Special Report

Bisphenol-A: A Techno-Commercial Profile

Part 1: Manufacture & Global Scenario
INTRODUCTION isphenol A (BPA) is an important industrial chemical used primarily to make polycarbonate (PC) resin and epoxy resins, both of which find wide application.

processes, the reaction is catalyzed by acids such as hydrogen chloride, aqueous hydrochloric acid, or strong acid ion exchange resins. Reaction mechanism The first step in the acid catalysed reaction consists of the reaction of acetone and the strong acid to form a carbonium ion. This ion adds one mole of phenol and subsequently forms the second carbonium ion, which eliminates a mole of water and then reacts with a second mole of phenol to form BPA. Besides BPA, several by-products are formed in the process, which reduce reaction selectivity. These include particularly the ortho, para-isomer, which can be partly isomerised to give back additional amounts of the desired para, para-product. Raw materials Crude reaction mixtures of phenol and acetone, made from the cumene hydroperoxide (CHP) process for phenol (and acetone) production, can be

For example, PC is used in eyeglass lenses, medical equipment, water bottles, digital media (e.g. CDs and DVDs), cell phones, consumer electronics, computers and other business equipment, electrical equipment, household appliances, safety shields, construction glazing, sports safety equipment, and in automobiles. Among the many uses for epoxy resins are industrial floorings, adhesives, industrial protective coatings, powder coatings, automotive primers, can coatings and printed circuit boards. Manufacture BPA is prepared by the reaction of one mole of acetone and two moles of phenol to give primarily the para, paracondensation product. In commercial

used to make BPA. Since 0.62-kg of acetone is made per kg of phenol in the CHP process and 0.26-kg of acetone is used per kg of phenol in BPA production, the mixture must be depleted in acetone by distillation or enriched in phenol by addition to adjust to the desired ratio for BPA synthesis. Since the reactants used in the production of BPA can come from a number of sources, this can introduce varying types and quantities of impurities and trace materials in BPA production feed. For example, acetone can be produced from the oxidation of isopropyl alcohol (IPA) which is less common or, more commonly, by the decomposition of CHP. Acetone produced by the first mentioned route is called on purpose acetone and is known to be low in impurities such as methanol. However, it is not widely produced on a commercial basis. In contrast, most BPA is produced in integrated chemical manufacturing plants by the decomposition of CHP. This is typically found mixed with at least about 200ppm methanol, which will azeotrope with acetone. Catalyst systems A number of acidic catalysts can also be used in BPA production processes:  Strong mineral acids, such as hydrochloric or sulphuric acid can be used as catalysts. The former is much preferred due to its lower boiling point and relative ease of removal from the reaction mixture.  Instead of strong mineral acids, strongly acidic cation exchange resins, such as the styrene/ divinylbenzene type can be used, with or without activity enhancing modifiers.
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Figure 1: The chemistry behind BPA manufacture

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Resin catalysts eliminate catalyst recycle and greatly mitigate equipment corrosion and wastewater treatment problems. To compensate for any activity deficit, reaction temperatures can be increased to 70-80C, compared to 50C with concentrated aqueous or gaseous dry HCl catalyst. Due to these advantages, in recent years, acidic cation exchange resins have become the overwhelming choice for BPA production. Strongly acidic sulphonated polystyrene ion exchange resins are particularly useful in this regard. Two different techniques for employing acidic ion exchange resins as catalysts predominate in industrial practice. Free co-catalyst technique In one technique, called the free co-catalyst technique, the co-catalyst typically an organic mercaptan, such as methyl or ethyl mercaptan is freely circulated in the reactor with the reaction feed to enhance the selectivity and/or activity of the reaction. The acidic sites of the resin are left available, i.e., largely unbound to the cocatalyst. This provides flexibility in adjusting the optimal concentration of co-catalyst, given the particular reaction conditions in question. The co-catalyst can be put in the presence of reactants and catalyst in a number of ways and can be readily replenished as needed. This enables refinement of the reaction through the differential treatment of the catalyst and co-catalyst. If, for example, cocatalyst is removed from the reactor along with reactor products, it can be separated from the reaction products and recycled back into the reactor in a subsequent step. However, if a catalyst problem is encountered, the catalyst may be treated without necessarily involving any adjustments to the co-catalyst. While this is an advantage of the free co-catalyst method, it
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must also be acknowledged that it nevertheless introduces more variables into process control than might otherwise be encountered and makes for somewhat complex reaction dynamics. Fixed modified resin technique In this technique for employing acidic ion exchange resins in the production of bisphenols, the resin is modified by appending co-catalytic agents such as aminoalkylmercaptans to some of the acid sites on the resinous catalyst. Typically, organo mercaptan promoter groups are attached to the backbone sulphonate ion by covalent or ionic nitrogen linkages. The fixed modified resin technique requires less direct handling and treatment of co-catalysts such as the noxious mercaptans. The ability to refine the process by differential treatment of the resin and co-catalyst is greatly reduced, but there are fewer problems and reaction dynamics are less complicated than seen in the free co-catalyst technique. The acidic catalysts used in either technique show a tremendous proclivity for rapid deactivation. There are many possible reasons for this, including catalyst poisoning. As noted above, any number of materials other than phenols and ketones may be present in the feed and could interfere with the catalyst. For example, metal poisoning is a possibility; additionally, thermal perturbations can cause a loss of the acidic functional groups from the resins on which they are supposed to be bound. Further, the presence of bisphenolic tars and other reaction residuals can greatly reduce mass transfer in the reaction. Typical process A typical process for BPA involves the following steps:  Synthesis of BPA in a two-stage reactor system;

 Purification and separation of the phenol-BPA adduct by suspension crystallization and then centrifugal separation;  Formation of BPA through adduct decomposition, followed by phenol distillation;  BPA granulation;  Removal of acetone and water from crystallization phenolic liquors;  Recovery of acetone and phenol; and  Catalytic decomposition and rearrangement of by-products to BPA. Commercial processes Though BPA production by both the resin-catalysed and HCl-catalysed processes is well developed, continuous improvements have been made to both routes. In the late 90s, there were five licensors of BPA process technology, three offering resin-catalysed processes and two offering HCl-catalysed processes. In addition, several major producers had their own technology, which were available for licensing under special circumstances. Dow Chemicals Dow Chemicals, which has extensive experience in BPA technology and manufacture, has been producing BPA since 1960 for use in production of epoxy resins. Its first BPA plant was located in Midland (Michigan, USA). Dows continuous process development and improvements in the late 1960s led to a new technology based on proprietary cation exchange resin catalysts to produce PC grade BPA. In 1972, Dow started up its first commercial plant based on this improved resin technology at Freeport (Texas, USA). Since then, Dow has continued to improve the technology, especially in the areas of product quality, higher operating efficiency and reduced capital costs.
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At present, Dow is one of the leading producers of BPA with a total production capacity of 370-ktpa in four plants in Texas (US) and Stade (Germany). The company directly offers its QBIS technology for licensing and has tied up with M.W. Kellogg Co, an engineering company, to license the technology. The first plant licensed to be built using this technology was 90ktpa plant of Nan Ya Plastics, a part of Formosa Plastics, in Mailiao, Taiwan. The plant was brought on-stream in early-1999 and expanded to 100-ktpa in 2005. Dow has continued to improve its BPA process and successfully demonstrated its High-Purity BPA Generation II process at its Stade site. The BPA reaction is catalysed by a Dowex cation exchange resin and is batchpromoted via a proprietary system to achieve proper selectivity to the para, para isomer. A comparison of the economics of the HCl catalyst process and the Dow High-Purity BPA Generation II, carried out by Chemsystems, reveals that:  The net raw material costs are essentially the same for both processes;  The ion exchange resins process has lower utility costs; and  Investment related expenses, such as maintenance, insurance, property taxes and general plant overheads are lower for the ion exchange resin catalysed process. Chiyoda process The CT-BISA [Chiyoda Thoroughbred Bisphenol A] process is a catalytic route for BPA from phenol and acetone also using an ion exchange resin as catalyst. The process was developed and offered by Chiyoda Corporation (Japan) and the first plant based on this techChemical Weekly

nology was operated in Tobata, Japan in 1997. Mitsubishi Chemical Corporation (MCC) acquired this technology from Chiyoda and improvised it, including developing a new technology termed 4PET. MCC continues to license the technology. In November 2006, it signed a technology licensing agreement with PTT Phenol Company Ltd. for a 150-ktpa BPA plant to be built at Map Ta Phut (Thailand). STC process Sinopec Technology Company (STC) (China) also developed a technology for producing BPA from phenol and acetone. ABB Lummus Global of USA offers the technology under license from STC. Polish process ICSO (Poland) claims to have established five BPA plants using the first version of its technology: PCC Synteza (13,000-tpa), Taiwan (20,000tpa), China (12,000-tpa), India (7000tpa) and Iran (30,000-tpa). The technology has been developed further and is now offered as the Chemwik BIS Process by Chemwik Sp. Zoo Company (Poland). The modified process is claimed to have better catalyst life, better energy efficiency and offers higher purity of BPA as compared to the earlier version. Health concerns associated with BPA BPA has been attracting the attention of environmentalists over health issues ever since research on laboratory animals showed it can adversely affect brain development and behaviour in foetuses, infants and children. Consequently, the chemical has been included in a group termed hormone disruptors or endocrine disruptors, that are able to disrupt the

chemical messenger system in the body. There is growing international concern about manmade endocrine disrupting chemicals, because they can de-rail the development of offspring exposed in the womb. It is feared that they may be partly responsible for the decline in sperm counts, and the increased rates of hormone related cancers, such as cancers of the breast, testes and prostate. They are also suspected of causing birth defects of the reproductive tract, and other hormone related effects, such as earlier puberty in girls. The fears arise on account of the fact that BPA can be released from PC plastic bottles containing hot liquids. This has prompted calls for a ban on BPA in plastic baby bottles and other food containers. The American Chemistry Council (ACC), an industry trade group, has claimed that fears about BPA are overblown, citing research that the levels ingested by most people are far too low to have adverse effects. Scientific evidence The scientific evidence supporting the safety of BPA has been repeatedly and comprehensively examined by government and scientific bodies worldwide. In every case, these assessments support the conclusion that BPA is not a risk to human health at the extremely low levels to which people might be exposed. In January 2007, the European Food Safety Authority released a comprehensive assessment of BPA that was conducted by a panel of 21 independent scientific experts from the European Union. Based on their review of the most recent scientific information, the panel increased by a factor of five the safe intake level for BPA that was established in 2002. The increase was based on the panels view
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that there is now more certainty about the safety of BPA. In June 2006, a panel of scientific experts reported the results of their weight-of-the-evidence evaluation of low-dose reproductive and developmental effects of BPA. Considering studies published through February 2006 and the results of a 2004 evaluation, the panel concluded the weight of evidence does not support the hypothesis that low oral doses of BPA adversely affect human reproductive and developmental health. In January 2006, the German Federal Institute for Risk Assessment released a statement with their views on the safety of PC baby bottles. They noted The BfR does not recognize any health risk for babies that are fed from baby bottles made of PC. A November 2005 statement from the US Food and Drug Administration on the safety of food contact products made from PC concluded based on all the evidence available at this time, FDA sees no reason to change its long-held position that current uses with food are safe. In November 2005, a comprehensive risk assessment on BPA conducted by scientists at the Japanese National Institute of Advanced Industrial Science and Technology concluded that current exposure levels of BPA will not pose any unacceptable risk to human health. In March 2005, the Japanese Ministry of Environment (MoE) reported the results of their own tests on BPA, including a comprehensive reproductive test in laboratory animals. MoE concluded that there were no clear endocrine disrupting effects at low doses and that no regulatory action is required to manage risks.
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Authorities take action Not withstanding these studies, the pressure on PC use for baby bottles and for other food contact and packaging applications is expected to mount. In May this year, Chicago became the first major city in the US to ban the sale of baby bottles and sipper cups that contain BPA for use by children under the age of three. Earlier, Minnesota became the first US state to ban the use of BPA in baby bottles from 2010. Earlier this year, Suffolk County, New York was the first local government in the US to introduce such a ban. In 2008, U.S. retailers such as WalMart and Toys R Us announced plans to phase out baby bottles containing BPA. In May this year, Sunoco Chemicals, a relatively small US producer of BPA, announced it would no longer sell BPA to customers who could not guarantee the product will not be used in food and water containers for children under the age of three. The impact of these restrictions on BPA demand may not be significant. Low dose exposure to BPA occurs mainly through food contact applications of this chemical, yet these applications represent just a small per cent of this chemicals wide variety of uses across multiple sectors. Alternatives to BPA for food contact applications Despite industry and government assurances, many consumers and manufacturers have moved away from this chemical in food contact uses and have embraced products they believe to be safer. The market for PC plastic bottles has been particularly impacted by this shift.

Replacement options for PC Speciality polyesters The primary replacement for BPA in reusable water bottles is Tritan copolyester, which was introduced in October 2007 by Eastman Chemical Company. Tritan is cleared for food contact applications in the US. In August this year, the European Food Safety Authority (EFSA), the European Unions agency responsible for food and feed safety, issued a favourable opinion that supports the safety of Tritan copolyester. The opinion is expected to pave the way for the European Commission to amend Directive 2002/72/ EC to add a key monomer used in Tritan to its list of acceptable monomers for the production of plastics intended for use in food packaging. Eastmans main Tritan production plant (capacity: 50-ktpa) is under construction in Kingsport (Tenn., US) and will be fully operational late 2009/early 2010. Alternative materials Glass, steel and aluminium are also seen as non-BPA, non-plastic options for PC. Alternatives to epoxy resins The vast majority of food and beverage cans are coated with epoxy resins made from BPA. This specific food-contact application offers a route of exposure to low doses of this chemical. While alternatives to epoxy coatings have been developed for certain niche applications, no currently available BPA-free alternative seems to be in a position to broadly replace epoxies in metal food and drink can applications. Possible non-BPA-based epoxy resin replacements include polyesterbased coatings, oleoresinous materials and other types of epoxy.
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Are the alternatives safer? While the safety of BPA has certainly been called into question, common alternatives to this chemical could pose new health risks. Consumers want to believe that these alternatives have been adequately tested, yet many experts believe the regulatory system lacks a complete set of testing requirements to ensure this has happened. In 2004, the Danish Environmental Protection Agency published a study on alternatives to BPA. They found that the screening of environmental and health properties of the polyester and polyamide alternatives (to BPA in food contact applications) indicates that these groups are possibly less harmful to health and the environment than BPA. On the other hand, [other] alternatives may cause the same effects or more hazardous effects on both environment and health as BPA. Global supply scenario Global 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%). Table 1 Global supply and demand for BPA [2008] [Kilotons per annum] Region America Europe Asia China Japan Korea Taiwan Other Asian Total Asia Others Total Capacity 1,226 1,438 Demand 972 1,040 Country America Europe China Japan Korea Taiwan Thailand Others Total 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 onstream from 2008, while new BPA capacity has also been added in Asia, Table 2 Major producers of BPA [2005] [Kilotons per annum] Company Capacity Sabic Innovative Plastics Hexion Specialty Chemicals Dow Chemical Bayer Mitsui Chemicals Sunoco Chemicals Mitsubishi Chemical Nan Ya Plastics Total 1,225 640 580 900 330 110 200 290 5,160

pushing the market back into oversupply. All US producers make BPA through the acid-catalyzed (hydrochloric acid) condensation of phenol

Table 3 US BPA capacity [2007] [Kilotons per annum] Company Bayer Polymers Dow Chemical Sabic Innovative Plastics Sabic Innovative Plastics Hexion Specialty Chemicals Sunoco Chemicals Total
Source: ICIS Chemical Business

Location Baytown, Texas Freeport, Texas Burkeville, Alabama Mount Vernon, Indiana Deer Park, Texas Haverhill, Ohio

Capacity 190 190 75 265 250 110 1,080

Table 4 Capacity build-up expected for BPA [Kilotons per annum] Capacity in 2008 1,226 1,438 261 615 345 645 250 380 5,160 New capacity in 2009 211 158 67 436 New capacity in 2010 40 67 68 150 325 Total capacity in 2011 1,226 1,438 512 615 570 780 400 380 5,921

261 615 345 645 480 2,346 150 5,160

651 415 336 341 550 2,293 74 4,379

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with acetone, and usually a promoter like methyl mercaptan is present. All companies have captive phenol and acetone supplies for BPA production and all except Sunoco have captive BPA requirements for downstream resins. Sabic Innovative Plastics captively uses all BPA produced at its two plants, in the manufacture of PC resins and polyetherimides. The economic downturn has had an impact of BPA markets and producers have responded by slashing operating PC dominates BPA use in US
Others 6% Epoxy resins 30%

rates and even shutting plants. In May 2009, Hexion Specialty Chemicals, Inc. announced it plans to indefinitely idle its BPA3 production unit, at its manufacturing complex in Deer Park (Texas, US). The unit, which has a rated capacity of 190 million pounds (about 87-ktpa), will be taken off line and idled once the BPA4 unit with a capacity of 310 million pounds (140-kt) is operational. Global demand scenario The main market for BPA, globally, ..... and elsewhere in the world

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 markets The 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. One of the problems is the poor scratch resistance of PC, although PC manufacturers now claim that multi-layer products have been developed to overcome this problem. The higher cost, compared to glass, could be another 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.
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Epoxy resins 21%

TBBA 2% PC 73% Other resins 2% PC 66%

Figure 2: BPA demand by end-use: US & world [2006]

Packaging (inc bottles) accounts for small share of PC demand (2.9 mt in 2006)
Medical 3% Packaging 3%

Construction 13% Others 2%

Optical Media 32%

Blends 15% Automotive 9% Electronics 23% Figure 3: Global PC demand by end-use

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Table 5 Global PC capacity [2006] [Kilotons per annum] Company Bayer MaterialScience Sabic Innovative Plastics Dow Chemical* Teijin PC Formosa Idemitsu Thai PC Mitsubishi Other Total
Note: * Includes joint ventures

Capacity 1,210 975 415 200 175 140 125 440 3,680

Epoxy resins The 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. Growth prospects Global BPA consumption has increased at an average rate of almost 10% per year from 2003 to 2006, driven by PC demand 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 2005, growth in the Chinese market was mainly due to epoxy resins. However, with the start-up of PC capa-

city 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 2000-2006, 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 2010, with PC and epoxy resins growing at 4.5% per year and 3.5% per year respectively. US demand is expected to increase from 1.06mt in 2006 to reach 1.25-mt tons in 2010. In 2006, 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. [Forthcoming: Indian BPA scenario]

Some North American retailers have removed PC baby bottles and water bottles from shelves, while Canada has announced plans to ban PC baby bottles. However, the impact on BPA/PC demand is expected to be small as total packaging applications only account for 3% of overall PC demand.

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