MXPA05001408A

MXPA05001408A - Process for the production of bisphenol-a.

Info

Publication number: MXPA05001408A
Application number: MXPA05001408A
Authority: MX
Inventors: Chen-Chou Chang
Original assignee: Calgon Carbon Corp
Priority date: 2002-08-06
Filing date: 2003-08-06
Publication date: 2005-04-11
Also published as: WO2004013075A1; IL166631A0; KR20050062527A; CA2494850A1; JP2005534698A; CN1684932A; EP1527037A1; TW200404767A; AU2003258130A1

Abstract

The invention provides a process for the continuous production of bisphenol-A by continuously reacting phenol using an acid catalyst resin and continuously or essentially continuously removing water from the system. Continuous removal of water allows for increased catalytic activity of the resin and therefore improved productivity. Removal is facilitated by conducting the process in a carousel simulated moving bed device. Process efficiency is further enhanced by conducting the process in a device configured to have a combination of series, parallel or reverse flows which are optionally arranged so the process results in higher yield and lower impurities.

Description

PROCESS FOR. THE PRODUCTION OF BISPHENOL-A DESCRIPTION Background and field of the invention This invention relates to a process for preparing bisphenol-A, by continuously reacting phenol with acetone using a heterogeneous acid catalyst resin and continuously removing the water from the system.

Bisphenol-A ("BPA") is an important raw material for the production of polycarbonate plastics and epoxy resins. It is most often produced by acid catalyzed condensation of phenol with acetone by means of the following reaction: 2 Phenol + Acetone? Bisphenol-A + Water Although a homogeneous acid catalyst such as hydrogen chloride has been used for many years, heterogeneous catalyst systems have become the most popular technique for producing BPA. Most heterogeneous catalysts are sulfonated polystyrene ion exchange resins. These catalysts provide a variety of advantages. Are not 1 corrosive and are easily separated from the reaction mixture. The catalysts work with continuous processes such as continuous fixed bed technology using a fixed bed reactor. For example, a mixture of phenol / acetone is continuously fed through a bed of a heterogeneous ion exchange resin catalyst and, in steady state, the water is constantly generated from the reaction and removed with the continuous flow of the phenol through of the resin bed. The desired product of BPA is then collected by crystallization and further purified by recrystallization. A disadvantage of this technology is that the water by-product significantly reduces the activity of the resin catalyst. This is because water strongly hydrates the acid groups, thus competing for these sites with the reactants. As the amount of water fixed by adsorption increases at the catalytic sites, the activity of the resin decreases. Without some means for the removal of water, the catalytic activity of the resin becomes slow unacceptable. As a result of this inhibition, BPA reactors may require higher resin volumes adding cost to the BPA plant. Cocatalysts can be used to increase the reaction rate, adding cost to the catalyst. As well 2 Higher temperatures can be used to achieve the desired productivity, thus leading to greater by-product formation. Researchers have long tried to solve the problem of water inhibition by developing reaction systems that continuously remove the reaction water from the reaction zone. U.S. Patent No. 5,087,767 describes a reaction system in which pervaporation is used to continuously remove water from the reactor. The process uses a membrane (organic or ceramic) permeable to water but not acetone, phenol or BPA. More recently, U.S. Patent No. 5,679,312 describes a reactive / extraction process to continuously extract water from a BPA reactor. The reactor consists of a multi-stage distillation column. One of the disadvantages of this technology is that it requires the use of a stream of nitrogen to extract the water from the reaction liquid. The traditional simulated moving bed ("SMB") process is one where a plurality of beds packed with solid media is used to perform a continuous separation. The beds are connected in series circuit with unidirectional fluid flow through the system. 3 Each bed is equipped with inlet and outlet ports that are switched on and off to create a simulated movement of the solid. The liquid flow combined with the movement of simulated countercurrent solids produces the separation of the components having various affinities for the solid media. If a reaction is added to the system, a continuous reaction / separation system is created. For a general review of SMB technology, see Preparative and Production Scale Chromatography, Ganetsos, G., Barker, P. E., Eds.; Chromatographic Science Series Vol.61; Marcel Dekker Inc .: New York, 1993; Chapters 12-13. Recently, a group of researchers has investigated the potential to use a device to perform the reaction of ??? and is described in The Simulated Moving-Bed Reactor for Production of Bisphenol A, Kawase, M .; Inoue, Y .; Araki, K .; Hashimoto,.; Catalysis Today, Vol. 48, p. 199-209 (1999). Based on laboratory kinetics and adsorption data they performed a numerical simulation of an SMB process. Although they assumed that SMB could be convenient for BPA production, no experiment was conducted to confirm the predictions of the simulation. There is no mention regarding the generation of impurities or the advantages that can be achieved 4 by using non-traditional SMB flow configurations. Accordingly, it is an object of one embodiment of the present invention to provide an efficient process for the production of BPA. Water is continuously removed to reduce the adverse effect of water on the reaction process and overcomes the disadvantages of water inhibition including its requirements for high reaction temperatures, large reactor volumes or the use of cocatalysts. In another embodiment, it is an object of the invention to provide a process for producing BPA that can be used on a commercial scale.

BRIEF DESCRIPTION OF THE INVENTION In general, the present invention provides a process for the continuous production of bisphenol-A which comprises reacting the phenol with acetone using an acidic catalyst resin and removing the water from the reaction of the process. Simultaneously or sequentially as the phenol reacts with the acetone, the water is removed continuously or almost continuously with a continuous reaction / separation device to allow a higher catalytic activity of the resin. The reaction can be continuous for as long as the reagent is present. 5 The device preferably contains a plurality of beds or columns containing the acidic catalyst resin and are connected movably in series or parallel to another column, i.e., connected in a series configuration, in a carousel, to simulate a flow of resin. Preferably, the high performance simulated carousel moving bed device ("HPC-SMB") available from Calgon Carbon Corporation is used. The columns are arranged to provide appropriate zones for the stages of elusion, enrichment and reaction of the process. The acetone is fed in two or more columns in the reaction zone. In the zone of water elution, the adsorbed water is removed from the resin with either phenol or another solvent. If a solvent with the exception of phenol is used to remove water from the resin, it will have to be regenerated and recycled to the elution zone. If phenol is used, enough phenol is added to the elution zone to dehydrate the resin and to provide enough excess phenol for the reaction zone. Downstream of the reaction zone, the crude BPA product as well as the excess phenol are extracted from the process. A portion of the extracted product can optionally be passed to a recharge zone to recover the phenol from the resin bed for reuse. 6 In one embodiment, the process is performed using columns connected in a serial flow configuration that has a unidirectional liquid flow through the system. In one embodiment, the process uses a SMB carousel reactor. Each column is equipped with inlet and outlet ports that are switched on and off to create a simulated movement of the catalytic acid resin. The acid catalyst resin is a heterogeneous catalyst. Conducting the process in a series configuration coincides with the operation of the traditional SMB process and exceeds the performance of a continuous fixed bed reactor because the continuous removal of water provides higher productivity. Another mode of the process uses unique flow configurations with an SMB carousel to achieve an advantageous result with higher production and lower impurities. The product water is simultaneously removed from the reaction by the simulated countercurrent movement of the resin bed against the flow of the reaction mixture. Particularly, HPC-SMB is configured to provide a flow configuration that is significantly different from traditional SMB flow configurations. Alternate flow configurations such as parallel and reverse flow can be used advantageously to increase productivity and reduce the formation of 7 byproducts. In one example, the process uses a parallel flow to allow dilution of the reagent, in such a way as to reduce the formation of by-products that result from the reaction of the reagent with itself. Reverse current (upflow) prevents buildup of pressure in the unit allowing the resin to expand rather than just swell in place and restrict fluid flow. This leads to greater productivity by reducing downtime. In one example, the columns contain a solid or a mixture of solids that act as a catalyst for the desired reaction and an adsorbent or separation medium to remove the reaction product or other desired components. There is a wide variety of solid catalysts and adsorbents available. These materials generally applied for catalysis and / or separation include, but are not limited to, activated carbon, silicone gels, aluminas, zeolites, zirconias, titanias, silicates, diatomaceous earths, and ion exchange resins. In one embodiment, a solid is used when it sufficiently performs the catalytic and adsorbent functions. In an example that uses two or more solids, one performs the catalytic function while the other performs the separation function. These materials are chosen to provide a better reaction and separation from a single material. Also, it is possible to select a solid resin that acts only as a separation medium while the catalyst is not part of the solid phase but preferably dissolves in the liquid phase. In one embodiment to produce BPA, the catalyst and the solid adsorbent is an ion exchange resin. In one example of the process of the invention, one or more eluents are used to selectively desorb the products, by-products or contaminant from the bed reaction using an isocratic elution or a gradient elution process. The eluent comprises or contains a liquid capable of displacing such product, by-product, or contaminant from the reaction of the adsorption bed. Examples of eluents include, for example, alcohols, ketones, esters, aliphatic hydrocarbons, aromatic hydrocarbons, amides, nitriles, water, or buffered solutions. Mixtures of eluents can also be used. The preferred eluent for BPA is phenol. Other features, aspects and advantages of the present invention will be better understood or will be apparent from a reading of the description and the following detailed examples of the invention and the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a schematic representation of the current invention using a traditional series configuration. Figure 2 shows a schematic representation of one embodiment of the current invention combining a series configuration with a parallel flow configuration using a reverse flow mode.

Description of the examples of the invention The present invention provides a process for the continuous production of BPn which comprises reacting phenol with acetone using an acidic catalyst resin and continuously or almost continuously removing the water from the reaction. This reaction and separation process is carried out in multiple columns comprising a solid or a mixture of solids connected in series, parallel or combination of such configurations. The reaction / separation can occur concurrently or sequentially. Each column can be operated independently with a liquid flow direction that runs from the top of the column to the bottom of the column or from the bottom of the column to the top of the column. 10 column (reverse current). A more detailed description of the variety of flow configurations can be found in the Applicant's application entitled High Performance Continuous Reaction / Separation Process Using A Continuous Liquid-Solid Contactor (Attorney Document No. 02-254 CIP CIP) presents simultaneously with the present. The columns move or rotate to simulate a medium flow. In one embodiment, the process uses acidic catalyst resin from Amberlyst 131. An eluent, phenol, is introduced into the inlet 15, as shown in Figure 1, in order to desorb water from the resin. A portion of the extract product at outlet 17 is pumped through the reaction zone to provide fluid flow in this part of the unit. The acetone is fed into the system at the inlet 11. A higher feed rate results in higher productivity with lower purity and a lower feed rate resulting in lower levels of impurities with lower productivity. In any given case, the level of acetone feed is adjusted to meet the needs of the producer. In this case, the feed level of the acetone is adjusted to give a molar ratio of phenol to acetone in the range of 6: 1 to 20: 1. In other examples, the relationship is in the range of eleven approximately 8: 1-15: 1 or 12: 1. The process is carried out in the temperature ranges from 50 ° C to 100 ° C. Other examples perform the processes in the range of 60 ° C-90 ° C or 70 ° C. In one embodiment, the invention is used in conjunction with a device that makes continuous liquid-solid contact. Devices that make continuous liquid-solid contact generally endeavor to move a liquid phase in countercurrent contact with a solid phase through various means. A general review of the devices can be found in the patent of the United States of America No. 5, 676,826 which is incorporated by reference. Although any of these devices may be used with the present invention, preferred devices include those described in United States of America Nos. 5,676,826; 4,808,317; 4,764,276; 4,522,726 and 6,431,202. Patent No. 6, 431, 202 is incorporated by reference. In one example, the process is carried out on a device packed with media that moves by indexing the columns so that it occurs so quickly that it is considered continuous. In one example, the process uses a device that has a control valve to conveniently use several beds, instead of many systems 12 traditional SMBs that employ several control valves. The lower examples demonstrate the process to continuously produce BPA by condensation of acetone with phenol. The skilled person would appreciate that these are described only for demonstration purposes and various modifications can be used, which are within the scope of the invention.

Example 1. Fixed bed continuous column A column that is 2.5 cm in diameter and 200 cm in length was packed with 522 grams (dry weight) of a strong acid ion exchange resin. Specifically, Amberlyst 131 from Rohm & Haas. Such resins are also commercially available from Dow, Bayer, and Mitsubishi, among others. The column was fed with a molar ratio of 12: 1 phenol / acetone at a rate of 1.84 ml / min. The temperature was kept constant at 70 ° C. In steady state, BPA was continuously produced at an acetone conversion level of 81%. The BPA content was determined by high performance liquid chromatography (HPLC). BPA occurred at a rate of 285 mg / min. The results are shown in table 1. 13 Example 2. Complete series flow of SMB of high performance carousel.

The following example illustrates one of the advantages of using a traditional SMB series flow configuration with the current invention on the continuous solid bed system of Example 1. In particular, HPC-SMB from Calgon Carbon Corporation was used. The process and the advantages are not limited to such an apparatus. Using the HPC-SMB packed with Amberlyst 131 resin from Rohm & Haas, the phenol was reacted with acetone to produce BPñ. In this example, the unit contains a set of 20 columns that are each 1 cm in diameter and 30 cm in length. Each column contained 11.8 grams (dry weight) of resin Amberlyst 131. As illustrated in figure 1, the zone of elusion (Zone IV) contains 6 columns, the zone of enrichment (Zone III) contains 2 columns and the reaction zone (Zone II) contains 12 columns. The unit is contained in an enclosure maintained at a constant temperature of 70 ° C. Phenosl was fed into the elution zone at inlet 15 at a rate of 13.00 ml / min. The phenol was moved in the enrichment zone at a rate of 2.25 ml / min and was withdrawn at outlet 17. The acetone was fed at a rate of 0.150 ml / min in the reaction zone at the feed inlet 11 where a 14 Condensation reaction with phenol occurs to form BPA. The strongly adsorbed water is continuously transported out of the reaction zone and into a water selection zone by a countercurrent movement of the resin catalyst against the flow of reactants. In the zone of water elution, the water fixed by adsorption is removed from the resin with the phenol at outlet 17. Ample replacement phenol is added at the inlet 15 to the elution zone to dehydrate the resin and to provide sufficient excess of phenol for the reaction zone. At the end of the reaction zone, the crude BPA product as well as the excess phenol were extracted from the process at outlet 19. A portion of the extracted product can optionally be passed to a recharge zone to recover some of the phenol for reuse. This example illustrates the improvement in productivity. The compositions were determined using high performance liquid chromatography (HPLC). Table 1 shows a comparison of the results obtained from this example of the serial flow configuration where productivity tripled. fifteen Table 1 Example 3. Partial parallel flow SMB of high performance carousel The following example illustrates only one of the advantages of using a non-SMB flow configuration of the present invention with a liquid-solid contact system. This example uses an enclosed unit that contains the same number and volume of columns arranged in similar zones as used in example 2. The concentrations, feed rates, resin and temperature are also the same as in example 2. According to 16 as illustrated in figure 2, for this example the first 4 columns in the reaction zone are connected in a parallel flow configuration and the remaining columns 8 are arranged with the serial flow configuration. Parallel flow columns also work in reverse current (upflow) mode. This allows a better distribution of reagent and products which increases the production of the BPA product while reducing the level of impurities. The compositions of the product were determined using high performance liquid chromatography (HPLC). Table 2 shows a comparison of the results obtained from this example of combining serial flow and parallel flow / reverse flow (partial) configurations.

Table 2 In contrast to this example 3, the use of the traditional SMB flow configuration requires that 17 all the columns are connected in a serial flow configuration, as shown in figure 1. In one embodiment, the current process, as illustrated in example 3, combines configurations of serial, parallel and inverse flow together in a unit in the reaction zone to advantageously improve the production of BPA, to reduce impurities and to prevent 1 to build up pressure in the columns. It is also not limited by the number of columns used in an area and the zones are established based on the objectives of the process. While the aforementioned has been arranged in detail, the examples and methods are presented for clarification and not for limitation. It will be appreciated from the description of the invention that a person with ordinary skill in the art can make various modifications and combinations of elements of the invention, variations, equivalents or improvements thereto and the same are within the scope of the invention as defined in the following claims. 18

Claims

1. A process for the continuous production of bisphenol-A, characterized in that it comprises continuously reacting phenol with acetone using an acidic catalyst resin to form BPA and water and continuously removing this water from the reaction.

2. The process according to claim 1, characterized in that an acid catalytic resin is provided in a simulated moving bed reactor of carousel.

3. The process according to claim 1, characterized in that the acidic catalyst resin is an ion exchange resin.

4. The process according to claim 1, further comprising the step of introducing an eluent into an elution zone of the reaction zone.

5. The process according to claim 4, characterized in that the eluent is phenol.

6. The process according to claim 2, characterized in that the molar ratio of phenol to acetone is in the range of about 6: 1 - 20: 1. 19

7. The process according to claim 2, characterized in that the temperature of the process is in the range of approximately 50-100 ° C.

8. The process according to claim 2, characterized in that the beds in the reactor are connected in series to have a unidirectional fluid flow.

9. A process according to claim 2, characterized in that at least one bed in the reactor is configured to have reverse flow or to provide a fluid flow direction opposite to the medium flow or to the top of the column or both . twenty