CN1059480A - The reparation technology of exchange resin catalyst used in bisphenol synthesis and device thereof - Google Patents
The reparation technology of exchange resin catalyst used in bisphenol synthesis and device thereof Download PDFInfo
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- CN1059480A CN1059480A CN 91108831 CN91108831A CN1059480A CN 1059480 A CN1059480 A CN 1059480A CN 91108831 CN91108831 CN 91108831 CN 91108831 A CN91108831 A CN 91108831A CN 1059480 A CN1059480 A CN 1059480A
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Abstract
The reparation technology of exchange resin catalyst used in bisphenol synthesis and device thereof belong to producing of catalyzer.Be to utilize the part neutralisation that ion-exchange resin catalyst is carried out thiolated modified technology; Be with sulfhydrylization reagent, acid and water and swelling agent sulfhydrylization reagent aqueous solution dipping that form or that concentration is extremely low or cycle through the sulfhydrylation process that the immobilized storng-acid cation exchange resin carries out in container under room temperature and low temperature.The catalyst breakage rate of being produced is low, sulfydryl is evenly distributed, the activity high, selectivity is good, can be used for the industry of bisphenol synthesis effectively, can improve transformation efficiency, selectivity to a great extent, and quality product, with the catalyzer that technology of the present invention and device are produced, be applicable to and produce epoxy level and grade polymer dihydroxyphenyl propane.
Description
The present invention relates to producing of catalyzer
The industrialized preparing process of bis-phenol mainly contains two kinds, promptly is the hydrogen chloride of catalyzer and the ion-exchange-resin process of making catalyzer with storng-acid cation exchange resin with hydrogenchloride.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, is greatly developed in recent years.The particularly improvement of ion-exchange resin catalyst and activating technology thereof has made this production technique become the advanced method of synthetic high quality engineering plastics raw material dihydroxyphenyl propane.
In order to improve the reactive behavior of ion-exchange resin catalyst, introduce thereon usually and help catalytic group, as sulfydryl, it is carried out modification, thereby improve speed of response and selectivity.The method of sulfhydrylation is a lot, as partial reduction method, part neutralisation, partial esterification method with through the sulphonamide key sulfydryl to be received polymer backbone first-class, wherein easier with the part neutralisation, and have reactive behavior preferably, in industrial production, obtain widespread 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 technique of the described Dalian of " plastics industry " 1978 the 4th phase 6-9 page or leaf Paint Factory, Boyd WayneMcNutt and Benny Bryan Gammill, Dow Chomical Company, BP 1,183,564, on March 11st, 1970, name is called " ion-exchange resin catalyst of system bis-phenol " (An lon Catalyst for the manufacture 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 catalyzer " (Method and Catalyst For making Bisphenol), all is the aqueous solution that drips sulfhydrylation trial-production under 85 ℃ or 60-70 ℃ of heated and stirred, and then under this temperature stirred for several hour, carry out the part sulfhydrylation.Typical example is, earlier with resin water furnishing pulpous state, drips the sulfhydrylization reagent aqueous solution of high density then under heated and stirred, is 42.6% as the concentration of the mercaptoethylamine hydrochloride aqueous solution.Drip the back and continue reaction 3-5 hour in heating with under stirring.This method is because sulfhydrylization reagent solution is the high concentration solution, sulfydryl reaches the distribution of granule interior between resin particle, depend on to a great extent and stir and heating, cause the resin particle fragmentation, sulfydryl is between the Zeo-karb particle, shortcoming such as granule interior skewness particularly, thereby in the bisphenol synthesis process, limited the transformation efficiency raising.
The purpose of this invention is to provide a kind of part neutralisation of utilizing the ion-exchange resin catalyst of used in bisphenol synthesis is carried out thiolated modified technology and employed device, thereby obtain the used in bisphenol synthesis catalyzer of high-activity high-selectivity.
Main points of the present invention are that said sulfhydrylation process ties up under room temperature and the low temperature, with having the sulfhydrylization reagent solution impregnation resin of specific composition or this sulfhydrylization reagent solution being undertaken by the storng-acid cation exchange resin that remains static in container.
The sulfhydrylization reagent solution that the present invention is used is made up of sulfhydrylization reagent, acid and water, wherein also can be added with organic swelling agent of energy swelling ion exchange resin.
Said sulfhydrylization reagent is the organic acid salt or the inorganic acid salt of mercapto-amine.For example sulfydryl is organic primary, the hydrochloride of the second month in a season and tertiary amine, tosilate etc.Described acid is water miscible organic acid or mineral acid.As tosic acid, formic acid, acetate, oxalic acid, hydrochloric acid, nitric acid and sulfuric acid etc.Described water is deionized water or distilled water.Described swelling agent be can swelling ion exchange resin, and the organic liquid of removing easily or technology thereafter being had no adverse effect is as acetone, phenol, methylene dichloride etc.
The principal character of sulfhydrylization reagent solution of the present invention is, in the sulfhydrylization reagent solution, contains sulfhydrylization reagent, acid and water, also can contain swelling agent, perhaps is the extremely low sulfhydrylization reagent aqueous solution of concentration.
Sulfhydrylization reagent solution of the present invention can be (by weight):
(1) forms by following routine composition
1, sulfhydrylization reagent 0.01%～saturated solution is preferably 0.1-60%.
2, acid 0.01～50% is preferably 0.1-10%.
3, organic swelling agent 0～98% is preferably 0.1～50%.
4, water 2-99.98%
(2) the sulfhydrylization reagent aqueous solution that concentration is extremely low, its concentration≤1%.
Sulfhydrylization reagent solution of the present invention is applicable to 0-90 ℃, at the reactor of container, band stirring, or carries out sulfhydrylation in the tower reactor.
The present invention especially can be 0-50 ℃ and remain static following at matrix ion exchange resin under room temperature and low temperature, with sulfhydrylization reagent solution solvent impregnated resin in container, or sulfhydrylization reagent solution one or many passed through resinbed, for example, once or multiply simultaneously or multiply is repeatedly flooded or carry out drip or stream circulation fast through bypass, with the resin sulfhydrylation, then, through washing and drying process, obtain catalyzer.
Said ion exchange resin can be storng-acid cation exchange resin, and this resin can be gel-type, also can be macroporous type, with macroporous type for well.The ion exchange resin exchange capacity can be 2.0～5.5meq/g, is advisable with 4.0～5.5meq/g.The resin such as the Amberlite-118 that are suitable for, Amberlyst-15, Dowex-50; Homemade Doo1 series and 001 series etc., as NKC-9, D72, D50 and D54 etc.
Ion exchange resin can be in drying regime before adding sulfhydrylization reagent solution, also can be earlier with certain liquid with the matrix resin swelling, and then carry out sulfhydrylation process.The liquid of swelling matrix resin can be water, as distilled water, deionized water, acetone, phenol, alcohol (as methyl alcohol, ethanol etc.), phenol-acetone mixed solution, and the aqueous solution of above-mentioned substance, aqueous acid, or contain the above-mentioned solution of sulfhydrylization reagent, also can be organic swelling agent, as ethylene dichloride etc.
The device for making of exchange resin catalyst used in bisphenol synthesis is the container that ion exchange resin is remained static.For example reactor (not using stirring), bottle, jar etc. can make sulfhydrylization reagent solution drip or round-robin tower reactor, or have the devices such as tower reactor of chuck.In addition, the reactor of bisphenol synthesis production usefulness or continuous reaction device also can be used as mercaptolation device of the present invention.
Adopt the exchange resin catalyst used in bisphenol synthesis that the present invention produced, can be used for the industry of bisphenol synthesis effectively, be applicable to and produce epoxy level and grade polymer dihydroxyphenyl propane.Because it is inner and surperficial that sulfydryl can be distributed in ion-exchange resin particles well, therefore, good catalytic activity and selectivity arranged.
Further specify content of the present invention below in conjunction with embodiment
Example 1, be that sulfonic acid macroporous type vinylbenzene-divinyl benzene series ion exchange resin 30g of 4.66meq/g packs in the Glass Containers with exchange capacity, again 3.2g mercaptoethylamine hydrochloride is dissolved in 65ml concentration and is in 5% the hydrochloric acid soln, in the above-mentioned Glass Containers that resin is housed of gained solution impouring, dipping 2 round the clock under 26-29 ℃ of room temperature, be neutral with deionized water thorough washing to water liquid, dried by the fire 6 hours down in 80 ℃, dried by the fire 12 hours under 72 ℃ of vacuum then, the exchange capacity that records resin is 3.87meq/g.Sulfhydryl content is 16.95%.
With 130g phenol and 10g acetone in the presence of the above-mentioned resin of 20g in 75 ℃ of stirring reactions 1 hour, acetone conversion is that the transformation efficiency of dihydroxyphenyl propane reaches 49.08%.If not hydrochloric in the above-mentioned sulfhydrylization reagent solution, and be the identical mercaptoethylamine hydrochloride aqueous solution of concentration, then under the same conditions during synthesis of bisphenol A its acetone conversion be that the transformation efficiency of dihydroxyphenyl propane only is 31.66%.
Example 2, be that NKC-9 resin (the sulfonic acid macroporous type vinylbenzene-dialkylene benzene series ion exchange resin) 30g of 4.74meq/g packs in the wide-necked bottle with exchange capacity, in addition, 3.23g mercaptoethylamine hydrochloride is dissolved in the 1950ml deionized water, and acquisition concentration is 0.165% sulfhydrylization reagent solution.The above-mentioned solution of 70ml is poured in the wide-necked bottle of above-mentioned dress resin, with resin swelling, the diameter of then resin being packed into is in the tower reactor of 4cm, with the speed of 447ml per hour the above-mentioned solution drip of remainder is cycled through resin layer with accurate volumetric infusion pump, in under 26～31 ℃ of room temperatures after 3 drip circulations round the clock, be washed to water liquid and be neutral, filter dried anhydrating, dried by the fire 6 hours down at 80 ℃, 72 ℃ of 10mmHg dried by the fire 12 hours down, the exchange capacity of gained resin is 3.8meq/g, and sulfhydryl content is 19.20%, and resin is not broken in sulfhydrylation process.
75 ℃ of following stirring reactions 1 hour, acetone conversion was that the transformation efficiency of dihydroxyphenyl propane reaches 53% with 130g phenol, 10g acetone and the above-mentioned resin of 20g.Chroman, 2,4-bis-phenol and content of bisphenol A are respectively 0.08,0.035 and 14.88%, do not detect triphenol and other impurity, and the selectivity of dihydroxyphenyl propane reaches 99.23%.
If with NKC-9 resin water furnishing pulpous state, dripping concentration down in 85 ℃ of stirrings is 51.2% the mercaptoethylamine hydrochloride aqueous solution, then 85 ℃ of stirring reactions 5 hours, be washed till neutrality with deionized water, dried by the fire 6 hours down in 80 ℃, 72 ℃ of 10mmHg dried by the fire 12 hours down, and the resin percentage of damage reaches 10%.When with this resin catalyst during by above-mentioned the same terms synthesis of bisphenol A, acetone conversion is that the transformation efficiency of dihydroxyphenyl propane only is 37.75%.
Example 3, be that the basic benzene series ion exchange resin of strongly-acid macroporous type vinylbenzene-two 60g of 4.74meq/g packs in the band ground-in wide-necked bottle, in another band ground-in wide-necked bottle, 6.46g mercaptoethylamine hydrochloride be dissolved in again in the solution that 30ml acetone and 100ml5% hydrochloric acid forms exchange capacity.Two port grinding bottles are closed the lid, in refrigerator, place under 0 ℃ and spend the night.Above-mentioned solution under 0 ℃ poured in 0 ℃ the above-mentioned resin,, wash to water liquid with the deionized water under 0 ℃ again and be neutrality in 0 ℃ of dipping 48 hours.Elimination water liquid dries by the fire resin 6 hours down at 80 ℃, and baking is 12 hours in 72 ℃ of 10mmHg vacuum drying ovens, and the exchange capacity that records resin is 3.84meq/g, and sulfhydryl content is 19%.
The reparation technology of exchange resin catalyst used in bisphenol synthesis provided by the present invention owing to remain static in reaction vessel at sulfhydrylation process intermediate ion exchange resin, has significantly reduced the percentage of damage of resin, has also improved the utilization ratio of sulfhydrylization reagent.For example adopt in the past that the percentage of damage of its ion exchange resin of heated and stirred technology is 10～15%, and utilize method of the present invention to produce, its percentage of damage＜1%, the utilization ratio of sulfhydrylization reagent is also very high.Under room temperature and low temperature, produce ion exchange resin and obviously brought simplified equipment and energy-conservation effect, and the thermal destruction that can alleviate resin.The present invention utilizes the ionic effect of sulfhydrylization reagent solution in addition, swelling effect, and dilute solution characteristic, by changing the composition and the sulfhydrylation technology of sulfhydrylation solution, improve sulfydryl reaches granule interior between the sulfonic acid ion exchange resin particle distribution, the used in bisphenol synthesis catalyst activity height of producing, selectivity is good.
The catalyzer that the present invention produced can be used for bisphenol synthesis effectively, has good product quality when for example producing dihydroxyphenyl propane by phenol and condensation of acetone, the advantage that productive rate is high.As described in example 1 and example 2, acetone conversion is that the transformation efficiency of dihydroxyphenyl propane can reach 49～53%, and selectivity reaches more than 99%.And the transformation efficiency of acetone can only arrive 37.3～40% when using the catalyzer synthesis of bisphenol A that existing corresponding technology produces before the present invention, and selectivity is 95.6%.Thereby technology provided by the present invention is an of great value technology in the industry of bisphenol synthesis.
Claims (7)
1, the reparation technology of exchange resin catalyst used in bisphenol synthesis, be ion exchange resin to be carried out sulfhydrylation with the part neutralisation, it is characterized in that sulfhydrylation process is to carry out with the sulfhydrylization reagent solution impregnation with specific composition or by be in static storng-acid cation exchange resin in container under room temperature or low temperature, 1. its sulfhydrylization reagent solution be made up of salt, acid and the water of sulfydryl organic amine, wherein also can add organic swelling agent; 2. the aqueous solution of the sulfydryl organic amine salt of lower concentration (≤1%).
2,, it is characterized in that said room temperature or low temperature are 0～50 ℃ according to the reparation technology of the said exchange resin catalyst used in bisphenol synthesis of claim 1.
3,, it is characterized in that the acid in the said sulfhydrylization reagent solution is water miscible organic acid and mineral acid according to the reparation technology of the said exchange resin catalyst used in bisphenol synthesis of claim 1.
According to the reparation technology of the said exchange resin catalyst used in bisphenol synthesis of claim 1, it is characterized in that 4, said swelling agent is the organic liquid of energy swelling ion exchange resin, for example acetone, phenol and ethylene dichloride etc.
5, according to the reparation technology of the said exchange resin catalyst used in bisphenol synthesis of claim 1, it is characterized in that, said sulfhydrylization reagent solution impregnation or pass through storng-acid cation exchange resin, being meant that ion exchange resin remains static in container once adds sulfhydrylization reagent solution down or multiply adds simultaneously, or multiply repeatedly adds dipping and discharging fast or carries out drip circulation, stream circulation fast.
6, exchange resin catalyst used in bisphenol synthesis device for making is characterized in that can be the container that ion exchange resin is remained static, as bottle, jar, still, tower reactor, liquid tower reactor capable of circulation etc.
7,, it is characterized in that it to be the reactor or the flow reactor of used in bisphenol synthesis according to the said exchange resin catalyst used in bisphenol synthesis device for making of claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91108831A CN1034398C (en) | 1991-09-16 | 1991-09-16 | Prodn. technology and apparatus of on-exchange resin catalyst used in bisphenol synthesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91108831A CN1034398C (en) | 1991-09-16 | 1991-09-16 | Prodn. technology and apparatus of on-exchange resin catalyst used in bisphenol synthesis |
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| Publication Number | Publication Date |
|---|---|
| CN1059480A true CN1059480A (en) | 1992-03-18 |
| CN1034398C CN1034398C (en) | 1997-04-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91108831A Expired - Fee Related CN1034398C (en) | 1991-09-16 | 1991-09-16 | Prodn. technology and apparatus of on-exchange resin catalyst used in bisphenol synthesis |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092628C (en) * | 1996-04-24 | 2002-10-16 | 中国石油化工集团公司 | producing bisphenol by using modified ion exchange rerin with special porous structure as catalyst |
| CN102886277A (en) * | 2003-09-01 | 2013-01-23 | 出光兴产株式会社 | Preparation method of modified catalyst for bisphenol A preparation |
| CN110545916A (en) * | 2017-04-24 | 2019-12-06 | 巴杰许可有限责任公司 | Catalyst system and process for the preparation of bisphenol A |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3634341A (en) * | 1970-03-06 | 1972-01-11 | Dow Chemical Co | Ion exchange catalysts for the preparation of bisphenols |
| US4423252A (en) * | 1980-08-07 | 1983-12-27 | Mitsubishi Chemical Industries Limited | Process for preparing bisphenols |
| US4595704A (en) * | 1984-08-13 | 1986-06-17 | The Dow Chemical Company | Preparation of ion-exchange catalysts |
| US4820740A (en) * | 1986-10-30 | 1989-04-11 | Shell Oil Company | Process and catalyst for production of bisphenol-A |
| US4847432A (en) * | 1987-12-28 | 1989-07-11 | General Electric Company | Method for the purification of ion exchange resins used in the production of bisphenol A |
-
1991
- 1991-09-16 CN CN91108831A patent/CN1034398C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092628C (en) * | 1996-04-24 | 2002-10-16 | 中国石油化工集团公司 | producing bisphenol by using modified ion exchange rerin with special porous structure as catalyst |
| CN102886277A (en) * | 2003-09-01 | 2013-01-23 | 出光兴产株式会社 | Preparation method of modified catalyst for bisphenol A preparation |
| CN102886277B (en) * | 2003-09-01 | 2016-04-27 | 出光兴产株式会社 | Preparation method of modified catalyst for bisphenol A preparation |
| CN110545916A (en) * | 2017-04-24 | 2019-12-06 | 巴杰许可有限责任公司 | Catalyst system and process for the preparation of bisphenol A |
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| Publication number | Publication date |
|---|---|
| CN1034398C (en) | 1997-04-02 |
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