CN1118325C - Catalyst for synthesizing dimethyl carbonate and its application - Google Patents
Catalyst for synthesizing dimethyl carbonate and its application Download PDFInfo
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- CN1118325C CN1118325C CN 01110587 CN01110587A CN1118325C CN 1118325 C CN1118325 C CN 1118325C CN 01110587 CN01110587 CN 01110587 CN 01110587 A CN01110587 A CN 01110587A CN 1118325 C CN1118325 C CN 1118325C
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- carbonate
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Abstract
The present invention provides a catalyst of synthesizing dimethyl carbonate by methanol and ethylene carbonate or propylene carbonate, which comprises the constituents of the following weight percentage of 1% to 40% of alkali metal hydroxide, alkali carbonate, alkali metal nitrate or alkali earth metal nitrate and 60% to 99% of metal oxide, active carbon, alkali earth metal phosphate or alkali earth metal carbonate. The prepared catalyst has the advantages of easy separation from products, simple preparation, low cost, difficult loss of active constituents, etc., and the dimethyl carbonate can be synthesized with high activity and high selectivity under the condition that the molar ratio of the methanol and the propylene carbonate is low. Reaction temperature is from 50 to 130 DEG C, reaction pressure is from 0 to 1.0MPa, liquid airspeed is from 0.1 to 4 hr<-1>, and the feeding molar ratio of ester and alcohol is 1: (2 to 7).
Description
The invention belongs to a kind of solid alkali catalyst, carry out transesterification reaction, simultaneously Synthesis of dimethyl carbonate and dibasic alcohol by methyl alcohol and NSC 11801 or propylene carbonate.
As a kind of green basic chemical industry raw material and organic synthesis intermediate, the synthetic and application of methylcarbonate (Dimethyl Carbonate is called for short DMC) gets more and more people's extensive concerning in recent years.Jiang Qi etc. (gas chemical industry, 1997,22 (5), 1) study the transesterification reaction of propylene carbonate, think that sodium hydroxide, sodium methylate and yellow soda ash are the high activated catalysts of transesterification reaction.(chemical reaction engineering and technology such as Zhang Shaogang, the optimal reaction temperature of transesterification reaction is 60～65 ℃ when 1991,7 (1), 10) having determined that sodium methylate is made catalyzer, catalyst levels is 0.4%～0.45%, and the mol ratio of propylene carbonate and methyl alcohol is 1: 8～10.Because ester and pure mol ratio are higher, then cause unit volume throughput low, separation and purification equipment is huge, the cost of equipment height, and economic feasibility is relatively poor during industrial production.US 4661609 has reported the soluble salt of zirconium, titanium and tin or the catalyzer that complex compound also can be used as transesterification reaction, for example zirconium is made catalyzer, temperature of reaction is 130 ℃, and methyl alcohol and NSC 11801 mol ratio are 4.7 o'clock, and the transformation efficiency of NSC 11801 reaches 89%.US 4307032 reports use the catalyzer of thallium compound as transesterification reaction, under relative low temperature, low catalyst concentration, can obtain high speed of reaction.But above-mentioned reaction is a homogeneous reaction, and catalyzer is to the equipment requirements complexity, the product separation difficulty, and some reaction system is serious to equipment corrosion in reaction process, brings very big difficulty to industrial production.
The invention provides and a kind ofly have very high reactivity and stability, and solid catalyst that is easy to from product, separate and application thereof.
The objective of the invention is to realize by following steps, adopt alkali metal hydroxide, alkaline carbonate, base metal nitrate or alkine earth metal nitrate active component solution to be impregnated on metal oxide, gac, alkali earth metal phosphate or the carbonate carrier, make solid catalyst.
Its catalyst weight per-cent consists of: alkali metal hydroxide, alkaline carbonate, base metal nitrate or alkine earth metal nitrate 1-40%
Metal oxide, gac, alkali earth metal phosphate or alkaline earth metal carbonate 60-99%
Aforesaid alkali metal hydroxide is potassium hydroxide, sodium hydroxide, lithium hydroxide or cesium hydroxide.
Aforesaid alkaline carbonate is salt of wormwood, yellow soda ash, Quilonum Retard or cesium carbonate.
Aforesaid base metal nitrate is saltpetre, SODIUMNITRATE, cesium nitrate or lithium nitrate.
Aforesaid alkine earth metal nitrate is nitrocalcite or magnesium nitrate.
Aforesaid metal oxide is magnesium oxide, calcium oxide, zirconium white, zinc oxide or aluminum oxide.
Aforesaid gac is that specific surface area is a 700-1200 rice
2/ gram, particle diameter is less than 60 purpose coal activated carbon or active fruit shell carbons.
Aforesaid alkali earth metal phosphate is trimagnesium phosphate or calcium phosphate.
Aforesaid alkaline earth metal carbonate is magnesiumcarbonate, lime carbonate, Strontium carbonate powder or barium carbonate.
Catalyst activity component is preferably yellow soda ash, sodium hydroxide, and weight percent consists of 10-30%.
Carrier is preferably trimagnesium phosphate, calcium oxide, and weight percent consists of 70-90%.
Preparation method of the present invention adopts pickling process, with support of the catalyst 300-700 ℃ of following roasting 2 hours, by the composition of above-mentioned catalyzer with carrier impregnation in active constituent solution, left standstill 24 hours, through 120 ℃ of dryings, made catalyzer at 300-700 ℃ of following roasting 3-6 hour.The reaction conditions of catalyzer is as follows: temperature of reaction is 50-130 ℃, and reaction pressure is 0-1.0MPa, and the liquid air speed is 0.1-4hr
-1, the raw materials components mole ratio of ester and alcohol is 1: 2～7.
The present invention has following advantage:
(1) the solid alkali catalyst preparation is simple, cheap and easy to get, and catalyzer is easy to separate from product.
(2) under the lower condition of methyl alcohol and propylene carbonate mol ratio, high reactivity and highly selective Synthesis of dimethyl carbonate need not a large amount of methanol loop utilizations.
(3) the recyclable utilization of by-product glycol, the entire reaction course nontoxicity.
(4) solid alkali has the very strong resistant to carbon dioxide and the performance of water intoxication, and corrodibility is little, and active constituent is difficult for running off.
Embodiments of the invention are as follows:
Embodiment 1
By cesium carbonate is 1%, aluminum oxide is that 99% composition (weight percent) is impregnated into aluminum oxide in the cesium carbonate solution, left standstill 24 hours, through 120 ℃ of dryings, 500 ℃ of roastings made catalyzer in 4 hours, compression molding then is crushed in the reactor of packing into behind the 20-40 order, and transesterification reaction is carried out in continuous fixed bed reactor.When temperature of reactor is raised to preset temperature, respectively methyl alcohol and propylene carbonate are pumped in the reactor with liquid feeding, reaction conditions is as follows: normal pressure, temperature=120 ℃, air speed=0.1hr
-1Methyl alcohol/propylene carbonate mol ratio=4: 1, reaction product obtains following result through gas chromatographic analysis: the propylene carbonate ester products is formed (wt%) DMC yield transformation efficiency (%) the methyl alcohol DMC propylene glycol propylene carbonate (%) that distributes
43.63 42.91 15.11 16.09 25.89 38.01
Embodiment 2
By sodium hydroxide is 5%, and calcium oxide is that 95% composition (weight percent) is impregnated into calcium oxide in the sodium hydroxide solution, and all the other are with embodiment 1.Reaction conditions is as follows: pressure=0.1MPa, temperature=110 ℃, air speed=0.5h
-1Methyl alcohol/propylene carbonate mol ratio=3: 1, reaction product obtains following result through gas chromatographic analysis: the propylene carbonate ester products is formed (wt%) DMC yield transformation efficiency (%) the methyl alcohol DMC propylene glycol propylene carbonate (%) that distributes
50.3 45.69 18.14 18.95 17.22 45.5
Embodiment 3
By yellow soda ash is 10%, and trimagnesium phosphate is that 90% composition (weight percent) is impregnated into trimagnesium phosphate in the sodium carbonate solution, and all the other are with embodiment 1, and reaction conditions is as follows: pressure=0.2MPa, temperature=100 ℃, air speed=1.0h
-1Methyl alcohol/propylene carbonate mol ratio=2: 1, reaction product obtains following result through gas chromatographic analysis: the propylene carbonate ester products is formed (wt%) DMC yield transformation efficiency (%) the methyl alcohol DMC propylene glycol propylene carbonate (%) that distributes
65.05 31.09 20.86 21.46 26.59 52.99
Embodiment 4
By nitrocalcite is 15%; gac is that 85% composition (weight percent) is impregnated into 16-30 purpose gac in the calcium nitrate aqueous solution; left standstill 24 hours; through 120 ℃ of dryings; roasting is 4 hours under 600 ℃ of N2 gas shileds; reaction conditions is as follows: reaction conditions is as follows: pressure=0.3MPa, temperature=90 ℃, air speed=1.5h
-1Methyl alcohol/propylene carbonate mol ratio=4: 1, reaction product obtains following result through gas chromatographic analysis: the propylene carbonate ester products is formed (wt%) DMC yield transformation efficiency (%) the methyl alcohol DMC propylene glycol propylene carbonate (%) that distributes
35.5 46.1 12.6 11.9 29.4 31.2
Embodiment 5
By Quilonum Retard is 20%, and zinc oxide is that 80% composition (weight percent) is impregnated into zinc oxide in the lithium carbonate aqueous solution, and all the other are with embodiment 1.Reaction conditions is as follows: pressure=0.7MPa, temperature=80 ℃, air speed=2.0h
-1Methyl alcohol/propylene carbonate mol ratio=6: 1, reaction product obtains following result through gas chromatographic analysis: the propylene carbonate ester products is formed (wt%) DMC yield transformation efficiency (%) the methyl alcohol DMC propylene glycol propylene carbonate (%) that distributes
58.39 39.9 17.6 18.3 24.2 49.9
Embodiment 6
Saltpetre is 25%, and lime carbonate is that 75% composition (weight percent) is impregnated into lime carbonate in the potassium nitrate solution, and all the other are with embodiment 1.Reaction conditions is as follows: pressure=0.6MPa, temperature=70 ℃, air speed=2.5h
-1Methyl alcohol/propylene carbonate mol ratio=3: 1, the gained result is: the propylene carbonate ester products is formed (wt%) DMC yield transformation efficiency (%) the methyl alcohol DMC propylene glycol propylene carbonate (%) that distributes
45.63 38.9 16.11 17.09 27.8 39.01
Embodiment 7
Potassium hydroxide is 30%, and zirconium white is that 70% composition (weight percent) is impregnated into zirconium white in the potassium hydroxide solution, and all the other are with embodiment 1.Reaction conditions is as follows: pressure=0.4MPa, temperature=60 ℃, air speed=3.0h
-1Methyl alcohol/propylene carbonate mol ratio=7: 1, the gained result is: the propylene carbonate ester products is formed (wt%) DMC yield transformation efficiency (%) the methyl alcohol DMC propylene glycol propylene carbonate (%) that distributes
45.8 51.83 15.31 16.25 16.61 42.6
Embodiment 8
Strontium nitrate is 35%, and magnesium oxide is that 65% composition (weight percent) is impregnated into magnesium oxide in the strontium nitrate solution, and all the other are with embodiment 1.Reaction conditions is as follows: pressure=0.5MPa, temperature=50 ℃, air speed=3.5h
-1Methyl alcohol/propylene carbonate mol ratio=2: 1, the gained result is: the propylene carbonate ester products is formed (wt%) DMC yield transformation efficiency (%) the methyl alcohol DMC propylene glycol propylene carbonate (%) that distributes
27.8 44.21 8.79 9.65 37.35 19.6
Embodiment 9
By SODIUMNITRATE is 40%, and magnesiumcarbonate is that 60% composition (weight percent) is impregnated into magnesiumcarbonate in the sodium nitrate solution, and all the other are with embodiment 1.Reaction conditions is as follows: pressure=0.8MPa, temperature=100 ℃, air speed=1.5h
-1Methyl alcohol/propylene carbonate mol ratio=4: 1, reaction product obtains following result through gas chromatographic analysis: the propylene carbonate ester products is formed (wt%) DMC yield transformation efficiency (%) the methyl alcohol DMC propylene glycol propylene carbonate (%) that distributes
36.59 43.5 13.93 12.77 29.8 33.58
Embodiment 10
By salt of wormwood is 20%, and trimagnesium phosphate is that 80% composition (weight percent) is impregnated into trimagnesium phosphate in the solution of potassium carbonate, and all the other are with embodiment 1.Reaction conditions is as follows: pressure=1.0MPa, temperature=130 ℃, air speed=4.0h
-1Methyl alcohol/propylene carbonate mol ratio=3: 1, reaction product obtains following result through gas chromatographic analysis: the propylene carbonate ester products is formed (wt%) DMC yield transformation efficiency (%) the methyl alcohol DMC propylene glycol propylene carbonate (%) that distributes
45.42 45.35 15.72 12.60 26.33 41.85
Claims (11)
1. the catalyzer of a Synthesis of dimethyl carbonate is characterized in that catalyst weight per-cent consists of:
Alkali metal hydroxide, alkaline carbonate, base metal nitrate or alkine earth metal nitrate 1-40%
Metal oxide, gac, alkali earth metal phosphate or alkaline earth metal carbonate 60-99%.
2. the catalyzer of a kind of Synthesis of dimethyl carbonate as claimed in claim 1 is characterized in that described alkali metal hydroxide is potassium hydroxide, sodium hydroxide, lithium hydroxide or cesium hydroxide.
3. the catalyzer of a kind of Synthesis of dimethyl carbonate as claimed in claim 1 is characterized in that described alkaline carbonate is salt of wormwood, yellow soda ash, Quilonum Retard or cesium carbonate.
4. the catalyzer of a kind of Synthesis of dimethyl carbonate as claimed in claim 1 is characterized in that described base metal nitrate is saltpetre, SODIUMNITRATE, cesium nitrate or lithium nitrate.
5. the catalyzer of a kind of Synthesis of dimethyl carbonate as claimed in claim 1 is characterized in that described alkine earth metal nitrate is nitrocalcite or magnesium nitrate.
6. the catalyzer of a kind of Synthesis of dimethyl carbonate as claimed in claim 1 is characterized in that described metal oxide is magnesium oxide, calcium oxide, zirconium white, zinc oxide or aluminum oxide.
7. the catalyzer of a kind of Synthesis of dimethyl carbonate as claimed in claim 1 is characterized in that described gac is that specific surface area is a 700-1200 rice
2/ gram, particle diameter is less than 60 purpose coal activated carbon or active fruit shell carbons.
8. the catalyzer of a kind of Synthesis of dimethyl carbonate as claimed in claim 1 is characterized in that described alkali earth metal phosphate is trimagnesium phosphate or calcium phosphate.
9. the catalyzer of a kind of Synthesis of dimethyl carbonate as claimed in claim 1 is characterized in that described alkaline earth metal carbonate is magnesiumcarbonate, lime carbonate, Strontium carbonate powder or barium carbonate.
10. the catalyzer of a kind of Synthesis of dimethyl carbonate as claimed in claim 1 is characterized in that described catalyst weight per-cent consists of: yellow soda ash or sodium hydroxide 10-30%
Trimagnesium phosphate, calcium oxide or lime carbonate 70-90%.
11. the Application of Catalyst method of a Synthesis of dimethyl carbonate, temperature of reaction are 50-130 ℃, reaction pressure is 0-1.0MPa, and the liquid air speed is 0.1-4hr
-1, the raw materials components mole ratio of ester and alcohol is 1: 2～1: 7.
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| CN 01110587 CN1118325C (en) | 2001-04-16 | 2001-04-16 | Catalyst for synthesizing dimethyl carbonate and its application |
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| CN 01110587 CN1118325C (en) | 2001-04-16 | 2001-04-16 | Catalyst for synthesizing dimethyl carbonate and its application |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198744B (en) * | 2014-06-26 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of method of Synthesis of dimethyl carbonate |
| CN105272858B (en) * | 2014-07-24 | 2017-09-15 | 中国石油化工股份有限公司 | The production method of dimethyl carbonate |
| CN105344341B (en) * | 2015-10-26 | 2018-08-14 | 常州大学 | A kind of preparation method of solid catalyst for Synthesis of dimethyl carbonate |
| CN107915573B (en) * | 2016-10-08 | 2021-05-11 | 中国石油化工股份有限公司 | Method for synthesizing dimethyl carbonate |
| CN107649158B (en) * | 2017-10-19 | 2020-07-31 | 山东德普化工科技有限公司 | Catalyst for preparing dimethyl carbonate and method for preparing dimethyl carbonate |
| CN111545248A (en) * | 2020-05-15 | 2020-08-18 | 山东飞扬化工有限公司 | Solid phase catalyst for producing DMC and process thereof |
| CN114289040B (en) * | 2021-12-30 | 2023-09-19 | 天津大学浙江研究院 | Catalyst for gas phase synthesis of dimethyl carbonate and preparation method thereof |
| CN115463675A (en) * | 2022-10-26 | 2022-12-13 | 高化学（江苏）化工新材料有限责任公司 | Novel catalyst for synthesizing dimethyl carbonate and preparation method thereof |
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