CN102442992A - Method for synthesizing glycerol carbonate with biodiesel based crude glycerine and dimethyl carbonate - Google Patents
Method for synthesizing glycerol carbonate with biodiesel based crude glycerine and dimethyl carbonate Download PDFInfo
- Publication number
- CN102442992A CN102442992A CN2011103864666A CN201110386466A CN102442992A CN 102442992 A CN102442992 A CN 102442992A CN 2011103864666 A CN2011103864666 A CN 2011103864666A CN 201110386466 A CN201110386466 A CN 201110386466A CN 102442992 A CN102442992 A CN 102442992A
- Authority
- CN
- China
- Prior art keywords
- glycerine
- methylcarbonate
- reaction
- molecular sieve
- catalyzer
- 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.)
- Granted
Links
- JFMGYULNQJPJCY-UHFFFAOYSA-N OCC(CO1)OC1=O Chemical compound OCC(CO1)OC1=O JFMGYULNQJPJCY-UHFFFAOYSA-N 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a synthesis method of glycerol carbonate. With glycerin and dimethyl carbonate as raw materials, the method utilizes a cheap and easily available alkaline molecular sieve as a catalyst, and conducts a reaction at a temperature of 70-90DEG C for 2-10h. Cheap methanol can be adopted as a solvent, or no solvent is needed. With the process of the invention, glycerin has high conversion rate, glycerol carbonate has high selectivity, and the catalyst is stable, easy to recover and reusable. Meanwhile, the method employs dimethyl carbonate, glycerin and an alkaline molecular sieve catalyst as the raw materials, which are cheap and easily available and have mild reaction conditions. The glycerin conversion rate is high, and the generated glycerol carbonate has high purity which can be up to over 99% and less impurity. The method provided in the invention has the advantages of simple preparation process, no need for high temperature and high pressure equipment, non-toxic raw materials, low energy consumption, and great industrial prospects.
Description
Technical field
The present invention relates to a kind of compound method, specifically, is a kind of catalysis synthetic method of carbonic acid glyceride.
Background technology
Carbonic acid glyceride formal name used at school methylol dioxa penta cyclic ketones (molecular formula: C
4H
6O
4Molecular weight: 118.09, CAS:931-40-8) be a kind of important novel Chemicals; In the production of urethane foam, coating, washing composition, makeup, important use is arranged; Can be used as the new component of gas separation membrane, also can be used to produce Racemic glycidol, its verivate can be used as lithium battery electrolytes; And carbonic acid glyceride still is important midbody among the organic chemical industry.Because carbonic acid glyceride has boiling point height, flammable low, excellent characteristic such as toxicity is little, biodegradability, so the application of carbonic acid glyceride will progressively obtain promoting.
U.S. Pat P2446145 and Japanese Patent JP6009610-A have described the technology that a kind of glycerine and phosgene direct reaction prepare carbonic acid glyceride, and this technology has that temperature of reaction is low, transformation efficiency is high, good selective; But the raw material that this technology adopted (phosgene) severe toxicity, and when generating product, can discharge the hydrogenchloride that doubles product; Serious to equipment corrosion; Raffinate that is generated and waste water environmental pollution are serious, and operational condition is harsh, product aftertreatment difficulty; Basically, be eliminated at present, reaction formula is following:
European patent EP 0739888 and Japanese Patent JP6329663-A have reported the technology of glycerine and NSC 11801 prepared in reaction carbonic acid glyceride recently, and the catalyzer that adopts in the patent documentation is anionite-exchange resin, zeolite, MOX etc.; But utilizing this method that a great shortcoming is arranged, is exactly the generation along with the product carbonic acid glyceride, and the meeting generation waits the terepthaloyl moietie of amount of substance in the reaction; Since boiling point (197.85 ℃) height of terepthaloyl moietie, so the product separation difficulty is big, and be the process of a high energy consumption; Thereby increased production cost, be difficult to obtain purer carbonic acid glyceride; The carbonic acid glyceride of being sold in the market mainly adopts this technology, but purity has only 90% to 95%.The reaction formula of this technology is following:
German patent DE 4225870 has also been described a kind of glycerine and carbon monoxide and oxygen react carbonate synthesis glyceryl ester under cuprous chloride catalysis synthesis technique with U.S. Pat P5359094; But this method need be carried out under high temperature, high pressure; To the requirement of equipment than higher; And the raw material carbon monoxide is inflammable, and is explosive, and concrete reaction formula is following:
Catalysis Letters (the 56th volume in 1998; The 245-247 page or leaf) having proposed one under the effect imagines the method for glycerine and the direct carbonate synthesis glyceryl ester of supercritical co in the ethylene carbonate ester solvent, under catalyzer; But traditional solid acid-base, oxide catalyst all do not have activity.Within for some time subsequently, Journal of Molecular CatalysisA-Chemical (the 257th volume 149-153 page or leaf, 2006), modern chemical industry (the 28th volume; The 35-37 page or leaf; 2008) and the followed up on research of glycerine and carbonic acid gas direct reaction carbonate synthesis glyceryl ester of priority such as Journal ofMolecular Catalysis A-Chemical (the 304th volume, 1-7 page or leaf, 2009); Catalyst system therefor is organic bases and organo-tin compound in the document, and the yield of product is very low; But up to the present, this reaction of effective catalyzer catalysis does not efficiently also appear, and the pressure that this method need be very high, very high to the requirement of equipment, reaction formula is following:
Recently; World patent WO200050415-A, U.S. Pat 6025504, Chinese patent CN 101811971 A, Journal of Catalysis (the 268th volume, 106-114 page or leaf, 2009), Journal of Catalysis (the 269th volume; The 140-149 page or leaf; 2010), successively to have described with glycerine and urea again among the Catalysis Communication (the 12nd volume, 1458-1462 page or leaf, 2011) be the technology of feedstock production carbonic acid glyceride; Used catalyzer mainly contains hydrotalcite, MOX, zirconium phosphate, zinc Win 40350 etc., and the advantage of this method is that low in raw material cost is easy to get.But the most fatal shortcoming of this method is a reaction process need carry out under high vacuum (1-20Kpa), and the purpose of vacuum is to let the ammonia that generates leave reaction system gradually, and high to the energy consumption of the having relatively high expectations of equipment, process, reaction formula is following:
Japanese Patent 2001172277-A has described the method with glycerine and methylcarbonate carbonate synthesis glyceryl ester the earliest; The catalyzer that is adopted is an alkaline carbonate, but this catalyzer (be dissolved in glycerine and methylcarbonate, be homogeneous catalyst) separation difficulty such as salt of wormwood.Also the someone attempts solidifying lypase Novozym435 catalyzing glycerol and the synthetic carbon ester glyceryl ester of methylcarbonate (Journal of Molecular Catalysisi B-Enzymatic the 49th volume 75-78 page or leaf; 2007), remove methyl alcohol through in reaction system, adding the 5A molecular sieve, to increase speed of reaction; Good reaction result is arranged; But lypase costs an arm and a leg, easy inactivation, long reaction time.2009, bibliographical information has been arranged, and glycerine and methylcarbonate can prepare carbonic acid glyceride (Applied Catalysis A:General, the 366th volume under the quicklime effect; The 315-324 page or leaf; 2009), still, because quicklime is partly dissolved in the reaction system; Therefore catalyst loss is serious, is difficult to recycle; Simultaneously,, be difficult to direct reactivate and repeated use in air because quicklime is easy to and water and carbon dioxide reaction, need long roasting under the high temperature of 900 degree before sample uses; Deep research is further found: the high reactivity of quicklime in glycerine and dimethyl carbonate mainly is because quicklime can be dissolved in glycerine, generate homogeneous R-Glyceric acid calcium (Applied Catalysis A:General; The 15th volume; The 220-225 page or leaf; 2011), this not only causes catalyst loss, a large amount of by product to generate, and has brought great challenge for product separation and purification.
Recently, Chinese patent CN 101287710A has reported with Li/CaO to be catalyzer, with glycerine and methylcarbonate (cyclic carbonate) carbonate synthesis glyceryl ester.Chinese patent CN101717338A has reported that glycerine and methylcarbonate utilize the sequence of constant boiling and rectification coupling to prepare the method for carbonic acid glyceride; Used catalyzer is quicklime, strontium oxide, calcium methylate or calcium hydroxide; Equally; The reaction that quicklime, strontium oxide, sodium methylate, calcium hydroxide are made catalyzer is a homogeneous reaction, and there is separation difficulty in catalyzer, problem such as instability, easy inactivation in air.2010; Green Chemistry (the 12nd volume; The 578-581 page or leaf) reported to be the method for catalyzer, glycerine and dimethyl carbonate carbonate synthesis glyceryl ester with the magnesium aluminum-hydrotalcite; But this catalyst levels is big, and reaction needed is carried out in the solvent (N, N,N-DIMETHYLACETAMIDE, DMSO 99.8MIN. or acetonitrile) of costliness.2011; Applied Chemistry A:General (the 401st volume; The 153-157 page or leaf) reported also in the magnalium zirconium mixed oxide to be used for the method for glycerine and dimethyl carbonate carbonate synthesis glyceryl ester that have only 94% but glycerol conversion yield is the highest, reaction formula is following as catalyzer:
Document and patent specification above comprehensive can be found: with glycerine and methylcarbonate is that raw material carbonate synthesis glyceryl ester has and has many good qualities; By product (methyl alcohol) gentle such as: reaction conditions, that generate is easy to remove, does not need high pressure, also need not vacuumize, and material carbon dimethyl phthalate toxicity very little, do not need harsh especially production unit; Therefore this technology can overcome the shortcoming of other method, will become carbonic acid glyceride synthetic main flow gradually.But; The glycerine of having reported at present and the catalyzer of the direct carbonate synthesis glyceryl ester of methylcarbonate all have certain shortcoming; Is prone to inactivation such as: quicklime during as catalyzer, is prone to run off, and reaction is a part homogenous process that dissolved partially oxidation calcium has promoted the generation of R-Glyceric acid calcium in the reaction; Difficulty and cost that this has not only increased product separation and purification are difficult to obtain high-purity carbonic acid glyceride; And hydrotalcite is the solvent that transformation efficiency is low, reaction needed is expensive of glycerine as the catalyzer shortcoming, and final product is to purify through the distillatory method, so remaining glycerine can bring very high energy consumption.And immobilized enzyme is active low as catalyzer, costs an arm and a leg, and recycle is not good.
Summary of the invention
The object of the invention provides a kind of compound method of carbonic acid glyceride just to the deficiency of prior art, and this method is a raw material with glycerine and methylcarbonate, utilizes alkaline molecular sieve cheap and easy to get to be catalyzer, under 70-90 degree centigrade, carries out; Can adopt cheap methyl alcohol as solvent, also can not use solvent.Adopt this technology, glycerol conversion yield is high, the carbonic acid glyceride selectivity is high, and catalyzer is stablized, is prone to reclaim and reuse.
Concrete technical scheme of the present invention is following:
The present invention is the method for a kind of biodiesel base crude glycerine and methylcarbonate carbonate synthesis glyceryl ester, is raw material with glycerine and methylcarbonate, utilizes alkaline molecular sieve to be catalyzer, and reactions step is following:
(1) take by weighing a certain amount of glycerine and alkaline molecular sieve catalyst and join in the reactor drum that has reflux condensate device, the part by weight of control glycerine and catalyzer is 5～15: 1;
(2) in above-mentioned solution, add a certain amount of methylcarbonate, the mol ratio of control methylcarbonate and glycerine is 1～6: 1, stirs to make it to mix;
(3) mixed solution slowly is heated to the 70-100 degree, the reaction times was controlled at 2-10 hour;
(4) after reaction finishes, reaction solution is cooled to room temperature, centrifugal, separating catalyst; Underpressure distillation removes the methyl alcohol of dereaction generation and excessive methylcarbonate, obtains the bullion carbonic acid glyceride.
Alkaline molecular sieve catalyst of the present invention is NaBeta, NaX, any in the alkaline molecular sieve that NaY, other cationic exchange are crossed.
According to the preparation technology that the present invention adopted, required temperature of reaction low (70-100 ℃), reaction times short (2-10 hour), glycerol conversion yield high (40-100%), the yield of carbonic acid glyceride high (40-99%).
Beneficial effect of the present invention is following:
In the present invention, raw materials used is methylcarbonate, glycerine, alkaline molecular sieve catalyst, cheap and easy to get, and reaction conditions is gentle; Glycerol conversion yield is high, and the carbonic acid glyceride purity of generation is high, and impurity is few, and high carbon acid glyceryl ester purity can reach more than 99%; And preparation technology is simple, does not need high temperature, high-tension apparatus; Advantages of nontoxic raw materials, energy consumption is lower, and industrial prospect is arranged very much.
Embodiment
Through specific embodiment technical scheme of the present invention is further described below.
Embodiment 1
Take by weighing 5 gram glycerine and 0.5 gram NaY catalyzer (wherein the particle diameter of NaY alkaline molecular sieve catalyst is 820 nanometers), place 100 milliliters of three-necked flasks that have reflux condensate device; In above-mentioned solution, add 15 milliliters of methylcarbonates, stir and made it to mix in 10 minutes.Mixed solution slowly is heated to the 70-100 degree, reacted 4 hours.Reaction is cooled to room temperature with reaction solution, centrifugal, separating catalyst after finishing; Underpressure distillation removes the methyl alcohol of dereaction generation and excessive methylcarbonate; Add 10 ml methanol again, mix, underpressure distillation further steams lower-boiling impurity and solvent, obtains the bullion carbonic acid glyceride.
Under the table 1.NaY catalyzer under the differential responses temperature transformation efficiency of glycerine
| Temperature of reaction/℃ | 60 | 70 | 80 | 90 | 100 |
| Carbonic acid glyceride productive rate % | 45 | 80 | 90 | 98 | 100 |
Embodiment 2
With reference to the reaction conditions among the embodiment 1, different is that the adding catalyzer is that particle diameter is the NaY alkali type sieve catalyst of 1600 nanometers.Taking by weighing particle diameter is NaY catalyzer 0.5 gram of 1600 nanometers.Reaction conditions: temperature of reaction 70-100 ℃, in 5 hours reaction times, the transformation efficiency of glycerine is 99% in the time of 90 ℃, product through the productive rate of stratographic analysis carbonic acid glyceride be 96%, purity is 99%.
Embodiment 3
With reference to preparation process among the embodiment 1 and reaction conditions, the amount of different is all raw material glycerine, methylcarbonate, NaY catalyzer all expands original 10 times to.Take by weighing glycerine 50g, 150 milliliters of methylcarbonates, NaY catalyzer 5 grams, reaction conditions: 90 ℃ of temperature of reaction, in 4 hours reaction times, glycerol conversion yield is 98%; Product through the productive rate of stratographic analysis carbonic acid glyceride be 95%, purity is 99%.
Embodiment 4
With reference to preparation process among the embodiment 1 and reaction conditions, different is that the adding catalyzer is the NaBeta molecular sieve.Take by weighing NaBeta catalyzer 0.5 gram.Reaction conditions: temperature of reaction 70-100 ℃, reaction times 3-10 hour, 90 ℃ of reactions 7 hours, the transformation efficiency of glycerine was 95%; Product through the productive rate of stratographic analysis carbonic acid glyceride be 94%, purity is 99%.
Embodiment 5
With reference to preparation process among the embodiment 1 and reaction conditions, different is that the adding catalyzer is a K type X sieve catalyst.
Take by weighing K type X sieve catalyst 0.5 gram.Reaction conditions: temperature of reaction 70-100 ℃, reaction times 3-10 hour, 90 ℃ of reactions 3 hours, the transformation efficiency of glycerine was 97%; Product through the productive rate of stratographic analysis carbonic acid glyceride be 95%, purity is 99%.
Claims (2)
1. the method for biodiesel base crude glycerine and methylcarbonate carbonate synthesis glyceryl ester is characterized in that, is raw material with glycerine and methylcarbonate, utilizes alkaline molecular sieve to be catalyzer, and reactions step is following:
(1) take by weighing a certain amount of glycerine and alkaline molecular sieve catalyst and join in the reactor drum that has reflux condensate device, the part by weight of control glycerine and catalyzer is 5～15: 1;
(2) in above-mentioned solution, add a certain amount of methylcarbonate, the mol ratio of control methylcarbonate and glycerine is 1～6: 1, stirs to make it to mix;
(3) mixed solution slowly is heated to the 70-100 degree, the reaction times was controlled at 2-10 hour;
(4) after reaction finishes, reaction solution is cooled to room temperature, centrifugal, separating catalyst; Underpressure distillation removes the methyl alcohol of dereaction generation and excessive methylcarbonate, obtains the bullion carbonic acid glyceride.
2. the method for biodiesel base crude glycerine according to claim 1 and methylcarbonate carbonate synthesis glyceryl ester is characterized in that described alkaline molecular sieve is NaBeta, NaX, any in the alkaline molecular sieve that NaY, other cationic exchange are crossed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110386466.6A CN102442992B (en) | 2011-11-29 | 2011-11-29 | Method for synthesizing glycerol carbonate with biodiesel based crude glycerine and dimethyl carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110386466.6A CN102442992B (en) | 2011-11-29 | 2011-11-29 | Method for synthesizing glycerol carbonate with biodiesel based crude glycerine and dimethyl carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102442992A true CN102442992A (en) | 2012-05-09 |
| CN102442992B CN102442992B (en) | 2014-03-26 |
Family
ID=46005971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110386466.6A Expired - Fee Related CN102442992B (en) | 2011-11-29 | 2011-11-29 | Method for synthesizing glycerol carbonate with biodiesel based crude glycerine and dimethyl carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102442992B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436369A (en) * | 2013-09-04 | 2013-12-11 | 西安石油大学 | Method for synchronously preparing biodiesel and glycerol carbonate under acceleration action of methanol |
| CN104324753A (en) * | 2014-10-11 | 2015-02-04 | 江苏常州酞青新材料科技有限公司 | Preparation method of catalyst for carbon monoxide-method synthesis of glycerol carbonate |
| CN105038997A (en) * | 2015-09-01 | 2015-11-11 | 中国科学院广州能源研究所 | Method for synchronously preparing biodiesel and glycerol carbonate through ionic liquid and catalytic grease |
| CN109369392A (en) * | 2018-11-02 | 2019-02-22 | 安徽工程大学 | A kind of synthetic method of two carbonic ester of the dimethyl of straight chain containing ether-oxygen bond |
| CN114014338A (en) * | 2021-10-20 | 2022-02-08 | 中新国际联合研究院 | Method for preparing doped carbon by purifying sodium chloride through pyrolysis of organic waste salt |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0739888A1 (en) * | 1995-04-24 | 1996-10-30 | Organisation Nationale Interprofessionnelle Des Oleagineux- Onidol | Process for the preparation of glycerol carbonat from glycerol and a cyclic organic carbonat, especially ethylene or propylene carbonate |
-
2011
- 2011-11-29 CN CN201110386466.6A patent/CN102442992B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0739888A1 (en) * | 1995-04-24 | 1996-10-30 | Organisation Nationale Interprofessionnelle Des Oleagineux- Onidol | Process for the preparation of glycerol carbonat from glycerol and a cyclic organic carbonat, especially ethylene or propylene carbonate |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436369A (en) * | 2013-09-04 | 2013-12-11 | 西安石油大学 | Method for synchronously preparing biodiesel and glycerol carbonate under acceleration action of methanol |
| CN103436369B (en) * | 2013-09-04 | 2015-04-29 | 西安石油大学 | Method for synchronously preparing biodiesel and glycerol carbonate under acceleration action of methanol |
| CN104324753A (en) * | 2014-10-11 | 2015-02-04 | 江苏常州酞青新材料科技有限公司 | Preparation method of catalyst for carbon monoxide-method synthesis of glycerol carbonate |
| CN105038997A (en) * | 2015-09-01 | 2015-11-11 | 中国科学院广州能源研究所 | Method for synchronously preparing biodiesel and glycerol carbonate through ionic liquid and catalytic grease |
| CN109369392A (en) * | 2018-11-02 | 2019-02-22 | 安徽工程大学 | A kind of synthetic method of two carbonic ester of the dimethyl of straight chain containing ether-oxygen bond |
| CN109369392B (en) * | 2018-11-02 | 2021-11-23 | 安徽工程大学 | Synthesis method of ether oxygen bond-containing straight-chain dimethyl dicarbonate |
| CN114014338A (en) * | 2021-10-20 | 2022-02-08 | 中新国际联合研究院 | Method for preparing doped carbon by purifying sodium chloride through pyrolysis of organic waste salt |
| CN114014338B (en) * | 2021-10-20 | 2024-03-22 | 中新国际联合研究院 | Method for simultaneously preparing doped carbon by pyrolyzing and purifying sodium chloride from organic waste salt |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102442992B (en) | 2014-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101704751B (en) | Synthesis method of methyl ethyl carbonate | |
| CN102442992B (en) | Method for synthesizing glycerol carbonate with biodiesel based crude glycerine and dimethyl carbonate | |
| CN103467435B (en) | A kind of method preparing glycerol carbonate | |
| CN105344341B (en) | A kind of preparation method of solid catalyst for Synthesis of dimethyl carbonate | |
| CN102432565B (en) | Method for preparing 2-hydroxyethylpiperazine | |
| CN101717338A (en) | Method for preparing carbonic acid glyceride by catalytic reaction-azeotropic reification coupling | |
| CN110479258A (en) | A kind of high stability catalyst of levulic acid hydrogenation synthesis gamma-valerolactone and preparation method thereof | |
| CN102863335B (en) | Preparation method of diethyl succinate | |
| WO2014005417A1 (en) | Method for preparing dimethyl carbonate | |
| CN103721697A (en) | Catalyst for synthesizing propylene carbonate as well as preparation method and application of catalyst | |
| CN107089962B (en) | A method of maltol and homologue are prepared by molecular oxygen oxidation | |
| CN101830776A (en) | Method for synthesizing ethanol | |
| CN111423398A (en) | Method for preparing gamma-valerolactone from levulinic acid | |
| CN105013539B (en) | Solid phase catalyst for preparing methyl formate, preparation method therefor and application thereof | |
| CN101328125B (en) | Method for preparing diethyl carbonate by two-step coupling reaction | |
| CN106944050A (en) | A kind of catalyst for synthesizing 1,3 propane diols and its preparation method and application | |
| CN102993131B (en) | Method for utilizing o-chlorocyclohexanol to prepare cyclohexene oxide by cyclization | |
| CN106831391A (en) | The method that chemicals is prepared by microalgae Direct Hydrothermal oxidation | |
| CN102492559A (en) | Method for preparing biodiesel in novel alkaline ionic liquid | |
| CN102250051A (en) | Preparation method of glycerol carbonate | |
| CN104815683A (en) | Catalyst for synthesis of glycerol carbonate from carbon dioxide and glycerol | |
| CN108586193A (en) | A method of preparing 1,3-PD using 3- methoxy methyl propionates | |
| CN107597116A (en) | A kind of method that 1,4 pentanediols are prepared by copper-based catalysts direct hydrogenation levulic acid | |
| CN104098436A (en) | Method for low temperature synthesis of methanol | |
| Yu et al. | A simple multiple-amine heterogeneous composite for efficient conversion of CO2 to cyclic carbonates under atmospheric pressure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140326 Termination date: 20191129 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |