CN101733163A - Method for preparing polyacid crystal catalyst - Google Patents
Method for preparing polyacid crystal catalyst Download PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- crystal catalyst
- polyacid crystal
- preparation
- catalyst
- polyacid
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 239000013078 crystal Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 13
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 15
- 239000010935 stainless steel Substances 0.000 claims abstract description 15
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- 150000002460 imidazoles Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 29
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 abstract description 8
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 3
- 239000011259 mixed solution Substances 0.000 abstract 2
- 239000002253 acid Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HMWVNKJRYWXJGS-UHFFFAOYSA-N C(C)(=O)OC=C.[C] Chemical compound C(C)(=O)OC=C.[C] HMWVNKJRYWXJGS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910016525 CuMo Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
多酸晶体催化剂的制备方法，它涉及一种催化剂的制备方法。本发明解决了碳酸乙烯酯水解法制备乙二醇反应条件苛刻、成本高、催化剂不易回收，容易造成污染的问题。本发明如下：将NaAsO2、(NH4)6Mo7O24·4H2O、CuCl2·2H2O和咪唑加入到蒸馏水中搅拌得到混合液，将混合液封入内衬为聚四氟乙烯的不锈钢反应釜内，然后加热晶化，再室温冷却后，即得多酸晶体催化剂。本发明多酸晶体催化剂用于催化碳酸乙烯酯水解制备乙二醇的反应条件温和，在常温常压下反应，节约了成本。催化剂易回收，过滤即可，绿色环保。本发明多酸晶体催化剂催化碳酸乙烯酯水解的转化率为90～97％，对乙二醇的选择性为90～100％。The invention discloses a method for preparing a polyacid crystal catalyst, which relates to a method for preparing a catalyst. The invention solves the problems of harsh reaction conditions, high cost, difficult recovery of catalysts and easy pollution caused by ethylene carbonate hydrolysis method for preparing ethylene glycol. The present invention is as follows: add NaAsO 2 , (NH 4 ) 6 Mo 7 O 24 4H 2 O, CuCl 2 2H 2 O and imidazole into distilled water and stir to obtain a mixed solution, and seal the mixed solution into a liner of polytetrafluoroethylene In a stainless steel reaction kettle, then heated to crystallize, and after cooling at room temperature, the polyacid crystal catalyst is obtained. The multi-acid crystal catalyst of the present invention is used to catalyze the hydrolysis of ethylene carbonate to prepare ethylene glycol, and the reaction conditions are mild, and the reaction is carried out at normal temperature and pressure, thereby saving cost. The catalyst is easy to recycle, just need to be filtered, which is green and environmentally friendly. The polyacid crystal catalyst of the present invention catalyzes ethylene carbonate hydrolysis with a conversion rate of 90-97%, and a selectivity to ethylene glycol of 90-100%.
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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| Publication Number | Publication Date |
|---|---|
| CN101733163A true CN101733163A (en) | 2010-06-16 |
Family
ID=42457493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910311603A Pending CN101733163A (en) | 2009-12-16 | 2009-12-16 | Method for preparing polyacid crystal catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101733163A (en) |
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 |