar material. Hopper trucks and Hopper carsBoth hopper trucks and hopper cars are sealed containers that are loaded through roof hatches and gravity or pneumatically unloaded through bottom outlet nozzles.Containers should be inserted using inert gas containing less than 9.3% by volume oxygen.Gravity unloading can be fascilitated with the use of a mechanical vibrator.

Storage consideration:-Storage bins and silos are usually made of one of the following.

Concrete Alumunium Stainless steel Epoxy resin coated carbon steel

Most bins and silos have a cone shaped bottom with a slope of about 6o degrees or greater to minimise the tendency towards hanging up or plugging of material.Storage bins and silos should be grounded and padded with an inert gas such as nitrogen to reduce the risk of electric spark, dust explosion and moisture gain.Storage bins should be equipped with properly designed explosion relief devices.

Safety Considerations:-it would be wise to limit your exposure, not easily done since BPA is found in so many household products alone, but here are a few steps you can take to reduce your contact. Don't use plastic cling wrap, use waxed paper or paper towels. Don't use plastic containers in microwaves. Use glass or ceramic. Use non- polycarbonate plastics such as polypropylene and polyethylene. Most major

plastic consumer goods manufacturers now offer non-polycarbonate alternatives for drinking bottles, microwave bowls, and plastic liners.

You can check for BPA in the plastics you buy by looking for the stamped on the surface. Cut down on canned foods. To keep food from reacting with the metal of the can, a plastic coating made from bisphenol A is commonly applied to the inside of the can. This coating appears as a solid color on the inside of the can, and can leach into the food stored inside.

Avoid eating or drinking from polycarbonate plastics – used in such products as hard plastic baby bottles, 5 gallon water cooler bottles, hard plastic water bottles, plastic silverware, and Lexan products. You can check for the type of plastic on the bottom of the bottle – polycarbonate bottles may be labeled with recycling number 7 ("Other" type of plastic) or may contain the letters "PC" below the recycling symbol. Bisphenol A may leach out of these types of bottles into your beverage or food. Alternatives include bottles and other materials made from glass, stainless steel, or polypropylene bottles labeled number 5 on the bottom (translucent, not transparent).

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Chapter-5:Manufacturing processes

Bisphenol A. There are many processes for the industrial synthesis of this most important .Currently, hydrogen chloride or sulphonated cross-linked polystyrenes are used as the catalyst which are usually arranged as a fixed bed over which the reaction mixture is passed . The reaction of phenol and acetone takes place at 50-90 c, the molar ratio phenol –acetone is to 15:1. Bisphenol A crystallizes as an adduct with 1 mol phenol , after separation of the hydrogen chloride by distillation and neutralization. The use of ion exchangers is preferred to that of hydrogen chloride because they are less corrosive. The yield is normally 80-95%. To isolate the bisphenol , the whole reaction mixture can be fractionally distilled , wherby bisphenol A itself is distilled over particularly carefully under high vacuum, separated from resins byproducts , and subsequently recrystallized under pressure at elevated temperature . Crude bisphenol A can also be purified by extracting into hot heptanes or the mixtures of aromatics or by recrystallization from aromatics. A very high purity product with polyster quality is obtained if the bisphenol A-phenol 1:1 adduct is separated ,recrystallized from phenol, and the phenol removed by distillation . These processes are mostly carried out continuously . The acetone-phenol mixture produced in the hock phenol synthesis from cumene hydroperoxide can be used as starting material for bisphenol A synthesis.

Badger BPA Technology:-

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Applications:The Badger BPA technology is used to produce high-purity bishenol A (BPA) product suitable for polycarbonate and epoxy resin applications. The product is produced over ion-exchange resin from phenol and acetone in a process featuring proprietary purify cation technology.Description: Acetone and excess phenol are reacted by condensation in an ion exchange resin catalyzed reactor system (1) to produce p,p BPA, water and various byproducts. The crude distillation column (2) removes water and unreacted acetone from the reactor effl uent. Acetone and lights are adsorbed into phenol in the lights adsorber (3) to produce a recycle acetone stream. The bottoms of the crude column is sent to the crystallization feed pre-concentrator (4), which distills phenol and concentrates BPA to a level suitable for crystallization. BPA is separated from byproducts in a proprietary solvent crystallization and recovery system (5) to produce the adduct of p,p BPA and phenol. Mother liquor from the purifi cation system is distilled in the solvent recovery column (6) to recover dissolved solvent. The solvent free mother liquor stream is recycled to the reaction system. A purge from the mother liquor is sent to the purge recovery system (7) along with the recovered process water to recover phenol. The recovered purifi ed adduct is processed in a BPA fi nishing system (8) to remove phenol from product, and the resulting molten BPA is solidified in the prill tower (9) to produce product prills suitable for the merchant BPA market.Process features: The unique crystallization system produces a stable crystal that is efficiently separated from its mother liquor. These plants are extremely reliable and have been engineered to meet the operating standards of the most demanding refining and chemical companies. The catalyst system uses a unique upflow design that is beneficial to catalyst life and performance. High capacity operation has been fully demonstrated.Product quality: Typical values for BPA quality are:Freezing point, °C 157BPA w/w, wt% 99.95Methanol color, APHA 5Commercial plants: The first plant, among the largest in the world, began operation in 1992 at the Deer Park (Houston) plant now owned and operated by Resolution Performance Products LLC. Since that time, two otherworld-scale plants were licensed to the Asia-Pacific market.Licensor: Badger Licensing LLC.

The Sinopec/ Lummus Technology:-

Technology:The Sinopec/Lummus bisphenol –A technology is a fully continuous process that incorporates catalytic stripping, a novel reactor technology for the condensation of phenol and acetone. Developed by Sinopec Technology Company and marketed by ABB Lummus Global, this advanced technology maximizes yield and conversion using an environmentally preferred ion exchange resin catalyst.This new reaction system promotes the BPA condensation reaction under highly favourable conditions while simultaneously removing the water of reaction. The catalytic stripping reactor provides a very high effective phenol to acetone ratio that , together with an improved high activity and high selectivity catalyst, result in complete conversion of acetone and maximum phenol conversion , with low by-product formation. Much higher conversions and better selectivity are achieved then with other ion exchange resin catalyst system. This reduces recycles and utility consumption thereby reducing operating and capital costs.High phenol conversion permits a simple 1-stage crystallization system. In the Sinopec/Lummus process special crystallization technology is employed that produces large crystals with few impurities, crystallizer volume can be low due to the high BPA content of the reactor effluent. Continuous centrifuges are utilized for easier operation . These improvements further contribute to lower operating and capital costs.

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Ion exchange resin is today’s preferred catalyst system for bisphenol –A manufacture. It replaces older, acid based technologies by doing away with the acid based environment. All of the problems associated with handling acid , including corrosion and disposal of acid waste, are eliminated.

Process features: High activity ion exchange resin catalyst Catalytic stripping reactor Simpler 1-stage product portfolio

Advantages: High conversion/low recycle rate Lower capital investment Lower utility consumption No acid waste disposal problem Lower maintenance cost

Process description:Acetone is reacted with fresh and recycle phenol in the catalytic stripping reactor utilizing ion exchange resin as catalyst. Water of reaction is simultaneously stripped from the reaction mixture by a recirculating stream of nitrogen. Reaction mixture consist of unreacted phenol saturated with BPA, essentially free of acetone containing very low level of water and impurities, flow directly to primary crystallization where BPA adduct crystals are obtained. Adduct crystals are melted and distilled under vaccum to produce raw BPA. An evaporator remove residual trace phenol and BPA melt flow to product handling. Mother liquor from primary crystallization is conc. And phenol is dewatered by distillation in the phenol recovery unit. Dry phenol is recycled to the condensation reactor and waste water is purged. Recovered BPA and byproduct flow to the secondary crystallization unit. BPA adduct from secondary crystallization is returned to primary crystallization for recovery. Secondary mother liquor containing essentially all of the reaction by product is thermal cracked and catalytically rearranged. Rearrangement product is recycled for recovery of BPA. Tar residue is purged from the process and may be used as fuel.

Process chemistry:-

2C6H5OH + (CH3)2CO (C6H4OH)2C(CH3)2 + H2O Phenol Acetone Bisphenol A water

Mitsubishi Chemical Bisphenol-A Technology:

Bisphenol-A: (BPA)

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4,4’-bisphenol A (BPA) is an important industrial chemical, which is mainly used as a raw material of polycarbonate and epoxy resin. BPA is produced by acid catalyzed condensation reaction of two moles of phenol and one mole of acetone. Traditionally, commercial scale BPA production has been based on a strong mineral acid catalyst such as hydrochloric acid. Hydrochloric acid is highly corrosive, so the BPA plant requires expensive corrosion-proof materials. In addition, complicated waste water treatment facility is needed for the mineral acid catalyzed process. Since waste water from the process contains some amount of hydrochloric acid, it must be treated by neutralization with lime, precipitation of the calcium, and further biotreatment. An alternative catalyst now widely used is cation exchange resin. This type of catalyst mitigates equipment corrosion. Some components, which contain thiol groups, can improve BPA production rate and its yield.

Introduction of Mitsubishi BPA Technology MCC has been improving BPA process to realize lower raw material consumption and the stable operation. Even now, MCC continues to exert effort to achieve effective BPA process. MCC's BPA process (PROCESS) employs an improved ion exchange resin catalyst that exhibits higher activity and longer life compared to other resin catalysts. Impurities are significantly reduced, leading to improved raw material efficiency and finished product color.

Feature of Mitsubishi BPA process The characteristic and superiority of MCC BPA process are as follows. (1) Superior Product Quality (2) High Catalyst Performance (3) Low Construction Cost (4) MCC’s rich experience

Besides Bisphenol-A, small amounts of following major impurities are produced. 2,4-BPA isomer Methyl BPA Trisphenol Chromans p-Isopropenylphenol cyclic dimer p-Isopropenylphenol linear dimer

Simplified block flow

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CHEMWIK PROCESS:

Technology:Chemwik BIS process of technology, is based on the use of ion exchange resins with a chemically bound promoter of the reaction as a catalyst for BPA synthesis. Bisphenol A synthesis is carried out in original reactors in three reaction zones, through a system of filtration-injection nozzles located at several levels. Bisphenol A is recovered from the post-reaction mixture and refined by way of single- or double-step crystallization from a phenolic solution. This is followed by the thermal decomposition of a BPA-phenol adduct and distilling off of phenol. Post crystallization liquor is dewatered by distillation and recirculated to the synthesis unit. Any recovered acetone and phenol are recycled to the process. A standard bisphenol A product, obtained with the use of double-step crystallization from a phenolic solution, is characterized by a purity of min. 99.93 %, which is suitable for use in the manufacturing of polycarbonates and epoxy resins.

Advantages:-The Chemwik BIS process of technology has the following advantages: • High purity of bisphenol A, which satisfies requirements for the production of polycarbonates and epoxy resins,

• Low consumption of raw materials,

• It is an energy saving process, which results from the high BPA increments in the reaction, among other things,

• It is a fully automated process, enabling the number of plant operating personnel to be minimized.

Process description: In the Chemwik® BIS process to obtain bisphenol A (BPA) the product obtained is of a quality suitable for use as a raw material for making polycarbonates and specialty epoxy resins. When leaving the production facility, the final product is in the form of white pellets, which is very convenient for use in pneumatic transport systems. The pellets are obtained using a conventional pelletizer system. The Chemwik® BIS process comprises the following unit operations: ▪ Bisphenol A synthesis and by-products rearrangement in the presence of a promoted catalyst (Synthesis Unit I) ▪ Bisphenol A synthesis in the presence of a promoted catalyst (Synthesis Unit II)

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▪ Crystallization and separation of crude adduct ▪ Recrystallization and separation of pure adduct ▪ Separation of Bisphenol A by adduct decomposition and distilling off phenol ▪ Recovery of acetone and separation of water▪ Separation of heavy ends (residue), phenol recovery, and regeneration of Bisphenol A ▪ Product granulation and packing ▪ Phenol removal from water ▪ Technological off gas system

Bisphenol A synthesis in the presence of a promoted catalyst and rearrangement of byproducts (Synthesis Unit I) The catalyst for the Synthesis Unit I is a gel-type cation-exchange resin, crosslinked with 4% DVB, with a chemically bound reaction promoter in the form of 2,2-dimethylthiazolidine. The scope of known-how on offer includes a commercially proven methodology for the promoted catalyst preparation. An optimum lifetime of the promoted catalyst without replacement and without regeneration is 1-1.5 year. If larger reactors are used, the promoted catalyst lifetime may be extended to ab. 2.5 year. Bisphenol A is formed by condensation of a single mole of acetone with two moles of phenol, which reaction is catalyzed by an acid ion-exchange resin. The condensation reaction is exothermal and water is formed as its main byproduct.

In addition to p,p-bisphenol A, a number of byproducts are formed, for instance: ▪ bisphenol A o,p-isomer ▪ trisphenols ▪ dihydroxyindanes (DHI) ▪ Dianin compounds.

Synthesis Unit I comprises 85-100 m³ reactors with a solid catalyst bed. Each reactor is divided into three reaction zones by means of a system of filtration-injection nozzles which are located at various levels. The heat of the exothermal reaction is removed in a continuous manner by means of heat exchangers, which are located outside the reactors. By recirculating a stream of mother liquor, the byproducts are kept in the reaction at a constant concentration, close to an equilibrium (8-10 %), so that the phenol-acetone reaction in the Synthesis Unit I, produces mainly p,p-bisphenol A. What else takes place in the process is the rearrangement of part of the byproducts being formed (and referred to as being “capable of rearrangement”) into p,p-bisphenol A, adding to the reaction yield and selectivity.

Bisphenol A synthesis in the presence of a promoted catalyst (Synthesis Unit II) The catalyst used in the Synthesis Unit II is also a gel-type cation-exchange resin, crosslinked with 4% DVB, with a chemically bound reaction promoter as in the synthesis unit I. The feed to the reaction is a stream of phenol, composed of regenerated phenol and washings from adduct centrifugation after recrystallization, and an addition of acetone. The Synthesis Unit II comprises 20-85 m³ reactors with a solid catalyst bed.

Crystallization and separation of crude adduct The stream from the Synthesis Unit I reactors is sent to adduct crystallizers, where a crystalline adduct comprising bisphenol A and phenol in a 1:1 ratio by mole is obtained. Crystallization takes place as the result of cooling the solution. The crystalline suspension formed, is sent from the crystallizers to screen drum centrifuges. The crude crystalline adduct is washed with a stream of phenol in the screen section of the centrifuge drum and is then removed from the centrifuge. The crystalline adduct is sent to the recrystallization unit from phenolic solution while the mother liquor and the washings are recirculated to the Synthesis Unit I through the unit where acetone dewatering and recovery take place.

Recrystallization and separation of pure adduct Crude crystalline adduct is diluted in the Phenolic stream and sent to the crystallizers to obtain a pure adduct as the result of cooling the solution. The resulting crystalline suspension is sent to screen drum centrifuges. The crystalline pure adduct is washed with pure phenol in the screen section of the centrifuge drum and is then removed from the centrifuge. The crystalline pure adduct is caused to melt and is then sent to the phenol separation unit. In the process version where optical-grade bisphenol A is produced, falling-film melt-fractional crystallization is used instead of recrystallization for the final refining of the bisphenol-A product.

Separation of bisphenol A by adduct decomposition and distilling off of phenol

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The crystalline adduct is caused to melt and the phenol contained in it is stripped and recovered in thin-film evaporator and in a column with packing, where any residual phenol is steam-stripped. The resulting molten bisphenol A is sent to the pelletizer or, in the optical-grade BPA process, to the melt fractional crystallization unit.Recovery of acetone and separation of water Mother liquor from crude adduct centrifuges is fed to the dewatering column for removal of any unreacted acetone as well as water – a byproduct of the condensation reaction.

Separation of heavy ends, phenol recovery and regeneration of bisphenol A In order to separate heavy ends (residue), which have a content of contaminants that are “incapable of rearrangement”, a small portion of dewatered mother liquor is sent to the evaporator. The rest of the mother liquor, which contains bisphenol A and byproducts, is sent to a distillation reactor for catalytic decomposition in the presence of a catalyst, in high temperature and low pressure conditions in order to phenol recovery from the stream containing p-isopropenylphenol and phenol.

Product granulation and packing Liquid bisphenol A is fed from the phenol removal column or from the melt fractional crystallization unit, to the tank where the material is fed, at a constant pressure, to the spraying nozzle of the pelletizer. The sprayed bisphenol A is cooled down using nitrogen which is circulated and cooled down in a closed system. The finished product in the form of pellets, is sent by means of a pneumatic transport system to storage silos and then to hoppers and packing weighers where the bisphenol A product is packed to 1000 kg containers or to valve bags.

Phenol removal from water The phenolic water from the process, containing 7-8% phenol, is subjected to extraction by means of heavy ends which contain byproducts. Water resulting from the extraction and containing 0.5 –1,5 % phenol, is sent to the sorption unit for sorption by means of resins; a liquid waste with less than 50 ppm of phenol is formed as the result.

Technological offgas system Any material discharged from safety valves is to be sent to the flare, outside the plant. Any material discharged from nitrogen blankets and from plant purging is to be sent to combustion Gas disposal methods will be discussed separately, in the phase of basic design preparation.

Schematic representation of the ChemWik process technology:-

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Reference:

The Petrochemical production Processes book by Navid Naderpour Pg.no.134-135 Petrochemical process technology book by I.D.Mall Pg.no.334-336 The Dows chemical product safety assessment page

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http://msdssearch.dow.com/PublishedLiteratureDOWCOM/dh_069f/0901b8038069fd68.pdf?filepath=productsafety/pdfs/noreg/233-00250.pdf&fromPage=GetDoc

Integrated  chemical processes : synthesis, operation, analysis, and ... - Page 234 Petrochemicals   in Nontechnical Language - Page 258

Handbook of  petrochemicals   and  processes by G. Margaret Wells Pharmacokinetics Study in

http://www.bisphenol-a.org/human/herMetabolism.html Envioment safet and impacts from

http://www.bisphenol-a.org/pdf/M4.pdf Assessing Risks from Bisphenol-A

http://www.americanscientist.org/issues/feature/2010/1/assessing-risks-from-bisphenol-a/1 Petrochemicals in Nontechnical Language By Donald L. Burdick, William L. Leffler pg.no.258

http://books.google.com/books?id=hUhQKXnStS4C&pg=PA258&dq=petrochemical+processes;+bisphenol+a&hl=en&ei=zE5qTqrYOc_OrQfHsICiBQ&sa=X&oi=book_result&ct=result&resnum=4&ved=0CEAQ6AEwAw#v=onepage&q&f=false

Various grades fromhttp://www.kazanorgsintez.ru/index.php?page=catalogue&lang_id=2&aid=2625http://www.sriconsulting.com/PEP/Public/Reports/Phase_95/RW95-1-3/

Bisphenol a via Sinopec/ lummus technologyhttp://www.sriconsulting.com/PEP/Private/Reports/Phase_95/RW95-1-3/

Various applications, uses fromhttp://en.wikipedia.org/wiki/Bisphenol_A

Chemical Weekly September 1, 2009 Badger technology from

http://wenku.baidu.com/view/504d9a18227916888486d793.html

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