PRODUCTION OF BISPHENOL-A
RAHUL AGRAWAL (08431G) AAKASH SUMAN (08401G)
13 Sept.2011 Project Review-1
DEPARTMENT OF CHEMICAL ENGINEERING JAYPEE UNIVERSITY OF ENGINEERING AND TECHNOLOGY, A.B. ROAD, RAGHOGARH, DIST. GUNA -473226, M.P., INDIA
ACKNOWLEDGEMENT We wish to express deep sense of gratitude and sincere thanks to our project supervisor Dr. Ashish S. Chaurasia Assistant 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 valuable suggestions. We would like to thank Professor K. K. Tiwari, who is associated with JUET after his retirement from ICT Mumbai for his guidance and suggestions during this project work. We would like to thank Dr. G. K. Agrawal for his suggestions during this work. Our special thank to Dr. Hari Mahalingam – Head of Chemical Engineering Department for providing all the necessary facilities to complete this work. We would like to thank all other faculty members 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 --------------------------------------------------------------
G. “ PRODUCTION OF BISPHENOL A” to this university “ JAYPEE UNIVERSITY OF ENGINEERING AND TECHNOLOGY “. We are also thankful to this institution for providing this golden opportunity to this project successfully. We are thankful to our project guide Dr. The project contents have been planned in such a way that the general requirements can be fulfilled.GUNA.PREFACE
I am glad to present the project entitled. We are feeling great to do this project which has been provided by Dr. and other faculty members of this institution who has given us the adequate information and also encouraged us to do this project.we have observed that the basic information and and the fundamental concepts which has been incurred to make this project are sufficient. During our efforts which has been given to make this wonderful project .
RAHUL AGRAWAL 08431G AAKASH SUMAN 08401G
. K Agrawal . Ashish Chaurasia.
CHAPTER 1: HISTORICAL PROFILE NATURAL OCCURRENCE TRADITIONAL APPLICATIONS/USES MANUFACTURERS HISTORY OF PRODUCT IN INDIA CHAPTER 2: APPLICATIONS CURRENT APPLICATION VARIOUS GRADES/ SPECIFICATIONS/STANDARDS CHAPTER 3: ECONOMIC SCENARIO GLOBAL SUPPLY SCENARIO GLOBAL DEMAND AND SUPPLY GLOBAL DEMAND SCENARIO PRODUCT WISE MARKET PRICE AND PRICE VARIATION GROWTH ASPECTS COMPANY WISE CAPACITIES CHAPTER 4: PROPERTIES PHYSIO-CHEMICAL PROPERTIES -PHYSICAL PROPERTIES -CHEMICAL PROPERTIES BIO-ENVIRONMENTAL CHARACTERISTICS -ENVIRONMENTAL FATE AND IMPACTS -METABOLISM FATE AND IMPACTS HANDLING CONSIDERATIONS STORAGE CONSIDERATIONS SAFETY CONSIDERATIONS CHAPTER 5: MANUFACTURING PROCESSES BADGER BPA TECHNOLOGY SINOPEC/ LUMMUS TECHNOLOGY MITSUBISHI CHEMICAL BPA TECHNOLOGY CHEMWIK PROCESS TECHNOLOGY 5 5 6 7
10 10 11 11 12 12 12
15 16 16
17 19 20 21
products like canned foods to eyeglasses to vital medical equipment and food and beverage containers. medical and dental devices. as an antioxidant in some plasticizers. electronics and food containers. The overall reaction to give polycarbonate can be written: Polycarbonate plastic. It is a white powder and is an estrogen mimicker. It is a key monomer in production of epoxy resins and in the most common form of polycarbonate plastic. in Japan epoxy coating was mostly replaced by PET film. Bisphenol A is also a precursor to the flame retardant tetrabromobisphenol A. is used to make a variety of common products including baby and water bottles. Bisphenol A is mainly used as a bifunctional monomer in the manufacture of polycarbonate plastic and epoxy resins and as an antioxidant in PVC. and products containing bisphenol A-based plastics have been in commerce use since 1957. Some 63% of BPA is used to make polycarbonates. eyeglass lenses. due to BPA health concerns. and household electronics.
Traditional applications:BPA is a monomer used to make polycarbonate resins for applications such as construction. sports equipment. and was formerly used as a fungicide. and the remaining 10% is used for other products including speciality resins and flame retardants. and can cause hormone disrupting effects. and as a polymerization inhibitor in PVC. dental fillings and sealants. It is a relatively small synthetic. 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 .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. At least 8 billion pounds of BPA are used by manufacturers yearly. Bisphenol A is used primarily to make plastics. A further 27% goes into epoxy resin production. which is clear and nearly shatter-proof. 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
. CDs and DVDs. however. BPA is also used in the synthesis of polysulfones and polyether ketones. 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. organic compound with a molecular weight of 228. Epoxy resins containing bisphenol A are used as coatings on the inside of almost all food and beverage cans.
. High quality higher grade polycarbonates is needed to produce consumer goods such as glazing. scientists discovered that Bisphenol A. The first reported synthesis of BPA was from Thomas Zincke of the University of Marburg. baby bottles.
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. phenolic resins and processing of polyvinyl chloride. Indiana Hexion Specialty Chemicals Deer Park.
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. Bisphenol A on Timeline 1891: Bisphenol A. India Mitsubishi chemicals Ltd. a more potent artificial estrogen. Use of Bisphenol A slowed with the discovery of DES. clear plastic for items such as baby bottles and the lining of metal food cans. Germany. hard plastic called polycarbonate. Texas Sunoco Chemicals Haverhill. or BPA. Texas Sabic Innovative Plastics Burkeville.. In the 1940s and 1950s. Kesar petroproducts pvt. notices that control mice had many more defective eggs when stored in polycarbonate cages. Bisphenol A is primarily used in manufacturing of epoxy resins. the halogenated form is used as flame retardants. polyetherimide. This material was used in eyeglasses. The commercial production of bisphenol a started in india in 1970’s. Texas Dow Chemical Freeport.000 tonne per annum. 1998: Patricia Hunt. 1960s: Food manufacturers begin to use BPA to make hard. Idemitsu chemicals pvt. including liquid baby formula. Ltd china Shanghai Righton Co. when combined with the gas phosgene. Maharashtra with an installed capacity of 10. China Bayer Polymers Baytown. a geneticist at Washington State University. The glass fibre reinforced laminates of epoxy resins are light in weight and have the highest tensile strength for any reinforced plastics. Ohio Kesar Loteparhuram. later found to cause reproductive cancer in the children of mothers who took it. shatter-resistant lights and many other applications.Manufacturers: Jingjiang Concord Plastics Technology Co. Ltd. In India. unsaturated polyester resins and polyacrylate. Epoxy resins are thermosetting resins chiefly used for coating and adhesives.. polysulphone resins. Ltd. the alkylated form is used as stblizer and antioxidants for rubber and other plastics. other polysters. helped create a clear. 1930s: The chemical is used as a synthetic estrogen. 1968: The first Phenol producing plant was installed in india in 1968 with the commissioning of unit of Herdillia Chemicals Ltd at Thane. is developed. Alabama Sabic Innovative Plastics Mount Vernon.ltd. The Uses came into notice in 1930s when it was used as a synthetic estrogen product. India Mitsubishi chemicals ltd. compact disc and automotive parts. Other uses include flame retardants (mainly tetrabromobisphenol-A). electrical parts.
August 2008: The Food and Drug Administration declares BPA to be safe. Lawmakers start to call for a ban of the chemical in children's products. diabetes. Wal-Mart. Toys "R" Us and CVS pharmacies .announce plans to phase out use of the chemical in children's products. releases its report expressing some concern for how BPA affects the prostate and neural development of fetuses. including cancer. September 2008: The National Toxicology Program. 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. 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.including Nalgene. A study finds that even low levels of BPA can interfere with chemotherapy for breast cancer patients.000 studies are published showing harm to lab animals from BPA.2000-present: More than 1. infants and children. A study published in the Journal of the American Medical Association in September tied BPA to heart disease in humans. an advisory board to the FDA and Environmental Protection Agency. 2008: Annual sales of BPA exceed $6 billion.
. It also expressed concern about the chemical's effect on breast tissue and early puberty. reproductive failures and neurological disorders. obesity. Several manufacturers .
dialysers. food/catering industry. pharmaceutical industry.Chapter-2:Applications Current Applications:-
Some of the common applications of Bisphenol A-polycarbonate plastic include: CDs. ceilings. 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. metal roofing. e. respirators. coffee makers) Electrical kettles Plug connectors Electrical equipment. garage doors) Gardening tools and equipment Automotive parts and coatings Steel furniture Printed circuit boards Flooring (industrial/public buildings. TVs. machinery Construction panels(cladding. hairdryers. pipes. computers. windmill blades. cameras. 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. chemical plants. helmets. DVDs.g. aviation Adhesives Printing inks
. surfboards. hairspray) Collapsible tubes Coil coatings for household appliances Composites used for rackets. single-use operating instruments) Housings for electronic equipment (cell phones. hospitals) Food and drink cans/can ends General lined cans(oil. Blu-Ray and other discs Roof lights Covers for solar panels Security glazing. engines.
6 % min 156 min 300 max 0. Grade В 1 sort – for production of epoxy resins. Grade A is used for production of molding and extrusion polycarbonates.max.
wt % Celcius ppm ppm ppm ppm APHA
.В. Grade B 2 sort – for production of epoxy resins. adhesives and other products.93 156.Various Grades of Bisphenol A Bisphenol A has following grades: ВЧ.
Specifications for Bisphenol Aameter Value Molecular Formula Mol Wt CAS # Description Assay Crystallization Point in deg cel Free phenol in ppm Isomers (%) Moisture (%) C15H16O2 228.Б. Grade ВЧ.А.max. lacquers. Grade Б is employed in processes of production of epoxy resins and lacquers. АП are intended for production of optical polycarbonate.max.8 300 30 0. o. Ash. Value Unit
99.by GC. MELTING point. adhesives and other products. Phenol.p-isomer.max.min.1 1 5 . as well as extra grade polysulfones and epoxy resins.29 [80-05-7] White powder or flakes 99.1 max
Standards for Bisphenol A BISPHENOL A-STANDARD PRODUCT SPECIFICATIONS PARAMETER PURITY(asp.max Iron. Color25g/35cm3 MeOH.dry state).min.1 max 0.p-isomer.АП.
However.16-mtpa.226 1. Korea and Taiwan. while new BPA capacity has also been added in Asia.38-mt. followed by Korea and Taiwan (15% each). the market became relatively tight from mid-2007 due to a shortage of its raw material.179
. much new phenol capacity has started coming on stream from 2008.346 150 5. Indian scenario:.438 Demand 972 1. with an 18% share. Taiwan alone accounts for 27% of total Asian capacity. followed by Europe (28%) and America (24%) Within Asia.is totally opposite and shows a tight supply of the product
Global/ Indian supply and demand for BPA (KPA) Region America Europe Asia China Japan Korea Taiwan Other Asian(including India) Total Asia Others Total Capacity 1.040
261 615 345 645 480 2.793 174 5. Japan ranks second in terms of demand in Asia. Asia is the largest producing region. While BPA was in oversupply in 2005 and 2006. followed closely by Japan (26%) and Korea (15%). and increased demand from PC and epoxy resins. pushing the market back into over supply. phenol.160
651 565 436 691 650 2. and demand about 4. with 45% of total capacity. China has only 11% of Asian capacity for BPA. but accounts for 28% of total Asian demand. 68% of total capacity is in three countries – Japan.Chapter 3: Economic Scenario Global supply scenario Global BPA capacity in 2008 was around at 5.
Global/Indian demand scenario The main market for BPA. construction and aerospace industries.
Epoxy resins The second largest end use of BPA is epoxy resins. Automotive glazing offers potentially strong growth opportunities for BPA/PC producers. BPA will grow at an average annual rate of 5. CD-ROMs. although PC does offer weight savings. but those based on BPA and epichlorohydrin account for the majority. such as metal and glass. Other uses include flame retardants (mainly tetrabromobisphenol-A).5% during 2009–2014. While PC is being used in rear body parts. unsaturated polyester resins and polyacrylate. in automotive components while glazing and sheet products can be used in architectural. there has been strong resistance from automobile manufacturers in the more general replacement of glass. There are several types of epoxy resins. Over the next few years. the growth in this application is slowing significantly. including audio compact discs (CDs). compared to glass. However. Bisphenol A consumption for epoxy resins production will experience the fastest growth in Asia. applications are expected to widen into back lights and rear windows in truck cabins. flooring and paving applications.
. could be a limiting factor. driven primarily by increasing demand for PC resins. followed by electrical/electronic laminates. polyetherimide and polysulphone resins. security and transportation applications. Optical media. High performance coatings are one of the primary applications. mainly in the automotive. recordable CDs and digital versatile disks (DVDs). adhesives. due to the downloading of music and films from the Internet and other competing technologies becoming more popular. moveable side windows and vehicle top applications. The higher cost. globally. is in production of PC resins. PC Markets The market for BPA had been growing strongly at an average rate of 10% per year over the last few years. as the industry tries to recover volume lost during the recessionary years. followed by use for manufacture of epoxy resins. roof modules and fixed side windows. broader design options and easier handling that could bring efficiencies on the automotive production line. PC resins are also used in the place of traditional materials. had been driving growth in BPA demand via PC.
In short. Germany Stade. with the start-up of PC capacity in China by Teijin and Bayer and several projects planned.810-tons.500-tons. mainly China. with PC and epoxy resins growing at 4. BPA demand in China will be driven in the future by PC.11 per ton/Rs.USD 2661.
GLOBAL BISPHENOL A CAPACITY. In 2005-207. BPA imports were 4.121470. Germany Bergen op Zoom. growth has slowed considerably. as the global economic downturn hits markets. growth is expected to be flat.92/ ton There is no significant price change seen in past 2-3 years.122916/ ton Shanghai Sinopec Mitsui Chemicals co. US demand is expected to increase from 1. In Deer Park. However. Spain Pernis. Alabama Mount Vernon. Asian BPA markets grew at an average of 13% per year with PC pushing it at 19% year. Netherlands
140 160 100 110 210 110
East Europe Petro Borzesti ZC North America Aristech Bayer Dow GE Plastics Shell
Borzesti. Netherlands Cartagena. '000 TONNE/YEAR Company Location Capacity West Europe Bayer
Dow GE Plastics
Antwerp. Ohio Baytown. The US market is expected to grow at 4. PC will continue to be the main driver for BPA. driven by PC demand and improved epoxy resin markets.5% per year respectively. In Europe. Another driver behind BPA demand is the strong growth in Asia.USD 2629. ltd.5% per year and 3. Romania Blachownia.25-mt tons in 2011.06. with global growth forecast at 5-6% per year. as a whole. Texas Freeport. Poland
Haverhill. while the strongest growth will be in Asia. Future growth will be much lower. growth in the Chinese market was mainly due to epoxy resins. In 2007.81 per ton/ Rs. while exports were 34. Up to 2010.2% per year up to 2012. Texas Burkville. Growth prospects Global BPA consumption has increased at an average rate of almost 10% per year from 2007 to 2010. However. Texas
110 120 160 45 166 68 260 102 113
. Belgium Krefeld-Uerdingen.Price and Price variations:Bayer Shanghai chemicals ltd.mt in 2006 to reach 1.
Japan 95 Mitsui Pulau Sakra. Japan 60 Shin Nihon* Kyushu. Taiwan 72 Chang Chun Mailiao. Japan 80 Osaka.Asia Wuxi Resin Kesar Idemitsu Mitsubishi Mitsui
Wuxi. Singapore 70 Kumho P&B Yeochon. Japan 70 Kashima.
. India 7.5 Chiba. Taiwan 20 Taiwan 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. 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. Japan 80 Nagoya. most of them don’t see any further growth in manufacturing capacities except some of the Asian countries like India and China. S Korea 30 Nan Ya Mailiao. As the global market is already over supplied. China 10 Lote parshuram. The manufacturers presumed to increase their manufacturing capacities with level of demand they see in future.
The alkali salts of bisphenol are water soluble. greater than 99. alcohols Solubility in methylene chloride 1.9%. The alkali catalyzed cleavage of various Bisphenols has been investigated . Bisphenols which are alkylated ortho to the OH group readily trap radicals and are therefore suitable as stabilizers.4 kPa Heat of vaporization at 101. 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. water solubility of 120-300 milligrams per liter and a greater solubility at alkaline pH values.The purely thermal cleavage is generally less straight forward. Bisphenols are virtually insoluble in water. bisphenols with large aliphatic groups in the molecule are soluble in araliphatic and aliphatic hydrocarbons. the cleavage can also be catalyzed by acid to form indans and spirobisindans.
Bioenvironmental Characteristics’:Enviromental Fate of bisphenol A:• The vast majority of BPA produced.Chapter-4: Properties Physio-chemical Properties:Bisphenol are colorless. They therefore undergo the same reactions as the corresponding substituted monophenols.492g/cm3 360oC 240oC 222oC 404J/g 227oC 510oC 0.4 kPa 0.3kPa 1. Bisphenols are rarely distilled. Physical properties of industrially important Bisphenol A are:Density at 20oC 160oC Bulk density Bp at 101.3 kPa Flash point Ignition temperature Solubility of water at 83oC Solubility in acetone. 1998). Recent studies demonstrate that BPA degrades
. the aromatic rings and the alkyl bridge. is consumed at manufacturing sites to make products such as polycarbonate plastic or epoxy resins . Under hydrogenation condition of Bisphenol a is cleaved to give 4-isopropylphenol.04g/cm3 1. Whereas bisphenol A is the only readily soluble in polar media such as ethers and alcohols.065g/cm3 0. • The distribution of BPA in the environment can be predicted by its physical properties (Staples et al. For this reason and because of the decomposition frequently observed during boiling.Low levels may be released to the environment in the effluent water from biological wastewater treatment plants. odourless substances and most of them are solid at room temperature. 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. They are also suitable as building block for higher molecular mass linears polyesters are polyethers because of their bifuctionality. Bisphenol A is a solid with low volatility at ambient temperature conditions. The boiling points of bisphenols are very high because of the size of the molecules and its polarity. Rapid and extensive breakdown of BPA has been demonstrated in a variety of laboratory biodegradation tests. Both compounds are good to obtain by other methods. Based on these properties. Some important physical properties of bisphenols are summarized below. However their solubility decreases drastically with increasing substitution. Their solubility in organic solvent is determined by their substituents. alkali catalyzed cleavage gives 4-isopropylphenol in good yields.344 wt% good ca 1 wt%
Chemical properties of Bisphenol A:The chemical properties of Bisphenols are determines by Phenolic OH groups. • Biodegradation plays a major role in the removal of BPA from the environment. The melting point of most of the important Bisphenols are between 100-200C.
Health effects on human being and other organisms:Bisphenol A is an endocrine disruptor.5 micrograms/L respectively.S. but those safety levels are currently being questioned or under review as a result of new scientific studies.01 mg/kg body weight per day.S.00048 to 0. 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. Aquatic tests performed on a fresh water and salt water algae. and children at current human exposures to bisphenol A. is 50 mg/kg body weight per day. and This potential human exposure to BPA is more than 400 times lower than the maximum acceptable or "reference" dose for BPA of 0. and children at current human exposures to bisphenol A. which can mimic the body's own hormones and may lead to negative health effects.Effect-Level. A 2008 report by the U. The SCF estimated total dietary intake of BPA from all food contact sources to be in the range of 0. or both. This conclusion is based on the following key points: BPA is not carcinogenic and does not selectively affect reproduction or development. and some studies have linked prenatal exposure to later neurological difficulties.e. which is problematic because acute animal exposure studies are used to estimate daily human exposure to BPA. infants.life in the range of 1 to 4 days (i. Labor and Welfare. is less than 0. has confirmed the safety of polycarbonate plastic and epoxy resin food contact applications. they noted that while BPA is not persistent in the environment or in humans. suggest that bisphenol A is only moderately toxic to aquatic animals.016 and 0. which is derived from the No-Observed-Adverse. the European Commission's Scientific Committee on Food. or reduced birth weight and growth in their offspring. Europe and the United States. Food and Drug Administration.Impact:The trace amounts of BPA remaining in treated wastewater will continue to biodegrade in receiving waters and downstream of treatment plants. However. Early development appears to be the period of greatest sensitivity to its effects. 1983)."
. birth defects. A 2011 study. Regulatory bodies have determined safety levels for humans. Numerous publications have reported measured concentrations of BPA in streams and rivers in Japan. They added that measurement of BPA levels in serum and other body fluids suggests that either BPA intake is much higher than accounted for.
Human Metabolism Fate:Following the four-step procedure recommended by the United States National Academy of Sciences (NRC. Studies using real world surface water samples taken from various geographies demonstrate rapid degradation with a half.000118 mg/kg body weight/day.0016 mg/kg body weight per day..S. the Japanese Ministry for Health. The No-Observed-AdverseEffect-Level (NOAEL) for BPA. behavior. Environmental Protection Agency. infants.05 mg/kg body weight per day established by the U. time for 50% degradation). A 2011 study that investigated the number of chemicals to which pregnant women in the U. The median reported water concentrations from 21 European and 13 United States studies are 0. and no studies that had examined BPA pharmacokinetics in animal models had followed continuous low level exposures. 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. based on the results of multiple migration studies with consistent results. and other regulatory authorities worldwide. An independent analysis by the European Commission's Scientific Committee on Food (SCF). biomonitoring surveys indicate that exposure is continuous. confirmed in multiple laboratory animal tests. National Toxicology Program (NTP) later agreed with the panel." The NTP had "negligible concern that exposure of pregnant women to bisphenol A will result in fetal or neonatal mortality. are exposed found BPA in 96% of women. The use of polycarbonate plastic and epoxy resins for food contact applications has been and continues to be recognized as safe by the U. or that BPA can bioaccumulate in some conditions such as pregnancy." and "minimal concern for effects on the mammary gland and an earlier age for puberty for females in fetuses. Bio-concentration and metabolism studies have shown that bisphenol A has no significant bioaccumulation potential. expressing "some concern for effects on the brain. and prostate gland in fetuses. invertebrates and fish . the United Kingdom Food Standards Agency. which is below the Tolerable Daily Intake set by the SCF of 0. In 2007.S. using a similar methodology. The estimated dietary intake of BPA from food contact with polycarbonate plastic and epoxy resin.
Sacks should be stored in a clean. which "merits concern among scientists and public health officials".3% by volume oxygen.
Safety Considerations:it would be wise to limit your exposure. They were also less desirable to female mice. bulk sacks. Good housekeeping and controlling of dust is necessary to minimize dust ignition hazard. A 2011 mice study found that male mice exposed to BPA became demasculinized and behaved more like females in their spatial navigational abilities. A 2011 rodent study found that male rats exposed to BPA had lower sperm counts and testosterone levels than those of unexposed males. Storage bins should be equipped with properly designed explosion relief devices. Storage consideration:Storage bins and silos are usually made of one of the following. well ventilated area. Another 2009 review has concluded that "Eliminating exposures to (BPA) and improving nutrition during development offer the potential for reducing obesity and associated diseases". Bulk sacks are typically made of Ultraviolet (UV) resistant woven . alters breast development and increases breast cancer risk". Gravity unloading can be fascilitated with the use of a mechanical vibrator.Obesity A 2008 review has concluded that obesity may be increased as a function of BPA exposure.mechanical handling and fabrication. a species that is very similar to humans in regard to pregnancy and fetal development. Other reviews have come with similar conclusions.A 2009 review of available studies has concluded that "perinatal BPA exposure acts to exert persistent effects on body weight and adiposity".Polypropylene or similar material. 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. Sacks 25 kg Sacks are commonly used for Bisphenol A packaging. dust explosion and moisture gain. Before a sack is lifted . but here are a few steps you can take to reduce your contact. hopper trucks and cars that may help increase plant safety. Containers should be inserted using inert gas containing less than 9. Hopper trucks and Hopper cars Both hopper trucks and hopper cars are sealed containers that are loaded through roof hatches and gravity or pneumatically unloaded through bottom outlet nozzles. Lifting straps are attached to the bulk sack to allow the sack to be lifted by a tow motor or hoist. BPA may be similar to diethylstilbestrol caused birth defects and cancers in young women whose mothers were given the drug during pregnancy. Handling:Minimize exposure to product dust resulting to open transfer operations . Breast cancer A 2008 review has concluded that "perinatal exposure to low doses of BPA. Packaging consideration:Following are the controls for sacks. it should be inspected for snags and punctures. not easily done since BPA is found in so many household products alone.
. found that prenatal exposure to BPA causes changes in female primates' uterus development. A 2011 study using the rhesus monkey. Storage bins and silos should be grounded and padded with an inert gas such as nitrogen to reduce the risk of electric spark. 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". 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. Bulk Sacks 500-1000kgs Bulk sacks are commonly used for Bisphenol A packaging.
Avoid eating or drinking from polycarbonate plastics – used in such products as hard plastic baby bottles. Use non.
. Most major plastic consumer goods manufacturers now offer non-polycarbonate alternatives for drinking bottles. and Lexan products. To keep food from reacting with the metal of the can. or polypropylene bottles labeled number 5 on the bottom (translucent. microwave bowls. plastic silverware. You can check for BPA in the plastics you buy by looking for the stamped on the surface. Cut down on canned foods. Use glass or ceramic. hard plastic water bottles. Alternatives include bottles and other materials made from glass. 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. use waxed paper or paper towels. 5 gallon water cooler bottles. and can leach into the food stored inside.polycarbonate plastics such as polypropylene and polyethylene. and plastic liners. Bisphenol A may leach out of these types of bottles into your beverage or food. Don't use plastic containers in microwaves. stainless steel. not transparent). 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. Don't use plastic cling wrap.
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 . Licensor: Badger Licensing LLC. A very high purity product with polyster quality is obtained if the bisphenol A-phenol 1:1 adduct is separated .95 Methanol color.p BPA. after separation of the hydrogen chloride by distillation and neutralization. Bisphenol A crystallizes as an adduct with 1 mol phenol . These plants are extremely reliable and have been engineered to meet the operating standards of the most demanding refining and chemical companies. Acetone and lights are adsorbed into phenol in the lights adsorber (3) to produce a recycle acetone stream.
Badger BPA Technology:Applications:The Badger BPA technology is used to produce high-purity bishenol A (BPA) product suitable for polycarbonate and epoxy resin applications. The use of ion exchangers is preferred to that of hydrogen chloride because they are less corrosive. The recovered purifi ed adduct is processed in a BPA fi nishing system (8) to remove phenol from product. the whole reaction mixture can be fractionally distilled . The yield is normally 80-95%. began operation in 1992 at the Deer Park (Houston) plant now owned and operated by Resolution Performance Products LLC. the molar ratio phenol –acetone is to 15:1. The solvent free mother liquor stream is recycled to the reaction system. two other world-scale plants were licensed to the Asia-Pacific market. °C 157 BPA w/w. water and various byproducts.
. Since that time. wherby bisphenol A itself is distilled over particularly carefully under high vacuum. High capacity operation has been fully demonstrated. Crude bisphenol A can also be purified by extracting into hot heptanes or the mixtures of aromatics or by recrystallization from aromatics. Description: Acetone and excess phenol are reacted by condensation in an ion exchange resin catalyzed reactor system (1) to produce p. These processes are mostly carried out continuously . BPA is separated from byproducts in a proprietary solvent crystallization and recovery system (5) to produce the adduct of p. The bottoms of the crude column is sent to the crystallization feed preconcentrator (4). The catalyst system uses a unique upflow design that is beneficial to catalyst life and performance. separated from resins byproducts . There are many processes for the industrial synthesis of this most important .Chapter-5:Manufacturing processes Bisphenol A. The crude distillation column (2) removes water and unreacted acetone from the reactor effl uent. among the largest in the world. and the phenol removed by distillation . Mother liquor from the purifi cation system is distilled in the solvent recovery column (6) to recover dissolved solvent. which distills phenol and concentrates BPA to a level suitable for crystallization. Product quality: Typical values for BPA quality are: Freezing point. wt% 99.p BPA and phenol.recrystallized from phenol. and the resulting molten BPA is solidified in the prill tower (9) to produce product prills suitable for the merchant BPA market. The reaction of phenol and acetone takes place at 50-90 c. Process features: The unique crystallization system produces a stable crystal that is efficiently separated from its mother liquor.Currently. To isolate the bisphenol . APHA 5 Commercial plants: The first plant. and subsequently recrystallized under pressure at elevated temperature . A purge from the mother liquor is sent to the purge recovery system (7) along with the recovered process water to recover phenol. The product is produced over ion-exchange resin from phenol and acetone in a process featuring proprietary purify cation technology. The acetone-phenol mixture produced in the hock phenol synthesis from cumene hydroperoxide can be used as starting material for bisphenol A synthesis.
acid based technologies by doing away with the acid based environment. Developed by Sinopec Technology Company and marketed by ABB Lummus Global. All of the problems associated with handling acid . High phenol conversion permits a simple 1-stage crystallization system.
Process features: High activity ion exchange resin catalyst Catalytic stripping reactor Simpler 1-stage product portfolio Advantages: High conversion/low recycle rate
. This reduces recycles and utility consumption thereby reducing operating and capital costs. Much higher conversions and better selectivity are achieved then with other ion exchange resin catalyst system. Continuous centrifuges are utilized for easier operation . It replaces older. In the Sinopec/Lummus process special crystallization technology is employed that produces large crystals with few impurities. These improvements further contribute to lower operating and capital costs. together with an improved high activity and high selectivity catalyst. Ion exchange resin is today’s preferred catalyst system for bisphenol –A manufacture. crystallizer volume can be low due to the high BPA content of the reactor effluent. This new reaction system promotes the BPA condensation reaction under highly favourable conditions while simultaneously removing the water of reaction. including corrosion and disposal of acid waste. result in complete conversion of acetone and maximum phenol conversion . with low by-product formation. a novel reactor technology for the condensation of phenol and acetone.The Sinopec/ Lummus Technology:Technology: The Sinopec/Lummus bisphenol –A technology is a fully continuous process that incorporates catalytic stripping. are eliminated. The catalytic stripping reactor provides a very high effective phenol to acetone ratio that . this advanced technology maximizes yield and conversion using an environmentally preferred ion exchange resin catalyst.
flow directly to primary crystallization where BPA adduct crystals are obtained. (1) Superior Product Quality (2) High Catalyst Performance (3) Low Construction Cost (4) MCC’s rich experience
. An alternative catalyst now widely used is cation exchange resin. Mother liquor from primary crystallization is conc. leading to improved raw material efficiency and finished product color. Water of reaction is simultaneously stripped from the reaction mixture by a recirculating stream of nitrogen. so the BPA plant requires expensive corrosion-proof materials. complicated waste water treatment facility is needed for the mineral acid catalyzed process. Adduct crystals are melted and distilled under vaccum to produce raw BPA. Tar residue is purged from the process and may be used as fuel. can improve BPA production rate and its yield. precipitation of the calcium. Secondary mother liquor containing essentially all of the reaction by product is thermal cracked and catalytically rearranged.
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. commercial scale BPA production has been based on a strong mineral acid catalyst such as hydrochloric acid. and further biotreatment.4’-bisphenol A (BPA) is an important industrial chemical. BPA is produced by acid catalyzed condensation reaction of two moles of phenol and one mole of acetone. it must be treated by neutralization with lime. Traditionally. Feature of Mitsubishi BPA process The characteristic and superiority of MCC BPA process are as follows. Dry phenol is recycled to the condensation reactor and waste water is purged. And phenol is dewatered by distillation in the phenol recovery unit. MCC continues to exert effort to achieve effective BPA process. An evaporator remove residual trace phenol and BPA melt flow to product handling. Process chemistry:2C6H5OH + (CH3)2CO Phenol Acetone (C6H4OH)2C(CH3)2 + H2O Bisphenol A water
Mitsubishi Chemical Bisphenol-A Technology:
Bisphenol-A: (BPA) 4. In addition. which is mainly used as a raw material of polycarbonate and epoxy resin. Reaction mixture consist of unreacted phenol saturated with BPA. MCC's BPA process (PROCESS) employs an improved ion exchange resin catalyst that exhibits higher activity and longer life compared to other resin catalysts. which contain thiol groups. Hydrochloric acid is highly corrosive. Introduction of Mitsubishi BPA Technology MCC has been improving BPA process to realize lower raw material consumption and the stable operation. Recovered BPA and byproduct flow to the secondary crystallization unit. essentially free of acetone containing very low level of water and impurities. This type of catalyst mitigates equipment corrosion. Rearrangement product is recycled for recovery of BPA. Even now. Some components. BPA adduct from secondary crystallization is returned to primary crystallization for recovery. Impurities are significantly reduced. Since waste water from the process contains some amount of hydrochloric acid.
4-BPA isomer Methyl BPA Trisphenol Chromans p-Isopropenylphenol cyclic dimer p-Isopropenylphenol linear dimer
Simplified block flow
Technology: Chemwik BIS process of technology. Bisphenol A synthesis is carried out in original reactors in three reaction zones. through a system of filtration-injection nozzles located at several levels.Besides Bisphenol-A. is based on the use of ion exchange resins with a chemically bound promoter of the reaction as a catalyst for BPA synthesis. Post
. 2.or double-step crystallization from a phenolic solution. small amounts of following major impurities are produced. Bisphenol A is recovered from the post-reaction mixture and refined by way of single. This is followed by the thermal decomposition of a BPA-phenol adduct and distilling off of phenol.
so that the phenol-acetone reaction in the Synthesis Unit I.p-bisphenol A. 99.
. In addition to p. 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.2-dimethylthiazolidine. for instance: ▪ bisphenol A o. By recirculating a stream of mother liquor. among other things.crystallization liquor is dewatered by distillation and recirculated to the synthesis unit. The condensation reaction is exothermal and water is formed as its main byproduct. • It is an energy saving process. Any recovered acetone and phenol are recycled to the process. A standard bisphenol A product. with a chemically bound reaction promoter in the form of 2. 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) ▪ 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). close to an equilibrium (8-10 %). which reaction is catalyzed by an acid ion-exchange resin. crosslinked with 4% DVB.5 year. If larger reactors are used. adding to the reaction yield and selectivity.p-bisphenol A. An optimum lifetime of the promoted catalyst without replacement and without regeneration is 1-1. 2.p-isomer ▪ trisphenols ▪ dihydroxyindanes (DHI) ▪ Dianin compounds. phenol recovery. • It is a fully automated process. 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. the final product is in the form of white pellets. the byproducts are kept in the reaction at a constant concentration. • Low consumption of raw materials. Synthesis Unit I comprises 85-100 m³ reactors with a solid catalyst bed. obtained with the use of double-step crystallization from a phenolic solution. the promoted catalyst lifetime may be extended to ab.
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. 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. produces mainly p. a number of byproducts are formed. Bisphenol A is formed by condensation of a single mole of acetone with two moles of phenol. which is suitable for use in the manufacturing of polycarbonates and epoxy resins. enabling the number of plant operating personnel to be minimized. which are located outside the reactors.5 year. which is very convenient for use in pneumatic transport systems. When leaving the production facility. which results from the high BPA increments in the reaction. The scope of known-how on offer includes a commercially proven methodology for the promoted catalyst preparation. is characterized by a purity of min. Each reactor is divided into three reaction zones by means of a system of filtration-injection nozzles which are located at various levels.p-bisphenol A.93 %. The pellets are obtained using a conventional pelletizer system. The heat of the exothermal reaction is removed in a continuous manner by means of heat exchangers.
. composed of regenerated phenol and washings from adduct centrifugation after recrystallization. The sprayed bisphenol A is cooled down using nitrogen which is circulated and cooled down in a closed system. Separation of heavy ends. with a chemically bound reaction promoter as in the synthesis unit I. 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. in high temperature and low pressure conditions in order to phenol recovery from the stream containing p-isopropenylphenol and phenol. is sent to a distillation reactor for catalytic decomposition in the presence of a catalyst. The finished product in the form of pellets. Crystallization takes place as the result of cooling the solution. and an addition of acetone. Separation of bisphenol A by adduct decomposition and distilling off of phenol 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. Water resulting from the extraction and containing 0. The crystalline pure adduct is washed with pure phenol in the screen section of the centrifuge drum and is then removed from the centrifuge. crosslinked with 4% DVB. a liquid waste with less than 50 ppm of phenol is formed as the result. 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. Crystallization and separation of crude adduct The stream from the Synthesis Unit I reactors is sent to adduct crystallizers. 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. 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 pure adduct is caused to melt and is then sent to the phenol separation unit.5 % phenol. The feed to the reaction is a stream of phenol. Phenol removal from water The phenolic water from the process. 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. in the phase of basic design preparation. to the melt fractional crystallization unit. Any material discharged from nitrogen blankets and from plant purging is to be sent to combustion Gas disposal methods will be discussed separately. containing 7-8% phenol. where any residual phenol is steam-stripped. to the tank where the material is fed. in the optical-grade BPA process. In the process version where optical-grade bisphenol A is produced. at a constant pressure. is subjected to extraction by means of heavy ends which contain byproducts. falling-film melt-fractional crystallization is used instead of recrystallization for the final refining of the bisphenol-A product. to the spraying nozzle of the pelletizer. The resulting crystalline suspension is sent to screen drum centrifuges. The Synthesis Unit II comprises 20-85 m³ reactors with a solid catalyst bed. where a crystalline adduct comprising bisphenol A and phenol in a 1:1 ratio by mole is obtained. outside the plant. Technological offgas system Any material discharged from safety valves is to be sent to the flare. a small portion of dewatered mother liquor is sent to the evaporator.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. The rest of the mother liquor. which have a content of contaminants that are “incapable of rearrangement”. which contains bisphenol A and byproducts. is sent from the crystallizers to screen drum centrifuges. phenol recovery and regeneration of bisphenol A In order to separate heavy ends (residue). Product granulation and packing Liquid bisphenol A is fed from the phenol removal column or from the melt fractional crystallization unit. is sent to the sorption unit for sorption by means of resins. The crystalline suspension formed. The resulting molten bisphenol A is sent to the pelletizer or.
Schematic representation of the ChemWik process technology:-
258 http://books.org/human/herMetabolism.dow.html Envioment safet and impacts from
Chemical Weekly September 1..wikipedia.sriconsulting.pdf
Assessing Risks from Bisphenol-A http://www. 2009 Badger technology from http://wenku.no.com/PublishedLiteratureDOWCOM/dh_069f/0901b8038069fd68.pdf&fromPage=GetDoc Integrated chemical processes: synthesis.php?page=catalogue&lang_id=2&aid=2625
http://www.no.com/PEP/Public/Reports/Phase_95/RW95-1-3/ Bisphenol a via Sinopec/ lummus technology http://www.org/pdf/M4.334-336 The Dows chemical product safety assessment page http://msdssearch.Mall Pg.bisphenol-a.Reference: The Petrochemical production Processes book by Navid Naderpour Pg.D.+bisphenol+a &hl=en&ei=zE5qTqrYOc_OrQfHsICiBQ&sa=X&oi=book_result&ct=result&resnum=4&ved=0CEAQ6AEwA w#v=onepage&q&f=false Various grades from
http://www.134-135 Petrochemical process technology book by I..com/view/504d9a18227916888486d793.Page 234 Petrochemicals in Nontechnical Language . analysis.html
.ru/index. William L. Leffler pg.no.kazanorgsintez.Page 258 Handbook of petrochemicals and processes by G.baidu.org/issues/feature/2010/1/assessing-risks-from-bisphenol-a/1 Petrochemicals in Nontechnical Language By Donald L.americanscientist. Burdick.google.pdf?filepath=products afety/pdfs/noreg/233-00250.bisphenol-a. Margaret Wells Pharmacokinetics Study in http://www. uses from
http://en.com/PEP/Private/Reports/Phase_95/RW95-1-3/ Various applications. operation.com/books?id=hUhQKXnStS4C&pg=PA258&dq=petrochemical+processes. .sriconsulting. and .