CN1034397C - Equipment for producing ionic exchange resin catalyst used in synthesizing bisphenol - Google Patents
Equipment for producing ionic exchange resin catalyst used in synthesizing bisphenol Download PDFInfo
- Publication number
- CN1034397C CN1034397C CN91111615A CN91111615A CN1034397C CN 1034397 C CN1034397 C CN 1034397C CN 91111615 A CN91111615 A CN 91111615A CN 91111615 A CN91111615 A CN 91111615A CN 1034397 C CN1034397 C CN 1034397C
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- China
- Prior art keywords
- reactor
- exchange resin
- catalyst
- bisphenol
- resin
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- Expired - Fee Related
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
The present invention relates to a preparation device for an ion exchange resin catalyst for synthesizing bisphenol, which belongs to a preparation device of a catalyst. The device is a circulating system which is composed of a reactor, a filter and a container and enables ion exchange resin particles to be suspended in a solution in a slow floating rolling motion state. The device system is used for the sulfhydrylation process of the ion exchange resin catalyst for synthesizing the bisphenol, the prepared catalyst has good performance, and resin particle are basically not broken.
Description
The invention belongs to the device for making of catalyst.
The industrialized preparing process of bis-phenol mainly contains two kinds.Promptly be the hydrogen chloride of catalyst and the ion-exchange-resin process of making catalyst with storng-acid cation exchange resin with hydrogen chloride.Ion-exchange-resin process is simple because of its technology, no burn into requires low to equipment material and three wastes advantage such as less, be greatly developed in recent years, the particularly improvement of ion-exchange resin catalyst and activating technology thereof has made this technology become the advanced method of synthetic high-quality engineering plastics raw material bisphenol-A.
In order to improve the reactivity of ion-exchange resin catalyst, usually introduce thereon and help catalytic group, as sulfydryl, it is carried out modification, thereby improve reaction speed and selectivity, the method for sulfhydrylation is a lot, as partial reduction method, part neutralisation, partial esterification method with through the sulfonamide key sulfydryl to be received polymer backbone first-class, wherein easier with the part neutralisation, and have reactivity preferably, in industrial production, obtain extensive use.Carry out under stirring and heating condition industrial in part neutralisation before the present invention, sulfhydrylization reagent is the aqueous solution of sulfydryl organic amine salt hydrochlorate.
For example, Yang Zhenghui is in the production technology of 6～9 pages of " plastics industry " 1978 the 4th phases described Dalian Paint Factory, Boyd Wayne McNutt and Benny Bryan Gamill, Dow Chemical Company, BP1,183,564, on March 11st, 1970, name is called " ion-exchange resin catalyst of system bis-phenol " (Anlon Catalyst for themanufacture of Bisphenols), and Willey, Paul Rodman, General Electric Company, EP144,735, on June 19th, 1985, name is called the patent record of " method for making of bis-phenol and catalyst " (Method and Catalystfor making Bisphenol), all be to add the aqueous solution that drips sulfhydrylization reagent under the thermal agitation at 85 ℃ or 60～70 ℃, and then under this temperature stirred for several hour, carry out the part sulfhydrylation, typical example is, earlier with resin water furnishing pulpous state, adding under the thermal agitation sulfhydrylization reagent aqueous solution that drips high concentration then, is 42.6% as the concentration of the mercaptoethylmaine hydrochloride aqueous solution.Drip the back and continue reaction 3～5 hours, the catalyst that this method makes, percentage of damage height in heating with under stirring.
Purpose of the present invention provides and a kind ofly produces the mercaptolation device of exchange resin catalyst used in bisphenol synthesis with the part neutralisation, thereby obtains highly active used in bisphenol synthesis catalyst.
Main points of the present invention are, adopt special reaction unit, utilize the reacting fluid dynamics principle, resin particle evenly is suspended in the sulfhydrylation solution, and carry out slow float, between resin and resin particle, between resin and reactor member and wall, no strong collision, thus each particle can contact with the reactant liquor fluid that contains SR equably, and not broken, the catalyst that makes has uniform sulfhydryl content and high catalytic activity.
The feature of device of the present invention is, form by reactor, filter and external circulating system, reacting fluid constantly carries out interior outer circulation, the motive force of fluid motion is produced by the pump that is contained in the external circulating system, utilizes the effect of filter or gravity, prevents that resin particle from entering external circulating system, the mechanical movement of pump does not cause mechanism's damage to resin, under the effect of fluid motive force, resin particle is suspended among the reaction liquid equably, and continuous and new reactant liquor contacts.
Described filter for allowing the fluid freedom enter any device or the member of external circulating system by preventing particle, for example, can be pottery, sintered glass, open cell foamed plastic, glass from fiber, plastic optical fibre and fabric thereof, net or porous plate.
The said reactor of the present invention can be reactor, tubular reactor, tower reactor, reaction column, container, jar or bucket.In reactor, deflector can be set, also can be with heating jacket.The reactant liquor reservoir can be the container of bucket, jar, container, reactor or band baffle plate.Said pump can be the one-way pump that can make one-directional fluid flow, also can be to make the fluid can forward two-way pump that again can reverse flow.The lifting rate size of pump answers the resistance of visual response device capacity and the amount of resin and the circulatory system to select, can be with suspended state under the effect of pump, can make resin at reactor, and can be up and down roll to float among a small circle and be advisable.Sulfhydrylization reagent is sulfydryl organic amine and salt thereof.Mercaptolation can carry out at 0～90 ℃ temperature conditions, the circulatory system provided by the present invention, and its loop direction can also can also can be in laterally concerning reactor from bottom to top from top to bottom.
Fig. 1 is the device for making schematic diagram of exchange resin catalyst used in bisphenol synthesis.1-reactor among the figure, 2-filter, 3-circulating line, 4-reservoir, 5-pump.
Below in conjunction with implementing just, further specify content of the present invention.With exchange capacity is that the D001 wet resin 544g (moisture 66.7%) of 4.92mq/g is contained in internal diameter 40mm, in the tower reactor of high 590mm, 20.25g mercaptoethylmaine hydrochloride is dissolved in 6 liters of deionized waters, with pump with 14.1 liters speed per hour with the mercaptoethylmaine hydrochloride aqueous solution, import from the tower reactor lower end through filter from reservoir, be back to reservoir after filtering again by the upper end outflow and circulate continuously, this moment, reservoir adopted the still of 10 liters lining glass.Filter is sintered porous glass, and is that the glass tube of 8mm is connected to closed cycle system with reactor-filter-reservoir-pump-filter-reactor with the internal diameter.At this moment, the resin particle in tower reactor is under the percussion owing to the sulfhydrylization reagent solution that comes self-pumping, be suspended in the reactant liquor equably, and constantly contact with new reactant liquor, between particle, nothing clashes and rubs between particle and reactor wall and member.Reaction is at room temperature carried out, and after circulation in 24 hours, with deionized water drip washing from top to bottom in tower reactor, is neutral until flowing out liquid.Resin was dried by the fire 6 hours baking 12 hours under＜10mmHg in 72 ℃ of vacuum drying ovens in 80 ℃ of baking ovens.The ion-exchange resin catalyst of producing with above-mentioned method and apparatus by analysis, is respectively 3.91 and 3.86meq/g at the exchange capacity of its resin of the top and bottom of tower reactor.Molar equivalent percentage composition by the sulfonic group sulfydryl is respectively 20.53% and 21.54%, and both are very approaching.If the direction of circulation hockets, the resin properties of being produced homogeneous more then.
With the above-mentioned ion-exchange resin catalyst that makes of 20g, 100g phenol and 10g acetone reacted 1 hour under 70 ℃ of stirrings, and by bisphenol-A, the conversion ratio of acetone reaches 69%, the percentage of damage of resin＜1%.
If with NKC-9 resin water furnishing pulpous state, drip down the mercaptoethylmaine hydrochloride aqueous solution in 85 ℃ of stirrings, 85 ℃ of stirring reactions 5 hours, be washed till neutrality then with deionized water, in 80 ℃ of down bakings 6 hours, 72 ℃ of 10mmHg down baking 12 hours then the resin percentage of damage reach 10%.When with this resin catalyst during by above-mentioned the same terms synthesis of bisphenol A, acetone conversion is that the conversion ratio of bisphenol-A only is 37.75%.
Utilize the device for making of exchange resin catalyst used in bisphenol synthesis provided by the present invention, when producing ion-exchange resin catalyst, owing to be constantly to contact fresh sulfhydrylization reagent at circulatory system intermediate ion exchanger resin, and the particle of resin always is in and suspends and tumbling motion state up and down, help effectively carrying out of sulfhydrylation process, SR enters ion exchange resin easily equably, use the ion-exchange resin catalyst synthesis of bisphenol A of producing like this, the conversion ratio height of its acetone.In sulfhydrylation process, because ion exchange resin is in the suspended motion state in solution, between its particle, and nothing clashes and rubs between particle and container, and the percentage of damage of place resin is extremely low, so that not broken substantially.Device provided by the present invention in producing the sulfhydrylation technology of ion-exchange resin catalyst, has very high practical value.
Claims (3)
1. the device for making of exchange resin catalyst used in bisphenol synthesis, it is characterized in that, this device comprises: the reactor that the strong-acid ion exchange resin particle is housed, what be provided with respectively in described reactor above and below freely flows through fluid and prevents the filter that particle passes through, store the reservoir and the pump that is used for the pumping reagent treatment of reagent treatment, by pipeline filter, reservoir and the pump of above-mentioned reactor, reactor above and below are connected and form closed cycle system.
2. according to the described device of claim 1, it is characterized in that described reactor can be reactor, tower reactor, reaction column, container, jar or bucket.
3. according to the described device of claim 1, it is characterized in that described filter is to be selected from pottery, sintered glass, open cell foamed plastic, glass fibre, plastic optical fibre and fabric thereof, net, and the device of porous plate composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91111615A CN1034397C (en) | 1991-12-19 | 1991-12-19 | Equipment for producing ionic exchange resin catalyst used in synthesizing bisphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91111615A CN1034397C (en) | 1991-12-19 | 1991-12-19 | Equipment for producing ionic exchange resin catalyst used in synthesizing bisphenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1061354A CN1061354A (en) | 1992-05-27 |
| CN1034397C true CN1034397C (en) | 1997-04-02 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91111615A Expired - Fee Related CN1034397C (en) | 1991-12-19 | 1991-12-19 | Equipment for producing ionic exchange resin catalyst used in synthesizing bisphenol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1034397C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101678354A (en) | 2007-06-14 | 2010-03-24 | 陶氏环球技术公司 | The Preparation of catalysts that is used for bisphenol production |
| CN102086240B (en) * | 2010-12-22 | 2012-08-08 | 天津大学 | Equipment and method for producing uniform particle ion exchange resin beads |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0144735A1 (en) * | 1983-11-14 | 1985-06-19 | General Electric Company | Method and catalyst for making bisphenol |
-
1991
- 1991-12-19 CN CN91111615A patent/CN1034397C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0144735A1 (en) * | 1983-11-14 | 1985-06-19 | General Electric Company | Method and catalyst for making bisphenol |
Non-Patent Citations (1)
| Title |
|---|
| "化学反应技术基础" 1981.1.1 科学出版社 * |
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| Publication number | Publication date |
|---|---|
| CN1061354A (en) | 1992-05-27 |
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Address after: Beijing City Xiaoguan Andingmen Applicant after: China Petrochemical Corporation Co-applicant after: Tianjin University Address before: Seven Li station, Tianjin, Nankai District Applicant before: Tianjin University |
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| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
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| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |