Contact:

Dr Maciej Kiedik, MEXEO, ul. Energetyków 9, 47-225 Kędzierzyn-KoźleTel. +48-77 4873810; E-mail: mexeo@mexeo.pl

ADVANCE BPA – THE NEW BISPHENOL-A PRODUCTION TECHNOLOGY

A comparison of the developments in the BPA production technology, as reflected in the size of reaction units I and II, where KN is the reactor with the non-promoted catalyst,

and KP is the reactor with the promoted catalyst

The original technology: The hybrid technology: The new technology: ion-exchange CHEMWIK-BIS ADVANCE BPA

THE KEY REACTION UNITS I AND II OF THE BPA PRODUCTION TECHNOLOGY

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Consortium Partner:Institute for Engineering of

Polymer Materials and Dyes in Toruń

XME EOR

Consortium Leader:MEXEO

Kędzierzyn-Koźle

Information about the history of research leading to the new Polish BPA production technology

The first commercial BPA plant was commissioned in the “Blachownia” Chemical Works in Kędzierzyn-Koźle in 1978. The technology had been developed by Dr Kiedik and his team in cooperation with Prof. Edward Grzywa. The plant was one of the first BPA facilities in the world to use an ion exchanger resin as a catalyst in the process.

The ion-exchange process was then regularly improved based on the experience, gained in conducting commercial-scale tests in the working plant in the Blachownia Chemical Works in Kędzierzyn-Koźle (later renamed into PCC Synteza S.A.). In 1996, the then innovative hybrid technology was implemented in order to improve the reaction yield. The hybrid technology was based on two types of catalysts: one was in the form of an ion exchanger resin, the other was an ion exchanger with a chemically bound promoter. After being licensed eight times to licensees abroad (Taiwan, China, India, Korea, Iran), the BPA technology stopped being competitive in the year 2001 and no more contracts were entered into afterwards. The major disadvantage of that version of the Polish BPA technology was that its energy consumption was too high.

In 2004, Dr M. Kiedik started his independent effort to improve the technology in cooperation with PCC Synteza, as part of the company named BPA Procesy Jonitowe [BPA Ion-Exchange Processes]. More R&D works to improve and further develop the BPA process of technology have been continued since the year 2006 in the Institute for Engineering of Polymer Materials and Dyes in Toruń (IMPiB), in its Paints and Plastics Branch in Gliwice.

The method to obtain Bisphenol A is one of the most advanced processes of technology implemented in the chemical industry. The new generation technology is a considerable technological improvement compared with the earlier versions of the Polish process (i.e., the ion-exchange and the hybrid versions), resulting mainly from the use of the more effective, promoted catalyst in each of the two BPA synthesis units. The new BPA technology, now being offered as the “ADVANCE BPA” process, is based on the experience and commercial references obtained at PCC Synteza. In addition to the critical synthesis unit based on heterogenic catalysis and advanced both in terms of technology and engineering, the product manufacturing cycle comprises a number of additional unit operations and process streams, related to the separation and purification of the product with the BPA content of more than 99.9%. The general diagram in Fig. 1 shows the size and complexity of the BPA plant.

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A C E TO N

V309

N2

V201B

V323

4

V306A

V606V501V518V101B

V570V529 V508

SYNTEZA I SYNTEZA II KRYSTALIZACJA ROZKŁAD ADDUKTU

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WODA ODFENOLOWANA

POZOSTAŁOŚĆ

F E N O L

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REGENERACJA FENOLU OSUSZANIE FENOLU OSUSZANIE ŁUGÓW DESTYLACJA STRIPPINGOWA

EKSTRAKCJA FENOLU ROZKŁAD KATALITYCZNY REGENERACJA ACETONU

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2

3032

16

17

8

10

11

12

13

49

48

7

6

9

18

15

29

19

20

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34

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2324

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27

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2930

28 33

32

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46

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414243

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44

47

46a

46b

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44 50

5142

V526-2

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Fig. 1. Bisphenol A plant according to the offered technology – general diagram

The current process to obtain Bisphenol A is composed of 11 process unit and roughly 250 pieces of equipment, suitably designed to satisfy the requirements of the technology.

The ADVANCE BPA technology is a milestone, compared with the previous Bisphenol A processes. It has been proven in the 15,000 tpa BPA facility in PCC Synteza in Kędzierzyn-Koźle.

R&D works on the BPA process have been conducted in the Institute for Engineering of Polymer Materials and Dyes in Toruń (IMPiB) in cooperation with MEXEO (Project No. R05 007 02) as well as in the commercial BPA facility in PCC Synteza. The joint effort has provided the foundations of the new BPA process, now broadly protected with Polish, European, and international patents (PCT) and with the latest invention proposal Pat. P. 404819 of 27 July 2013), protecting the new-generation ADVANCE BPA process.

The results of the R&D works on the BPA production technology and the progress made in the key synthesis units I and II, are shown earlier in this information.

The economic effect of using less energy and raw materials, and obtaining a product with improved purity as the result of technological progress in the recent technology, as compared with its earlier versions, calculated for a 100,000 tpa BPA plant, is in the range of several to a dozen or so mln euros a year [Kiedik M., Kubica S., Chruściel A., Hreczuch W., "Projekt nowego procesu otrzymywania Bisfenolu A" [The proposed new process to obtain Bisphenol A ], Chemik nauka-technika-rynek, September 2013, in press], depending on the technological details used.

All major modification and improvement in the BPA process were proven in the 15,000 tpa facility in PCC Synteza by the end of 2009 and have a certified documentation of commercial references – this is of the key importance in evaluating the BPA process reliability.

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The technological improvements made the new-generation BPA technology more competitive, compared with other BPA processes, commercialized elsewhere in the world. The presently offered Bisphenol A technology has a closed research cycle, has successfully passed industrial tests and has a complete technical and economic documentation.

The R&D works in the IMPiB Institute were carried out by Dr Kiedik’s team with the use of a most advanced, microprocessor-controlled continuous lab-scale BPA plant in the presence of cation-exchanger catalysts. The lab plant was acquired for the purpose in the year 2007, as part of the R&D Project No. R05 007 02 of the Ministry of Science and Higher Education. The laboratory tests, in the scope referred to in this document, were contracted to and performed by MEXEO, Kędzierzyn-Koźle.

Information about the test results and the commercial reference plant performance are available in the internal reports of the IMPiB Institute, PCC Synteza and the cooperating entities (including MEXEO), and have been reported in the following sources:

1. Kiedik, M. Grzywa, E., Chruściel, A.Nowa energooszczędna technologia otrzymywania bisfenolu A [The new energy saving technology to obtain Bisphenol A],Przem. Chem. 2007, 86, No 1, 29

2. Kiedik, M., Chruściel, A., Sokołowski, A.: Wykorzystanie opracowanego modelu matematycznego węzła syntezy bisfenolu A do zwiększenia efektywności procesu produkcyjnego [The use of a developed mathematical model of the Bisphenol A synthesis unit to boost the production process efficiency]Przem. Chem. 2008, 87, No 9, 969,

3. Kiedik, M., Chruściel, A., Sokołowski, A.: Projekt nowej polskiej technologii otrzymywania Bisfenolu A o czystości poliwęglanowej w skali 50 tys. t/r. [The proposed new Polish technology to obtain 50,000 tpa of polycarbonate-grade Bisphenol A],Chemik 2009, No. 12, 484

4. Special Report: Bisphenol-A: A Techno-Commercial Profile, Part 1: Manufacture & Global Scenario, Chemical Weekly, 2009, September 1, 205 – 2011,

5. Kiedik, M., Kubica, S. Hreczuch, W., Basta, A.: Nowy proces wytwarzania bisfenolu A z zastosowaniem katalizatora promotorowanego [The new process to manufacture Bisphenol A using a promoted catalyst],Przem. Chem. 2012, 91, No 8, 1558

6. Kiedik, M., Kubica, S., Chruściel, A., Hreczuch, W.: Nowa generacja polskiej technologii otrzymywania Bisfenolu A [A new-generation Polish technology to obtain Bisphenol A] (in press),Chemik, in press – September 2013

in the patents and patent applications cited:

1. Kiedik, M. et al., European Patent Application No. EP08101300.5,A method to obtain polycarbonate-grade Bisphenol A, 2008,

2. Kiedik, M. et al., Polish Patent 212162, Sposób otrzymywania bisfenolu A o czystości poliwęglanowej [The method to obtain a polycarbonate-grade Bisphenol-A], 2010,

3. Kiedik, M. et al., Patent Application PCT/PL2011/000010,A method to obtain polycarbonate-grade Bisphenol A, 2011,

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4. Kiedik, M. et al., Polish Patent Application PL, No. P. 404819, 2013.,

and in the monograph:

1. Kiedik, M., Chruściel, A., Sokołowski, A., Nowe inicjatywy organizacyjne i technologiczne w zakresie chemii przemysłowej. Innowacja techniczna zamiast inwestycji. Bezinwestycyjne wdrożenie nowego energooszczędnego procesu otrzymywania Bisfenolu A w PCC Synteza” [monograph: New organizational and technological initiatives in industrial chemistry. Technological innovation as a replacement for investment. Implementation of a new energy-saving process to obtain Bisphenol A at PCC Synteza without having to invest”]Politechnika Opolska, ISBN: 978-83-60691-45-8, pp. 41–53. 2009

Moreover, information about the innovative process to obtain BPA was disclosed in the years 2009 and 2012, during the 6th and 7th Chemical Technology Congresses as a section paper and oral communication:

1. Kiedik, M., A. Sokołowski, A. Chruściel, „Proces Chemwik BIS – nowa energooszczędna technologia otrzymywania bisfenolu A o czystości poliwęglanowej” [The Chemwik BIS Process – a new energy-saving technology to obtain a polycarbonate-grade Bisphenol A],

2. Kiedik, M., S. Kubica, A. Chruściel, W. Hreczuch, „Projekt nowego procesu otrzymywania bisfenolu A” [The proposed new process to obtain Bisphenol A]

and in many other scientific conferences and seminars in Poland and abroad, including the following:

1. Kiedik, M., „Proces Chemwik BIS – nowa eksportowa technologia otrzymywania bisfenolu A o czystości poliwęglanowej”, [The Chemwik BIS process – a new export technology to obtain polycarbonate-grade Bisphenol A] Sci-Tech Conference: The Chemical Industry – Challenges and Barriers, Ustroń-Jaszowiec, presentation on 28.11.2008,

2. Kiedik, M., A.Chruściel, „The New Energy Saving Technology of Polycarbonate Grade Bisphenol A”,international conference: Advances in Plastics Technology APT’09 in Katowice, presentation on 03.11.2009,

3. Kiedik, M., „Projekt nowej technologii otrzymywania bisfenolu A o czystości poliwęglanowej”, [The proposed new technology to obtain polycarbonate-grade Bisphenol A] Sci-Tech Conference: The Chemical Industry – Challenges and Barriers, Ustroń-Jaszowiec, presentation on 27.11.2009,

4. Kiedik, M., A.Chruściel, „The new energy saving technology of polycarbonate-grade Bisphenol A”, seminar of the Polish-Chinese working group of the ADVANCE International Consortium for the Research, Development and Commercialization of Advanced Technology, Kędzierzyn-Koźle, 04.10.2009,

5. Kiedik, M., A. Sokołowski, Poszukiwanie alternatywnych sposobów finansowania rozwoju i komercjalizacji wyników badań na przykładzie nowej technologii otrzymywania bisfenolu A”,

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[In search of alternative ways to finance the development and commercialization of research findings, using the example of the new technology to obtain Bisphenol A”,]seminar: Innovative Solutions in the Chemical Industry, Opole, presentation on 18.11.2010,

6. Kiedik, M., „New process to obtain Bisphenol A” (film),international conference: Advances in Plastics Technology APT’11 in Katowice, presentation on 15.11.2011,

7. Kiedik M.,Lectures for the students of the Silesian University of Technology in the years 2008 - 2012.

According to the commercial references obtained, it has been proved that the innovative BPA technology is now competitive with those of the major global players in the chemical industry. Leading global manufacturers of BPA are usually not interested in selling their licenses, therefore, the new Polish ADVANCE BPA process of technology offers an opportunity to renew its export. The new ADVANCE BPA process of technology may also serve as an implementation basis for the project to build a facility in Poland as part of a production complex to produce polycarbonates, such as phenol, acetone, and bisphenol A.

In the years 2009/2010, the BPA plant in PCC Synteza S.A. was stopped because there was a slump in the economy caused by the global economic crisis, the plant capacity was too small and uneconomic for the current standards in the BPA business (even after its intensification to 15,000 tpa) and there were no direct links leading to the suppliers of raw materials and product processors who make plastics.

Before the BPA plant in PCC Synteza was stopped in 2010, the BPA process running in the reference plant had been documented as part of the Patent Plus project of the Ministry of Science and Higher Education: the major equipment and devices of the production plant were visualized and their operation was shown in the form of a film and a graphical animation. The presentations are available in the Polish, English, and Chinese languages on a CD (Fig. 2).

Fig. 2. Visualization of the major equipment and devices for the BPA technologyand a multimedia presentation of their operation

The advanced nature of the proposed solutions as compared with state-of the art in the area of Bisphenol A production technology

The use of essential and unique technological solutions in the ADVANCE BPA process, which were developed by the IMPiB Institute in cooperation with PCC Synteza and MEXEO, combined with the

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use of only the promoted catalysts in the BPA synthesis created conditions for making the BPA production more cost-effective by lowering the consumption of energy and raw materials. The basic design and the technical offer for the ADVANCE BPA process include the new method to operate the BPA synthesis in the presence of the promoted catalyst in two independent reaction units which are composed of reactors with a modified, improved design which enables an optimum contact of the reaction mixture having the desirable composition with the active catalyst as well as an effective heat transfer in the exothermal reaction. Owing to the technological modifications, mainly in the synthesis unit, and the use of the new catalyst which contains a chemically bound promoter (2,2-dimethyl-1,3-thiazolidine), the BPA concentration obtained in the reaction was increased to much higher levels (∆ BPA from 10% to more than 15%); consequently, much less energy was used for the separation and purification of the final product. The guaranteed quality of the resulting product complies with all the applicable standards in the international market.

As an option, in the ADVANCE BPA technology it is possible to replace the second step of suspension crystallization of the adduct with fractional crystallization of bisphenol A; this provides a final product with top levels of purity as well as high thermal stability.

The innovation of the proposed process, as compared with state-of-the-art solutions in the area is confirmed in the Polish patent: No. 212162 (2010) „A method to obtain a polycarbonate grade Bisphenol A” and, globally, with two international invention proposals, which include: The European Patent EP 2090562 A1 (2008) “A method to obtain polycarbonate-grade bisphenol A” and the international Patent Application No. PCT/PL2011/000010 (2011) “A method to obtain polycarbonate-grade bisphenol A” and the latest international Patent Application No. 404819 (July 2013). Moreover, the technology is the only commercially proven Polish BPA process which currently satisfies the requirements of international competition and is available for licensing.

The proposed new-generation process of technology to obtain BPA is essentially different from those Polish solutions which were known earlier, the ion-exchange process and the hybrid process, as well as from other competitive processes. The members of the ADVANCE BPA Consortium (IMPiB and MEXEO) as well as PCC Synteza (the owner of the reference plant) are the co-assignees of the invention proposals referred to earlier in this document. The ADVANCE BPA technology has the advantage that product quality is high and the consumption of both energy and raw materials is low (Table 1).

Table 1. Essential parameters of the BPA process of technology

Parameter

Purity of

BPA,%, min

Color,APHA,

max

Consumption of acetone,

t/t, max

Consumption of phenol,t/t, max

Increase in BPA

concentration in the

reaction**, %

Consumption of energy**,

GJ/t, max

The earlier, ion-exchange

process99.9 5 0.275 0.860 10 12.5

The new, „ADVANCE BPA” process

99.9399.99* 5 0.265 0.836 15 7

* For the variant with fractional crystallization, ** Proprietary data, not published

In economic terms, reducing phenol consumption by 24 kg/t in a 100,000 tpa plant is expected to generate a result of EUR 3.6 mln, given the current market prices.

Assuming the average price of EUR 2.5 per 1 GJ, the difference in energy consumption per unit, which is 5.5 GJ/t BPA, gives another EUR 1.4 mln per year. Moreover, a lower increase in BPA concentration (∆ BPA) in the synthesis unit entails a corresponding increase in energy consumption

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per unit (GJ/t) for product separation. Taking into account the above-mentioned differences, plus the associated plant operation costs, the resulting added economic effect obtained in the ADVANCE BPA technology per year may safely be assessed at a minimum of EUR 5 mln (50 EUR/t BPA).

The new, energy-saving BPA process offered by the ADVANCE BPA Consortium satisfies the most severe criteria of competitiveness.

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THE NEW BISPHENOL-A PRODUCTION TECHNOLOGY

The ADVANCE BPA Consortium has developed a NEW BISPHENOL-A PRODUCTION TECHNOLOGY which is protected with a European Patent, an international PCT Patent Application, and a most recent Polish Patent Application.

MEXEO as the Leader of the ADVANCE BPA Consortium and based on authorization from all the co-assignees to the patents covering the new technology referred to as the ADVANCE BPA Process offers the license, know-how, documentation and commercialization services, including technical supervision, supplies of the key equipment and the catalysts.

Information about the ADVANCE BPA process is included in the following:

• process description (Link 1), • film presentation (Link 2).

Those interested in the commercialization are invited to cooperate with us.

Contact: Dr Maciej Kiedik – the main author and representative of the other originators of the

technologyMEXEO, ul. Energetyków 9, 47-225 Kędzierzyn-Koźle

Tel. +48-77 4873810; E-mail: mexeo@mexeo.pl

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XME EOR

Consortium Partner:Institute for Engineering of

Polymer Materials and Dyes in Toruń

Consortium Leader:MEXEO

Kędzierzyn-Koźle