WO2004013075A1 - Procede de production de bisphenol-a - Google Patents

Procede de production de bisphenol-a Download PDF

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Publication number
WO2004013075A1
WO2004013075A1 PCT/US2003/024674 US0324674W WO2004013075A1 WO 2004013075 A1 WO2004013075 A1 WO 2004013075A1 US 0324674 W US0324674 W US 0324674W WO 2004013075 A1 WO2004013075 A1 WO 2004013075A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
resin
phenol
set forth
water
Prior art date
Application number
PCT/US2003/024674
Other languages
English (en)
Inventor
Chen-Chou Chiang
David L. Fair
Original Assignee
Calgon Carbon Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US10/213,580 external-priority patent/US20040031757A1/en
Application filed by Calgon Carbon Corporation filed Critical Calgon Carbon Corporation
Priority to AU2003258130A priority Critical patent/AU2003258130A1/en
Priority to CA002494850A priority patent/CA2494850A1/fr
Priority to JP2004526074A priority patent/JP2005534698A/ja
Priority to MXPA05001408A priority patent/MXPA05001408A/es
Priority to EP03767265A priority patent/EP1527037A1/fr
Publication of WO2004013075A1 publication Critical patent/WO2004013075A1/fr
Priority to IL16663105A priority patent/IL166631A0/xx

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
    • B01D15/1814—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns recycling of the fraction to be distributed
    • B01D15/1857—Reactive simulated moving beds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
    • B01D15/1864—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns using two or more columns
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2215/00—Separating processes involving the treatment of liquids with adsorbents
    • B01D2215/02—Separating processes involving the treatment of liquids with adsorbents with moving adsorbents
    • B01D2215/023—Simulated moving beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2215/00—Separating processes involving the treatment of liquids with adsorbents
    • B01D2215/02—Separating processes involving the treatment of liquids with adsorbents with moving adsorbents
    • B01D2215/023—Simulated moving beds
    • B01D2215/028—Co-current flow

Definitions

  • 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 water from the system.
  • BPA Bisphenol-A
  • heterogeneous catalyst systems have become the more popular technique for producing BPA.
  • Most of the heterogeneous catalysts are sulfonated polystyrene ion exchange resins. These catalysts provide a number of advantages. They are non-corrosive and easily separated from the reaction mixture.
  • the catalysts work with continuous processes such as continuous fixed bed technology which uses a fixed bed reactor. For example, a phenol/acetone mixture is continuously fed through a bed of a heterogeneous catalyst ion exchange resin and, at steady state, water is constantly generated from the reaction and removed with the continuous flow of phenol through the resin bed. The desired BPA product is then collected by crystallization and further purified by recrystallization.
  • a well-known drawback of this technology is that the by-product water greatly reduces the activity of the resin catalyst. This is because the water strongly hydrates the acid groups, thus competing for these sites with the reactants. As the amount of water adsorbed on the catalytic sites increases the resin activity decreases. Without some means for removal of the water, the activity of the resin catalyst becomes unacceptably slow. As a result of this inhibition, BPA reactors can require higher resin volumes adding to the cost of the BPA plant. Co-catalysts can be used to' boost the reaction rate, adding to the catalyst cost. Higher temperatures can be used to achieve the desired productivity thus leading to increased by-product formation.
  • 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 utilizes a membrane (organic or ceramic) permeable to water but not to acetone, phenol, and BPA. More recently, U.S. Patent No. 5,679,312 describes a reactive/stripping process for continuously stripping water from a BPA reactor. The reactor consists of a multi-stage distillation column. One of the drawbacks to this technology is that it requires the use of a nitrogen stream to strip the water from the reaction liquid.
  • the traditional simulated moving bed (“SMB”) process is one where a plurality of beds packed with solid media are used to carry out a continuous separation.
  • the beds are connected endlessly in series with a unidirectional fluid flow through the system.
  • Each bed is fitted 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 simulated counter current solid movement results in the separation of components that have different affinities for the solid media. If a reaction is added to the system, a continuous reaction/separation system is created.
  • water is continuously drawn off to reduce the adverse affects of water on the process reaction, and overcome disadvantages of water inhibition •including its requirements for high reaction temperatures, large reactor volumes or use of co- catalysts.
  • the present invention provides a process for the continuous production of bisphenol-A that comprises reacting phenol with acetone using an acid * catalyst resin, and removing water from the process reaction. Simultaneously or sequentially as the phenol reacts with acetone, the water is removed continuously or essentially continuously using a continuous reaction/separation device to allow for higher catalytic activity of the resin.
  • the reaction may be continuous for so long as reactant is present.
  • the device preferably contains a plurality of beds or columns containing acid catalyst resin and being moveably connected serially or parallel to another column, i.e., connected in a series configuration, in a carousel, to simulate a resin flow.
  • the High Performance Carousel Simulated Moving Bed (“HPC-SMB”) device available from Calgon Carbon Corporation is used.
  • the columns are arranged to provide appropriate zones for elution, enrichment and reaction stages of the process.
  • the acetone is fed into two or more columns in the reaction zone.
  • adsorbed water is removed from the resin with either phenol or another solvent. If a solvent other than 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 makeup phenol is added to the elution zone to both dehydrate the resin and to provide enough excess phenol for the reaction zone.
  • the crude BPA product as well as excess phenol are extracted from the process. A portion of the extracted product can optionally be passed to a reload zone to recover phenol from the resin bed for reuse.
  • the process is conducted using columns connected in a series flow configuration having a unidirectional fluid flow through the system.
  • the process uses a carousel SMB reactor. Each column is fitted with inlet and outlet ports that are switched on and off to create a simulated movement of the acid catalyst resin.
  • the acid catalyst resin is a heterogeneous catalyst. Conducting the process in a series configuration matches process performance of traditional SMB and exceeds the performance of a continuous fixed bed reactor because continuous removal of the water yields higher productivity.
  • Another embodiment of the process employs unique flow configurations with a carousel SMB to advantageously result in higher yield 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.
  • the HPC-SMB is configured to provide a flow configuration that is significantly different from the traditional SMB.
  • Alternative flow configurations such as parallel flow and reverse flow can be advantageously use to increase productivity and reduce the formation of by-products.
  • the process employs a parallel flow to allow for dilution of the reactant, thereby reducing the formation of by-products that result from the reaction of the reactant with itself.
  • the reverse flow prevents pressure build up in the unit by allowing the resin to expand rather than simply swell in place and constrict the fluid flow. This leads to increased productivity by reducing down time.
  • the columns contain a solid or mixture of solids that act as a catalyst for the desired reaction and an adsorbent or separation media for removing the reaction product or other desired components.
  • solid catalysts and adsorbents available. These materials generally applied for catalysis and/or separation include, but are not limited to, activated carbon, silica gels, aluminas, zeolites, zirconias, titanias, silicates, diatomaceous earths, and ion exchange resins.
  • a solid is used where it sufficiently performs both the catalytic and adsorbent functions. • In an example using two or more solids, one performs the catalytic function while the other performs the separation function.
  • the solid catalyst and adsorbent is an ion exchange resin.
  • one or more eluents are used to selectively desorb the reaction products, byproducts, or contaminant from the bed using an isocratic elution or a gradient elution process.
  • the eluent comprises or contains a liquid capable of displacing such reaction product, byproduct, or contaminant from the adsorption bed.
  • eluents include, for example, alcohols, ketones, esters, aliphatic hydrocarbons, aromatic hydrocarbons, amides, nitriles, water, or buffered solutions. Mixtures of eluents may also be used.
  • the preferred eluent for BPA is phenol. .
  • Figure 1 shows a schematic representation of the present invention using a traditional series configuration.
  • Figure 2 shows a schematic representation of an embodiment of the present invention that combines a series flow configuration with a parallel flow configuration that uses a reverse flow mode.
  • the present invention provides a process for the continuous production of BPA comprising reacting phenol with acetone using an acid catalyst resin and continuously or essentially continuously removing water from the reaction.
  • This reaction and separation process is conducted in multiple columns comprised of a solid or mixture of solids connected in series, parallel, or combination of such configurations.
  • the reaction separation can occur concurrently or sequentially.
  • Each column can be independently operated 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 (reverse flow).
  • a more detailed description of the variety of flow configurations can be found in applicants' application entitled High Performance Continuous Reaction/Separation Process Using A Continuous Liquid-Solid Contactor (Attorney Docket No. 02-254 CIP C ⁇ P) that is being filed simultaneously herewith.
  • the columns move or rotate to simulate, a media flow.
  • the process uses Amberlyst 131 acid catalyst resin.
  • An eluent, phenol is introduced at inlet 15, as shown in figure 1, for the purpose of desorbing water from the resin.
  • A. portion of the extract product at outlet 17 is pumped through the reaction zone to provide the fluid flow in this part of the unit.
  • the acetone is fed into the system at inlet 11.
  • a higher feed rate results in higher productivity with lower purity and a lower feed rate results in lower levels of impurities with lower productivity.
  • the acetone feed rate is adjusted to meet the needs of the producer.
  • the acetone feed rate is adjusted to give a mole ratio of phenol to acetone in the range of 6:1 to 20: 1.
  • the ratio is in the range of about 8:1 - 15:1, or at 12:1.
  • the process is conducted at temperature ranges from 50°C to 100°C.
  • Other examples conduct the process in the range of 60°C-90°C, or at 70°C.
  • the invention is used in combination with a continuous liquid-solid contacting device.
  • Continuous liquid-solid contacting devices generally strive to move a liquid phase in counter current contact with a solid phase through various means.
  • a general review of the devices can be found in U.S. Patent No. 5,676,826, which is incorporated herein by reference. Although any of these devices can be used with the present invention, preferred devices include those disclosed in U.S. Patent N S; 5,676,826; 4,808,317; 4,764,276; 4,522,726 and 6,431,202.
  • U.S. Patent No. 6,431,202 is incorporated herein by reference.
  • the process is conducted in a device packed with media moving by indexing of the columns in a rrfanner that takes place so quickly as to be considered continuous.
  • the process utilizes a device having one control valve to conveniently utilize multiple beds, rather than many traditional SMB systems that employ multiple valve control.
  • Example 2 illustrates one of the benefits of using a traditional SMB series flow configuration with the present invention over the continuous fixed bed system of Example 1.
  • Calgon Carbon Corporation's HPC-SMB was used. The process and advantages are not limited to such apparatus.
  • HPC-SMB packed with Amberlyst 131 resin from Rohm & Haas phenol was reacted with acetone to produce BPA.
  • the unit contains a set of 20 columns that are each 1.1 cm in diameter and 30 cm in length. Each column contained 11.8 grams (dry weight) of Amberiyst 131 resin. As illustrated in Figure 1, the elution zone (Zone IV) contains 6 columns, the enrichment zone (Zone L T) 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. Phenol was fed into the elution zone at inlet 15 at a rate of 13.00 mls/min. The phenol moves into the enrichment zone at a rate of 2.25 mls/min which was drawn off at outlet 17.
  • the acetone is fed at a rate of 0.150 mls/min to the reaction zone at feed inlet 11 where a condensation reaction with phenol occurs to form BPA.
  • the strongly adsorbed water is continuously carried out of the reaction zone and into a water election zone by a counter current movement of the resin catalyst against the flow of reactants.
  • adsorbed water is removed from the resin with the phenol at outlet 17.
  • Enough makeup phenol is added at intake 15 to the elution zone to both dehydrate the resin and to provide enough excess phenol for the reaction zone.
  • the crude BPA product as well as excess phenol were extracted from the process at outlet 19.
  • a portion of the extracted product can optionally be passed to a reload zone to recover some of the phenol for re-use. This example illustrates the improvement in productivity.
  • Table 1 shows a comparison of the results obtained from this example of the series flow configuration where the productivity was increased three-fold.
  • Example 2 illustrates just one of the benefits of using a non-SMB flow configuration of the present invention with a fluid-solid contacting system.
  • This example uses an enclosed unit containing the same number and volume of columns arranged in similar zones as used in Example 2. The concentrations, feed rates, resin, and temperature were also the same as in Example 2.
  • the first 4 columns in the reaction zone are connected in a parallel flow configuration and the remaining 8 columns are arranged with the series flow configuration.
  • the parallel flow columns are also run in the reverse flow - mode (up-flow). This allows for an improved distribution of reactants and products that increases the yield of the BPA product while reducing the level- of impurities.
  • the product compositions were determined using high performance liquid chromatography (HPLC). Table 2 shows a comparison of the results obtained from this example of combining series flow and (partial) parallel flow / reverse-flow configurations.
  • Example 3 use of the traditional SMB flow configuration requires that all of the columns be connected in a series flow configuration, as shown in Figure 1.
  • the present process as illustrated in Example 3, combines series, parallel and reverse flow configurations together in one unit in the reaction zone to advantageously improve BPA yield, reduce impurities, and prevent pressure build up in the columns. It is also not limited by the number of columns used in a zone and the zones are established based upon the process objectives.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de production en continu de bisphénol A, consistant à faire réagir du phénol en continu au moyen d'une résine catalyseur acide, et à éliminer l'eau du système en continu, ou sensiblement en continu. L'élimination en continu de l'eau permet d'accroître l'activité catalytique de la résine et, de ce fait, d'améliorer la productivité. L'élimination est facilitée en mettant en oeuvre le procédé dans un dispositif à lit mobile simulé, du type en carrousel. Le rendement du procédé est encore amélioré en mettant en oeuvre le procédé dans un disposiitif configuré de manière à présenter une combinaison d'écoulements en série, parallèles ou inverses qui sont agencés à volonté, de manière à avoir un procédé ayant un rendement plus élevé avec une quantité d'impuretés réduite.
PCT/US2003/024674 2002-08-06 2003-08-06 Procede de production de bisphenol-a WO2004013075A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AU2003258130A AU2003258130A1 (en) 2002-08-06 2003-08-06 Process for the production of bisphenol-a
CA002494850A CA2494850A1 (fr) 2002-08-06 2003-08-06 Procede de production de bisphenol-a
JP2004526074A JP2005534698A (ja) 2002-08-06 2003-08-06 ビスフェノール−ａの生産プロセス
MXPA05001408A MXPA05001408A (es) 2002-08-06 2003-08-06 Proceso para la produccion de bisfenol-a.
EP03767265A EP1527037A1 (fr) 2002-08-06 2003-08-06 Procede de production de bisphenol-a
IL16663105A IL166631A0 (en) 2002-08-06 2005-02-01 Process for the production of bisphenol-a

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US10/213,580 2002-08-06
US10/213,580 US20040031757A1 (en) 2002-07-29 2002-08-06 High performance continuous reaction/separation process using a continuous liquid-solid contactor
US10/412,180 US6933416B2 (en) 2002-07-29 2003-04-11 Process for the production of bisphenol-A
US10/412,180 2003-04-11

Publications (1)

Publication Number Publication Date
WO2004013075A1 true WO2004013075A1 (fr) 2004-02-12

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2003/024674 WO2004013075A1 (fr) 2002-08-06 2003-08-06 Procede de production de bisphenol-a

Country Status (10)

Country Link
EP (1) EP1527037A1 (fr)
JP (1) JP2005534698A (fr)
KR (1) KR20050062527A (fr)
CN (1) CN1684932A (fr)
AU (1) AU2003258130A1 (fr)
CA (1) CA2494850A1 (fr)
IL (1) IL166631A0 (fr)
MX (1) MXPA05001408A (fr)
TW (1) TW200404767A (fr)
WO (1) WO2004013075A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2979252A1 (fr) * 2011-08-26 2013-03-01 IFP Energies Nouvelles Procede et dispositif de production de paraxylene en contre-courant simule a grande flexibilite
US10155709B2 (en) 2014-07-15 2018-12-18 Sabic Global Technologies B.V. Sythesis of bisphenols
CN117717980A (zh) * 2023-12-14 2024-03-19 天津大学 双酚a生产工艺及装置

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11228455A (ja) * 1998-02-18 1999-08-24 Japan Organo Co Ltd 有用物質の製造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11228455A (ja) * 1998-02-18 1999-08-24 Japan Organo Co Ltd 有用物質の製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199944, Derwent World Patents Index; Class A14, AN 1999-522628, XP002259538 *
KAWASE, MOTOAKI ET AL: "The simulated moving - bed reactor for production of bisphenol A", CATALYSIS TODAY (1999), 48(1-4), 199-209, XP002259537 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2979252A1 (fr) * 2011-08-26 2013-03-01 IFP Energies Nouvelles Procede et dispositif de production de paraxylene en contre-courant simule a grande flexibilite
US8658848B2 (en) 2011-08-26 2014-02-25 IFP Energies Nouvelles Highly flexible process and apparatus for the simulated counter-current production of para-xylene
US10155709B2 (en) 2014-07-15 2018-12-18 Sabic Global Technologies B.V. Sythesis of bisphenols
CN117717980A (zh) * 2023-12-14 2024-03-19 天津大学 双酚a生产工艺及装置

Also Published As

Publication number Publication date
CA2494850A1 (fr) 2004-02-12
CN1684932A (zh) 2005-10-19
JP2005534698A (ja) 2005-11-17
EP1527037A1 (fr) 2005-05-04
KR20050062527A (ko) 2005-06-23
AU2003258130A1 (en) 2004-02-23
MXPA05001408A (es) 2005-04-11
TW200404767A (en) 2004-04-01
IL166631A0 (en) 2006-01-15

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