CN101733163A - Method for preparing polyacid crystal catalyst - Google Patents
Method for preparing polyacid crystal catalyst Download PDFInfo
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- CN101733163A CN101733163A CN200910311603A CN200910311603A CN101733163A CN 101733163 A CN101733163 A CN 101733163A CN 200910311603 A CN200910311603 A CN 200910311603A CN 200910311603 A CN200910311603 A CN 200910311603A CN 101733163 A CN101733163 A CN 101733163A
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- polyacid crystal
- crystal catalyst
- preparation
- catalyst
- polyacid
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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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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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
- Y02P20/584—Recycling of catalysts
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Abstract
The invention provides a method for preparing a polyacid crystal catalyst and relates to a preparation method for a catalyst. The invention solves the problems that reaction condition for preparing ethylene glycol with a carbonic ethylene ester hydrolyzing method is acuity, cost is high, catalyst is difficult to recycle and environment is polluted easily. The method of the invention comprises the steps of: adding NaAsO2, (NH4)6Mo7O24.4H2O, CuCl2.2H2O and iminazole into distilled water and stirring in order to obtain mixed solution, sealing the mixed solution in a stainless steel reaction kettle which is lined with polytetrafluoroethylene inside, heating and crystallizing, and then cooling to room temperature in order to acquire the polyacid crystal catalyst. The polyacid crystal catalyst of the invention has mild reaction condition for catalyzing preparing ethylene glycol with the carbonic ethylene ester hydrolyzing method. The reaction can be preformed at normal temperature and under normal pressure thereby saving the cost. The catalyst is easy to recycle by filtering thereby protecting environment. The conversion rate of carbonic ethylene ester hydrolyzing by catalyzing with the polyacid crystal catalyst is 90 to 97 percent and the selectivity to ethylene glycol is 90 to 100 percent.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method.
Background technology
Ethylene glycol is a kind of important chemical material, has purposes widely.China all needs a large amount of ethylene glycol of import every year.Carbon current vinyl acetate Hydrolyze method prepares ethylene glycol and need (react under the 2.0MPa～4.0MPa), exist severe reaction conditions, cost height, catalyst and be difficult for reclaiming the problem that pollutes easily at high temperature (140 ℃～180 ℃), high pressure.
Summary of the invention
Technical problem to be solved by this invention is to prepare glycol reaction condition harshness, cost height, catalyst and be difficult for reclaiming in order to solve the ethylene carbonate Hydrolyze method, and the problem that pollutes easily provides a kind of preparation method of ethylene glycol catalyst.
The method of polyacid crystal catalyst of the present invention is as follows: one, with NaAsO
2, (NH
4)
6Mo
7O
244H
2O, CuCl
22H
2O and imidazoles join in the distilled water, stir 30min～60min, obtain mixed liquor; Two, the mixed liquor of step 1 gained being enclosed liner is in the stainless steel cauldron of polytetrafluoroethylene (PTFE), compactedness is 75%～82% in the reactor, then stainless steel cauldron is put into 130 ℃～150 ℃ baking oven heating crystallization 4 days～6 days, after the room temperature cooling, promptly get polyacid crystal catalyst again; NaAsO in the step 1
2, (NH
4)
6Mo
7O
244H
2O, CuCl
22H
2The mol ratio of O, imidazoles and distilled water is 3.4: 1: 1.3: 4.5: 1247.
Polyacid crystal catalyst of the present invention is used for the reaction condition gentleness of catalysis preparing ethyl glycol by hydrolysis of ethylene carbonate, and cost has been saved in reaction at normal temperatures and pressures.Catalyst easily reclaims, and filters and gets final product environmental protection.The conversion ratio of using polyacid crystal catalyst catalyzed carbon vinyl acetate of the present invention hydrolysis is 90～97%, is 90～100% to the selectivity of ethylene glycol.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
The specific embodiment one: the method for polyacid crystal catalyst is as follows in the present embodiment: one, with NaAsO
2, (NH
4)
6Mo
7O
244H
2O, CuCl
22H
2O and imidazoles join in the distilled water, stir 30min～60min, obtain mixed liquor; Two, the mixed liquor of step 1 gained being enclosed liner is in the stainless steel cauldron of polytetrafluoroethylene (PTFE), compactedness is 75%～82% in the reactor, then stainless steel cauldron is put into 130 ℃～150 ℃ baking oven heating crystallization 4 days～6 days, after the room temperature cooling, promptly get polyacid crystal catalyst again; NaAsO in the step 1
2, (NH
4)
6Mo
7O
244H
2O, CuCl
22H
2The mol ratio of O, imidazoles and distilled water is 3.4: 1: 1.3: 4.5: 1247.
Present embodiment gained polyacid crystal catalyst is tested, and productive rate is 83% (in molybdenum).Show that through the elementary analysis test result each element mass content theoretical value (experiment value) is as follows: C 7.83% (7.87%); H 0.88% (0.93%); N6.09% (6.05%).Chemical formula is C
12H
20As
6CuMo
6N
8O
30
Present embodiment is used for the catalysis preparing ethyl glycol by hydrolysis of ethylene carbonate with polyacid crystal catalyst, and method is as follows: one, polyacid crystal catalyst roasting 4h under 200 ℃ of conditions is activated; Two, with 0.02g～0.04g polyacid crystal catalyst, 0.8g～1.2g ethylene carbonate and 1.0ml～3.0ml H
2O reacts 5h～10h under 80～100 ℃ condition, filter then, obtain the solid polyacid crystal catalyst, again filtrate is distilled, with online mensuration product component of gas-matter and content, calculate conversion ratio and selectivity, drawing the conversion ratio of using the polyacid crystal catalyst ethylene carbonate is 90%～97%, and the selectivity of ethylene glycol is 100%.
Compare with other process conditions, the operational advantages of this seminar is bigger, and the process conditions gentleness does not need high pressure, and cost is low, and the catalyst environmental protection is easily separated.
The specific embodiment two: what present embodiment and the specific embodiment one were different is that mixing time is 40min～50min in the step 1.Other is identical with the specific embodiment one.
The specific embodiment three: what present embodiment was different with the specific embodiment one or two is that mixing time is 45min in the step 1.Other is identical with the specific embodiment one or two.
The specific embodiment four: present embodiment and the specific embodiment one to three are different be in the step 2 in the reactor compactedness be 78%～81%.Other is identical with the specific embodiment one to three.
The specific embodiment five: present embodiment and the specific embodiment one to four are different be in the step 2 in the reactor compactedness be 80%.Other is identical with the specific embodiment one to four.
The specific embodiment six: present embodiment and the specific embodiment one to five are different is in the step 2 stainless steel cauldron to be put into 132 ℃～148 ℃ baking oven heating crystallization.Other is identical with the specific embodiment to five.
The specific embodiment seven: present embodiment and the specific embodiment one to six are different is in the step 2 stainless steel cauldron to be put into 135 ℃～145 ℃ baking oven heating crystallization.Other is identical with the specific embodiment one to six.
The specific embodiment eight: present embodiment and the specific embodiment one to seven are different is in the step 2 stainless steel cauldron to be put into 138 ℃～142 ℃ baking oven heating crystallization.Other is identical with the specific embodiment one to seven.
The specific embodiment nine: present embodiment and the specific embodiment one to eight are different is in the step 2 stainless steel cauldron to be put into 140 ℃ baking oven heating crystallization.Other is identical with the specific embodiment one to eight.
The specific embodiment ten: present embodiment and the specific embodiment one to nine are different be in the step 2 heating crystallization time be 5 days.Other is identical with the specific embodiment one to nine.
Claims (10)
1. the preparation method of polyacid crystal catalyst is characterized in that the method for polyacid crystal catalyst is as follows: one, with NaAsO
2, (NH
4)
6Mo
7O
244H
2O, CuCl
22H
2O and imidazoles join in the distilled water, stir 30min～60min, obtain mixed liquor; Two, the mixed liquor of step 1 gained being enclosed liner is in the stainless steel cauldron of polytetrafluoroethylene (PTFE), compactedness is 75%～82% in the reactor, then stainless steel cauldron is put into 130 ℃～150 ℃ baking oven heating crystallization 4 days～6 days, after the room temperature cooling, promptly get polyacid crystal catalyst again; NaAsO in the step 1
2, (NH
4)
6Mo
7O
244H
2O, CuCl
22H
2The mol ratio of O, imidazoles and distilled water is 3.4: 1: 1.3: 4.5: 1247.
2. the preparation method of polyacid crystal catalyst according to claim 1 is characterized in that mixing time is 40min～50min in the step 1.
3. the preparation method of polyacid crystal catalyst according to claim 1 is characterized in that mixing time is 45min in the step 1.
4. the preparation method of polyacid crystal catalyst according to claim 1 and 2 is characterized in that the interior compactedness of reactor is 78%～81% in the step 2.
5. the preparation method of polyacid crystal catalyst according to claim 1 and 2 is characterized in that the interior compactedness of reactor is 80% in the step 2.
6. the preparation method of polyacid crystal catalyst according to claim 4 is characterized in that in the step 2 stainless steel cauldron put into 132 ℃～148 ℃ baking oven heating crystallization.
7. the preparation method of polyacid crystal catalyst according to claim 4 is characterized in that in the step 2 stainless steel cauldron put into 135 ℃～145 ℃ baking oven heating crystallization.
8. the preparation method of polyacid crystal catalyst according to claim 4 is characterized in that in the step 2 stainless steel cauldron put into 138 ℃～142 ℃ baking oven heating crystallization.
9. the preparation method of polyacid crystal catalyst according to claim 4 is characterized in that in the step 2 stainless steel cauldron put into 140 ℃ baking oven heating crystallization.
10. according to the preparation method of claim 1,2 or 6 described polyacid crystal catalysts, it is characterized in that the heating crystallization time is 5 days in the step 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910311603A CN101733163A (en) | 2009-12-16 | 2009-12-16 | Method for preparing polyacid crystal catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910311603A CN101733163A (en) | 2009-12-16 | 2009-12-16 | Method for preparing polyacid crystal catalyst |
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|---|---|
| CN101733163A true CN101733163A (en) | 2010-06-16 |
Family
ID=42457493
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910311603A Pending CN101733163A (en) | 2009-12-16 | 2009-12-16 | Method for preparing polyacid crystal catalyst |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103418440A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Catalyst for ethylene glycol preparation through ethylene carbonate hydrolysis |
| CN108440608A (en) * | 2018-04-03 | 2018-08-24 | 黑龙江科技大学 | A kind of hybrid inorganic-organic molybdenum arsenic acid salt crystal and its preparation method and application |
| CN110273181A (en) * | 2019-07-29 | 2019-09-24 | 合肥学院 | A kind of more molybdenum oxygen hydrochlorate crystalline materials of the cupric of hybrid inorganic-organic and preparation method thereof |
-
2009
- 2009-12-16 CN CN200910311603A patent/CN101733163A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103418440A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Catalyst for ethylene glycol preparation through ethylene carbonate hydrolysis |
| CN103418440B (en) * | 2012-05-16 | 2015-08-12 | 中国石油化工股份有限公司 | The catalyst of preparing ethyl glycol by hydrolysis of ethylene carbonate |
| CN108440608A (en) * | 2018-04-03 | 2018-08-24 | 黑龙江科技大学 | A kind of hybrid inorganic-organic molybdenum arsenic acid salt crystal and its preparation method and application |
| CN110273181A (en) * | 2019-07-29 | 2019-09-24 | 合肥学院 | A kind of more molybdenum oxygen hydrochlorate crystalline materials of the cupric of hybrid inorganic-organic and preparation method thereof |
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Open date: 20100616 |