CN101780418B - Catalyst for preparing propylene carbonate and application thereof - Google Patents
Catalyst for preparing propylene carbonate and application thereof Download PDFInfo
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- CN101780418B CN101780418B CN2010101107879A CN201010110787A CN101780418B CN 101780418 B CN101780418 B CN 101780418B CN 2010101107879 A CN2010101107879 A CN 2010101107879A CN 201010110787 A CN201010110787 A CN 201010110787A CN 101780418 B CN101780418 B CN 101780418B
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- carbon dioxide
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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
Abstract
The invention relates to a catalyst for preparing propylene carbonate through the reaction of carbon dioxide and propylene oxide and the application thereof. The catalyst comprises a main catalyst ruthenium pyridine compound and an auxiliary catalyst quaternary. The molar ratio of the main catalyst to the auxiliary catalyst is 1:1 to 2, and the molar ratio of the main catalyst to the is 1:800 to 10000. The catalyst is used to catalyze the reaction of the carbon dioxide and the propylene oxide, so as to synthesize the propylene carbonate with high yield and high selectivity. The catalyst can be reused.
Description
Technical field
The present invention relates to a kind of catalyst that is used to prepare propene carbonate, and be used for application by carbon dioxide and propylene oxide propene carbonate as catalyst.
Background technology
Carbon dioxide is main greenhouse gases, is a low pollution of stabilizing carbon dioxide, eco-friendly effective way through carbon dioxide and epoxide prepared in reaction cyclic carbonate.Propene carbonate (PC) by carbon dioxide preparation is a kind of higher boiling, aprotic organic solvent and organic synthesis intermediate of function admirable, and, dimethyl carbonate production by transesterification synthetic at fine chemicals, ring-opening polymerisation prepare fields such as macromolecular compound, decarbonizing urea, gas separation, battery electrolyte and metal extraction and be used widely.
The catalyst of having reported at present that is used for catalysis carbon dioxide and propylene oxide propene carbonate mainly is (Angew.Chem.Int.Ed. such as quaternary ammonium salt, phosphonium salt, alkali metal salt, Mg-Al composite oxides, aluminium phthalocyanine-MCM41, Schiff alkali complex, ionic-liquid catalyst; 2009; 48,2946; J.Mol.Catal.A:Chem., 2008,284,52; US 7,365, and 214; US5,283,356; US 6,258, and 962; US 6,924, and 379; ZL 200610169682.4; ZL0214733.0).Shortcomings such as these catalyst exist respectively more or less that catalytic activity is low, poor selectivity, severe reaction conditions, product and catalyst separation difficulty, accessory substance are many, catalyst cost height.Therefore develop the catalytic activity height, selectivity is good, reaction condition is gentle, the catalyst of economic environmental protection, is the research content of utilizing carbon dioxide and epoxide prepared in reaction cyclic carbonate.
According to bibliographical information, ruthenium porphyrin complex (catalysis journal, 2007,28; 287) and 2,2 '-bipyridyl ruthenium complex (J.Mol.Catal.A:Chem., 2007; 277,35) in the presence of co-catalyst, the cycloaddition reaction of carbon dioxide and epoxide had advantages of high catalytic activity; Can be under relatively mild reaction condition catalytic synthesis of C acid propylene ester, but the Preparation of Catalyst cost is higher, is unfavorable for that commercial production uses.
Summary of the invention
The purpose of this invention is to provide a kind ofly under gentle relatively condition, have high activity, high selectivity and can be repeatedly used, be used for the catalyst of catalysis carbon dioxide and propylene oxide reaction synthesizing acrylic ester.
Technical scheme of the present invention is following.
A kind of catalyst that is used for synthesizing acrylic ester, said catalyst is made up of major catalyst and co-catalyst:
Major catalyst is to be the ruthenium pyridine complex of feedstock production by pyridine, ruthenium trichloride etc., and structural formula is:
The concrete preparation of this complex can carry out with reference to pertinent literature (for example referring to Inorg.Chem., 1995,34,593; Acta Cryst., 1994, C50,1406 etc.).
Co-catalyst is that chemical formula is R
1R
2 3NX
1Quaternary ammonium salt, wherein, R
1Be C
1～18Alkyl, R
2Be C
1～8Alkyl or aryl, X are Cl, Br or I.
Major catalyst and co-catalyst mol ratio are 1: 1～2.
The co-catalyst quaternary ammonium salt is preferably TBAB, tetrabutylammonium chloride, dodecyl trimethyl ammonium iodide, hexadecyltrimethylammonium chloride or softex kw.
The above-mentioned catalyst of being made up of major catalyst and co-catalyst is prepared propene carbonate as the catalyst of carbon dioxide and propylene oxide reaction.
Is 1: 1～2 to put into pre-dry stainless steel autoclave after preparing with major catalyst and co-catalyst according to mol ratio; Vacuumize; With air in high pure nitrogen or the carbon dioxide replacement still; In agitated reactor, add the expoxy propane that purifying is crossed with syringe then, feed carbon dioxide, cooling stops reaction behind the reacting by heating certain hour; Reactant liquor is moved to vacuum distillation apparatus, and cut is collected in decompression distillation, promptly makes propene carbonate.
Its reaction condition is, the mol ratio of major catalyst and expoxy propane is 1: 800～10000, and reaction temperature is 50～120 ℃, and the carbon dioxide initial pressure is 1～4MPa, and the reaction time is 1～8 hour, does not add any solvent in the course of reaction.Be, when confirming the ratio of catalyst and reactant, to be benchmark therefore what this described with the major catalyst because major catalyst and co-catalyst mol ratio are 1: 1～2.
The bottoms of synthesizing acrylic ester can repeat to carry out catalytic reaction next time as catalyst; Bottoms are not seen accessory substances such as Merlon and polyethers through analyzing, and reaction generates the selectivity of cyclic carbonate near 100%.
Compared with prior art, the invention has the advantages that:
1. Preparation of Catalyst is simple, and catalytic efficiency is high, and selectivity is good, and catalyst can repeatedly simply be reused and keep catalyst activity constant basically, and need not do any processing before the catalyst repeated use.
2. utilize catalyst synthesizing acrylic ester of the present invention, catalytic reaction condition is gentle relatively, and catalyst amount is less, and yield is high, and selectivity is good, and is simple to operate; Product and catalyst separation are easy, and purity is high.
The specific embodiment
Below in conjunction with embodiment the present invention is further described, but be not limited to the following example.
Among the embodiment below, py representes pyridine.
Embodiment 1
With 0.12 * 10
-3The major catalyst Ru (py) of mole
4Cl
2With 0.12 * 10
-3The co-catalyst softex kw of mole is put into pre-dry 100mL stainless steel autoclave; Vacuumize drying; Change air in the still with the high pure nitrogen device, add the expoxy propane 16mL (0.228 mole) that purifying is crossed, heat temperature raising to 80 ℃; Feed carbon dioxide to 3MPa, cooling stops reaction behind the reaction 4h.Reactant liquor is moved into vacuum distillation apparatus, decompression distillation, the cut of 76-78 ℃/3mmHg of collection is propene carbonate, weighs 23.0 grams, and yield is 98.6%.Bottoms are transferred to autoclave, to carry out catalytic reaction next time as catalyst.
Embodiment 2
Residue with distillation propene carbonate among the embodiment 1 is transferred in the autoclave identical with embodiment 1, and circulation is used as catalyst; Add the expoxy propane 16ml that purifying is crossed once more, react, reaction condition is with embodiment 1; Get propene carbonate 22.9 grams, yield is 98.3%.
Embodiment 3
Using in the identical equipment with embodiment 1, under identical condition, co-catalyst replaces softex kw with TBAB; React, heat temperature raising to 100 ℃ feeds carbon dioxide to 2.5MPa; Reaction 6h obtains propene carbonate 22.4 grams, and yield is 96.1%.
Embodiment 4
Using in the identical equipment with embodiment 1, under identical condition, co-catalyst replaces softex kw with dodecyl trimethyl ammonium iodide; React; Heat temperature raising to 75 ℃ feeds carbon dioxide to 2.5MPa, reaction 7h; Obtain propene carbonate 22.7 grams, yield is 97.4%.
Embodiment 5
Using in the identical equipment with embodiment 1, under identical condition, major catalyst is with 0.033 * 10
-3The Ru (py) of mole
4Cl
2, co-catalyst is with 0.049 * 10
-3The softex kw of mole adds the expoxy propane 4ml (0.057 mole) that purifying is crossed, and heat temperature raising to 100 ℃ feeds carbon dioxide to 2.0MPa, reacts, and reaction 4h obtains propene carbonate 5.5 grams, and yield is 94.5%.
Embodiment 6
Using in the identical equipment with embodiment 7, under identical condition, heat temperature raising to 60 ℃ feeds carbon dioxide to 4.0MPa, react, reaction 8h, propene carbonate 4.1 grams, yield is 70.4%.
Claims (4)
1. catalyst that is used to prepare propene carbonate is characterized in that said catalyst is made up of major catalyst and co-catalyst, and wherein major catalyst is the ruthenium pyridine complex, and its structural formula is:
Co-catalyst is to be TBAB, tetrabutylammonium chloride, dodecyl trimethyl ammonium iodide or softex kw, and the mol ratio of major catalyst and co-catalyst is 1: 1～2.
2. method by carbon dioxide and propylene oxide propene carbonate; It is characterized in that adopting the described catalyst of claim 1 as catalyst; Wherein the mol ratio of major catalyst and expoxy propane is 1: 800～10000, and reaction temperature is 50～120 ℃, and the carbon dioxide initial pressure is 1～4MPa; Reaction time is 1～8 hour, does not use any solvent in the course of reaction.
3. the method for synthesizing acrylic ester according to claim 2 is characterized in that the bottoms of synthesizing acrylic ester repeat to carry out catalytic reaction next time as catalyst.
4. catalyst according to claim 1 is used for the application by carbon dioxide and propylene oxide propene carbonate as catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101107879A CN101780418B (en) | 2010-02-10 | 2010-02-10 | Catalyst for preparing propylene carbonate and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101107879A CN101780418B (en) | 2010-02-10 | 2010-02-10 | Catalyst for preparing propylene carbonate and application thereof |
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| CN101780418A CN101780418A (en) | 2010-07-21 |
| CN101780418B true CN101780418B (en) | 2012-03-14 |
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| CN2010101107879A Expired - Fee Related CN101780418B (en) | 2010-02-10 | 2010-02-10 | Catalyst for preparing propylene carbonate and application thereof |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106831583B (en) * | 2017-01-19 | 2019-05-10 | 河南大学 | N, N- dialkyl group substituted pyrazolecarboxylic ionic liquid, preparation method and its method for catalyzing and synthesizing propene carbonate |
| CN114917892A (en) * | 2022-06-07 | 2022-08-19 | 中国科学技术大学 | Preparation method of carbon-based metal monatomic catalyst in carbon dioxide cycloaddition reaction |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5283356A (en) * | 1992-08-03 | 1994-02-01 | Texaco Chemical Company | Process for manufacturing alkylene carbonates using metal phthalocyanine catalysts |
| CN1775356A (en) * | 2005-12-01 | 2006-05-24 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing propylene carbonate and its preparing method and use |
| CN1947842A (en) * | 2006-11-07 | 2007-04-18 | 郑州大学 | Catalyst for synthesizing propene carbonate, and its application method |
| CN1955152A (en) * | 2005-10-28 | 2007-05-02 | 华东理工大学 | Method for continuous preparing 1,2,-propylene glycol |
-
2010
- 2010-02-10 CN CN2010101107879A patent/CN101780418B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5283356A (en) * | 1992-08-03 | 1994-02-01 | Texaco Chemical Company | Process for manufacturing alkylene carbonates using metal phthalocyanine catalysts |
| CN1955152A (en) * | 2005-10-28 | 2007-05-02 | 华东理工大学 | Method for continuous preparing 1,2,-propylene glycol |
| CN1775356A (en) * | 2005-12-01 | 2006-05-24 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing propylene carbonate and its preparing method and use |
| CN1947842A (en) * | 2006-11-07 | 2007-04-18 | 郑州大学 | Catalyst for synthesizing propene carbonate, and its application method |
Non-Patent Citations (1)
| Title |
|---|
| Kim et al..New Mechanistic Insight into the Coupling Reactions of CO2 and Epoxides in the Presence of Zinc Complexes.《Chemistry-A European Journal》.2003,第9卷(第3期),P678-686. * |
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