CN1424141A - Catalyst of synthetic propylene and application thereof - Google Patents
Catalyst of synthetic propylene and application thereof Download PDFInfo
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- CN1424141A CN1424141A CN 02158701 CN02158701A CN1424141A CN 1424141 A CN1424141 A CN 1424141A CN 02158701 CN02158701 CN 02158701 CN 02158701 A CN02158701 A CN 02158701A CN 1424141 A CN1424141 A CN 1424141A
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- catalyst
- expoxy propane
- sylvite
- acrylic ester
- iodomethane
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Abstract
A catalyst for synthesizing the propylene carbonate is composed of potassium salt (10-20 wt%), and activated carbon, metal oxide, or molecular sieve (80-90 wt%). The propylene carbonate is prepared through reaction between potassium salt, epoxy propane and iodomethane at 120-180 deg.C and 2-6 MPa for 0.5-2 hr. Its advantages are high catalytic activity, low cost and cyclic use.
Description
Affiliated field:
The invention belongs to a kind of Catalysts and its preparation method of synthesizing acrylic ester, relate in particular to a kind of catalyst and application thereof that is used for carbon dioxide and expoxy propane synthesizing acrylic ester.
Background technology:
Carbon dioxide and expoxy propane generate propene carbonate under the effect of catalyst be one of stabilizing carbon dioxide efficient ways, and product has multiple use.Department is as the extractant of dispersant, alkene and the aromatic hydrocarbons of plasticizer, spin solvent, water-soluble dye and the decarburizer in the nitrogen fertilizer production; in lithium ion battery, adopt propene carbonate to make electrolyte graphite anode is protected, and can be used as the raw material of environmental friendliness chemicals dimethyl carbonate and Merlon.Carrying out cycloaddition reaction catalyst commonly used by carbon dioxide and expoxy propane is halogen compounds, n-Bu
3Sn+nBu
4PI organic transition metal halide and metal ether load potassium iodide catalyst (Journal of Molecular Catalysis, 1998,6,409) have all obtained higher activity, however the Preparation of catalysts relative complex.The complex catalyst of the high bridge of Japan and a kind of alkali halide of friend (JP71-128778) proposition and crown ether can make and carry out smoothly under the condition that is reflected under the lower temperature and pressure and obtain higher yield, but crown ether toxicity is big, and costs an arm and a leg.Although of a great variety, still there is the Preparation of Catalyst complexity in the course of reaction, costs an arm and a leg, toxic, catalyst activity component problem such as loss easily, caused the propene carbonate preparation cost higher.
Summary of the invention:
The purpose of this invention is to provide a kind of high activated catalyst and application thereof from carbon dioxide and expoxy propane synthesizing acrylic ester, this catalyst cost is low, active component is difficult for running off and can reusing.
Catalyst weight percentage of the present invention consists of:
Sylvite 10-20%
Active carbon, metal oxide or molecular sieve 80-90%
Aforesaid sylvite is potassium hydroxide, potash, potassium nitrate, potassium acetate.
Aforesaid metal oxide is zirconia, zinc oxide, aluminium oxide, magnesia.
The specific area of aforesaid active carbon is a 700-1000 rice
2/ gram, particle diameter is less than 80 orders.
Aforesaid molecular sieve is A, X, Y type.
Preparation method of the present invention is as follows:
Method one: with metal oxide or molecular sieve carrier 300-700 ℃ of roasting 3 hours, form the carrier incipient impregnation in the aqueous solution of sylvite by above-mentioned catalyst then, left standstill 12-24 hour, and, obtained catalyst at 450-650 ℃ of roasting 3-6 hour through 60-120 ℃ of drying.Method two: absorbent charcoal carrier was handled 3-5 hour in 600-900 ℃ in nitrogen or argon gas atmosphere earlier.Vacuumize activation 30-60 minute, will form the carrier incipient impregnation in the aqueous solution of sylvite by above-mentioned catalyst then, left standstill 12-24 hour,, in nitrogen or argon gas atmosphere, activate 3-6 hour down and obtain catalyst in 500-700 ℃ through 60-120 ℃ of drying.
Catalyst process condition of the present invention is that the mol ratio by sylvite in the catalyst and expoxy propane and iodomethane is a sylvite: expoxy propane: iodomethane=0.003-0.01: 1: 0.02-0.03, sylvite, expoxy propane and iodomethane are added in the reactor, and the carbon dioxide of feeding 2.0-6.0MPa, under stirring condition, be warming up to 120-180 ℃, reacted 0.5-2 hour.
Catalyst of the present invention compared with prior art has following advantage:
(1) manufacturing is simple, the catalyst cost is low.
(2) under the reaction condition of gentleness, can obtain higher activity.
(3) environmentally safe, active component are difficult for running off.
Embodiments of the invention are as follows:
Embodiment 1
By potash is 20%, and zirconia is that 80% composition (percentage by weight) is impregnated into Zirconia carrier in the solution of potassium carbonate, leaves standstill 24 hours, and through 120 ℃ of dryings, 600 ℃ of roastings made catalyst in 4 hours.Cycloaddition reaction is carried out in autoclave.In autoclave, add earlier catalyst, expoxy propane and iodomethane, its addition is a potash: expoxy propane: iodomethane=0.01: 1: 0.025 (mol ratio), feed the carbon dioxide of 3.0MPa then, under stirring condition, be warming up to 150 ℃, reacted 1 hour, bleed off residual gas and filtration after the cooling, catalyst is separated with product, product is through gas chromatographic analysis, and the conversion ratio of expoxy propane is 99.4%, and the yield of propene carbonate is 98.1%.
Embodiment 2
By potash is 10%, and aluminium oxide is that 90% composition (percentage by weight) is impregnated into alumina support in the solution of potassium carbonate, leaves standstill 24 hours, and through 120 ℃ of dryings, 600 ℃ of roastings made catalyst in 4 hours, and all the other conditions are with embodiment 1.Reaction condition is as follows: pressure=3.0MPa, temperature=140 ℃, potash: expoxy propane: iodomethane mol ratio=0.003: 1: 0.02, reaction time is 1 hour, product is through gas chromatographic analysis, and the conversion ratio of expoxy propane is 83.6%, and the yield of propene carbonate is 80.1%.
Embodiment 3
By potassium hydroxide is 10%, and magnesia is that 90% composition (percentage by weight) is impregnated into magnesium oxide carrier in the potassium hydroxide solution, leaves standstill 24 hours, and through 120 ℃ of dryings, 600 ℃ of roastings made catalyst in 4 hours, and all the other conditions are with embodiment 1.Reaction condition is as follows: pressure=2.0MPa, temperature=120 ℃, potassium hydroxide: expoxy propane: iodomethane mol ratio=0.003: 1: 0.02, reaction time is 0.5 hour, product is through gas chromatographic analysis, the conversion ratio of expoxy propane is 76.4%, and the yield of propene carbonate is 72.3%.
Embodiment 4
By potassium nitrate is 20%, and active carbon is that 80% composition (percentage by weight) is impregnated into absorbent charcoal carrier in the potassium nitrate solution, leaves standstill 24 hours, and through 120 ℃ of dryings, activation made catalyst in 3 hours in 600 ℃ of following nitrogen atmospheres, and all the other conditions are with embodiment 1.Reaction condition is as follows: pressure=5.0MPa, temperature=170 ℃, potassium nitrate: expoxy propane: iodomethane mol ratio=0.006: 1: 0.028, reaction time is 0.5 hour, product is through gas chromatographic analysis, and the conversion ratio of expoxy propane is 98.8%, and the yield of propene carbonate is 96.9%.
Embodiment 5
By potassium hydroxide is 20%, A type molecular sieve be 80% composition (percentage by weight) the A type molecular sieve carrier impregnation in potassium hydroxide solution, left standstill 24 hours, through 120 ℃ of dryings, 550 ℃ of roastings made catalyst in 4 hours, all the other conditions are with embodiment 1.Reaction condition is as follows: pressure=4.0MPa, temperature=160 ℃, potassium hydroxide: expoxy propane: iodomethane mol ratio=0.01: 1: 0.024, reaction time is 1 hour, product is through gas chromatographic analysis, and the conversion ratio of expoxy propane is 96.6%, and the yield of propene carbonate is 93.4%.
Embodiment 6
By potassium acetate is 15%, and zinc oxide is that 85% composition (percentage by weight) is impregnated into zinc oxide carrier in the liquor kalii acetici, leaves standstill 24 hours, and through 120 ℃ of dryings, 600 ℃ of roastings made catalyst in 4 hours, and all the other conditions are with embodiment 1.Reaction condition is as follows: pressure=6.0MPa, temperature=140 ℃, potassium acetate: expoxy propane: iodomethane mol ratio=0.007: 1: 0.025, reaction time is 1.5 hours, product is through gas chromatographic analysis, and the conversion ratio of expoxy propane is 93.2%, and the yield of propene carbonate is 90.2%.
Embodiment 7
By potassium hydroxide is 20%, and X type molecular sieve is that 80% composition (percentage by weight) is impregnated into X type molecular sieve carrier in the potassium hydroxide solution, leaves standstill 24 hours, and through 120 ℃ of dryings, 550 ℃ of roastings made catalyst in 4 hours, and all the other conditions are with embodiment 1.Reaction condition is as follows: pressure=5.0MPa, temperature=180 ℃, potassium hydroxide: expoxy propane: iodomethane mol ratio=0.01: 1: 0.025, reaction time is 1.5 hours, product is through gas chromatographic analysis, the conversion ratio of expoxy propane is 97.1%, and the yield of propene carbonate is 95.6%.
Embodiment 8
By potash is 15%, Y zeolite be 85% composition (percentage by weight) the Y zeolite carrier impregnation in solution of potassium carbonate, left standstill 24 hours, through 120 ℃ of dryings, 550 ℃ of roastings made catalyst in 4 hours, all the other conditions are with embodiment 1.Reaction condition is as follows: pressure=4.0MPa, temperature=130 ℃, potash: expoxy propane: iodomethane mol ratio=0.004: 1: 0.03, reaction time is 2 hours, product is through gas chromatographic analysis, and the conversion ratio of expoxy propane is 77.9%, and the yield of propene carbonate is 75.3%.
Claims (6)
1. the catalyst of a synthesizing acrylic ester is characterized in that catalyst weight percentage consists of:
Sylvite 10-20%
Active carbon, metal oxide or molecular sieve 80-90%
2. the catalyst of a kind of synthesizing acrylic ester according to claim 1 is characterized in that described sylvite is potassium hydroxide, potash, potassium nitrate or potassium acetate.
3. the catalyst of a kind of synthesizing acrylic ester according to claim 1 is characterized in that described metal oxide is zirconia, zinc oxide, aluminium oxide or magnesia.
4. the catalyst of a kind of synthesizing acrylic ester according to claim 1, the specific area that it is characterized in that described active carbon is a 700-1000 rice
2/ gram, particle diameter is less than 80 orders.
5. the catalyst of a kind of synthesizing acrylic ester according to claim 1 is characterized in that described molecular sieve is A, X, Y type.
6. according to the Application of Catalyst method of each described a kind of synthesizing acrylic ester of claim 1-5, it is characterized in that comprising the steps:
Mol ratio by sylvite in the catalyst and expoxy propane and iodomethane is a sylvite: expoxy propane: iodomethane=0.003-0.01: 1: 0.02-0.03, sylvite, expoxy propane and iodomethane are added in the reactor, and the carbon dioxide of feeding 2.0-6.OMPa, under stirring condition, be warming up to 120-180 ℃, reacted 0.5-2 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021587019A CN1151118C (en) | 2002-12-26 | 2002-12-26 | Catalyst of synthetic propylene and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021587019A CN1151118C (en) | 2002-12-26 | 2002-12-26 | Catalyst of synthetic propylene and application thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1424141A true CN1424141A (en) | 2003-06-18 |
| CN1151118C CN1151118C (en) | 2004-05-26 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718964A (en) * | 2012-07-09 | 2012-10-10 | 广西民族大学 | Preparation method of non-isocyanate polyurethane and application of non-isocyanate polyurethane in spraying polyurea |
| CN105214731A (en) * | 2014-07-03 | 2016-01-06 | 中国石油化工股份有限公司 | Catalyst and the method thereof of ethylene carbonate is prepared for oxirane and carbon dioxide |
| CN107417660A (en) * | 2017-04-11 | 2017-12-01 | 山东德普化工科技有限公司 | A kind of device, technique and the solid catalyst of vapor phase method synthesizing acrylic ester |
-
2002
- 2002-12-26 CN CNB021587019A patent/CN1151118C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718964A (en) * | 2012-07-09 | 2012-10-10 | 广西民族大学 | Preparation method of non-isocyanate polyurethane and application of non-isocyanate polyurethane in spraying polyurea |
| CN105214731A (en) * | 2014-07-03 | 2016-01-06 | 中国石油化工股份有限公司 | Catalyst and the method thereof of ethylene carbonate is prepared for oxirane and carbon dioxide |
| CN105214731B (en) * | 2014-07-03 | 2018-02-13 | 中国石油化工股份有限公司 | The catalyst and its method of ethylene carbonate are prepared for oxirane and carbon dioxide |
| CN107417660A (en) * | 2017-04-11 | 2017-12-01 | 山东德普化工科技有限公司 | A kind of device, technique and the solid catalyst of vapor phase method synthesizing acrylic ester |
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| Publication number | Publication date |
|---|---|
| CN1151118C (en) | 2004-05-26 |
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