CN104815683A - Catalyst for synthesis of glycerol carbonate from carbon dioxide and glycerol - Google Patents
Catalyst for synthesis of glycerol carbonate from carbon dioxide and glycerol Download PDFInfo
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- CN104815683A CN104815683A CN201510145723.5A CN201510145723A CN104815683A CN 104815683 A CN104815683 A CN 104815683A CN 201510145723 A CN201510145723 A CN 201510145723A CN 104815683 A CN104815683 A CN 104815683A
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- catalyst
- carbon dioxide
- glycerol
- glycerine
- carbonate
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Abstract
The invention discloses a catalyst for synthesis of glycerol carbonate from carbon dioxide and glycerol. The catalyst is prepared by adopting an immersion method with meso-porous alumina as a carrier and one or more of alkali metal halides, alkali metal hydroxides and alkali metal carbonates as an active component, wherein the load capacity of the active component is 5-50wt%. An application process of the catalyst is characterized in that glycerol and epoxide are added to an autoclave according to a molar ratio of 1:1-10, the addition amount of the catalyst is 1-10% of the mass of glycerol, the initial pressure of carbon dioxide is 0.5-20MPa, the reaction temperature is 80-200DEG C, and the reaction time is 1-24h. A preparation method of the catalyst has the advantages of simplicity, high reaction efficiency, low cost, and green process due to adoption of carbon dioxide and glycerol as raw materials.
Description
Technical field
The invention belongs to the catalyst preparation technology of Industrial Catalysis technical field, particularly the preparation method of carbon dioxide and glycerine synthesis of glycerol carbonate catalyst and application.
Background technology
Along with wideling popularize of " green energy resource " production of biodiesel; output as its by-product glycerin also increases sharply, and drug on the market for glycerol market, how Appropriate application biological glycerol; be further converted to high value added product, biodiesel large-scale development is had important practical significance.Glycerol carbonate (GC) is a kind of important glycerol derivatives, main reaction intermediate, solvent, the electrolyte of lithium ion battery, the constituent of gas separation membrane, coating and the surfactant etc. being used as field of medicaments, or react with isocyanates, acrylate series products and produce polymer for fields such as coating, adhesive and lubricants.In addition, also can be used for the preparation of polyesters compound, as Merlon and polyurethane etc.
At present, the synthetic method of glycerol carbonate mainly contains phosgenation, carbonyl process, alcoholysis of urea and ester-interchange method etc.It is raw material that US Patent No. 2446145 is mentioned with glycerine, prepares carbonic acid glyceride with phosgene reaction.But the raw material phosgene of this method application is extremely toxic substance, and a large amount of hydrogen chloride produced in course of reaction easily cause environmental pollution, are eliminated gradually.US Patent No. 5359094 reports glycerine and carbon monoxide/oxygen reaction carbonate synthesis glyceride.The method is raw materials used inflammable and explosive and be toxicant, and reaction condition is comparatively harsh, and Industry Promotion is restricted.Ester-interchange method and alcoholysis of urea are the focuses of research always, but these two kinds of methods all have certain limitation.US Patent No. 6025504, Chinese patent CN101811971B and CN102285957B report glycerine and urea generation alcoholysis reaction prepares carbonic acid glyceride.In order to the NH produced in removing process
3, reaction must be carried out under the low pressure of 20 ~ 50mbar, and follow-up separation process is also more complicated.US Patent No. 2915529, Japan Patent JP2001172277 and Chinese patent CN101717338A report glycerine and organic carbonate (as: dimethyl carbonate, ethylene carbonate, propene carbonate) respectively, carry out transesterification and obtain glycerol carbonate under base catalyst exists.But the price of raw material organic carbonate is relatively expensive, cause its high cost, be unfavorable for the industrial applications of this route.Comparatively speaking, be that glycerol carbonate directly prepared by raw material process route with glycerine reaction has more Research Significance with carbon dioxide, it both make use of the glycerine of biodiesel byproduct, while also effectively make use of " greenhouse gases " carbon dioxide.But the activity of catalyst needs to improve further, reaction system needs to optimize further.
Summary of the invention
In order to improve the efficiency that carbon dioxide and glycerine synthesis of glycerol carbonate react, the present invention proposes the catalyst of a kind of selective height, good stability.This catalyst, using meso-porous alumina as carrier, has higher specific area, pore volume and narrower pore-size distribution, and be more conducive to load and the dispersion of active component, catalyst reaction efficiency is higher, is applicable to commercial Application.
Technical scheme of the present invention is as follows:
The described catalyst for carbon dioxide and glycerine synthesis of glycerol carbonate is using meso-porous alumina as carrier, using one or more in alkali halide, alkali metal hydroxide or alkali carbonate as active component, adopts infusion process to obtain.
Described activity component load quantity is 5 ~ 50wt%.
Described mesoporous alumina carrier is using aluminium isopropoxide as aluminium source, with non-ionic surface active agent P123 (EO
20pO
70eO
20) the mesoporous Ordered Materials prepared as template.Meso-porous alumina can oneself manufacture, and also can buy from market.(preparation method can bibliography " J.Am.Chem.Soc. " 131 (2009) 12896-12897.)
Alkali metal in described alkali halide, alkali metal hydroxide or alkali carbonate is Cs, K or Na.
The described catalyst for carbon dioxide and glycerine synthesis of glycerol carbonate is prepared from by following each step:
(1) by catalyst composition, one or more in alkali halide, alkali metal hydroxide or alkali carbonate are dissolved in appropriate amount of deionized water, are mixed with the maceration extract that concentration is 3 ~ 30wt%;
(2) get appropriate mesoporous alumina carrier to join in maceration extract prepared by step (1), wherein the mass ratio of meso-porous alumina and maceration extract is 1 ~ 2, carries out incipient impregnation 8 ~ 24h under room temperature;
(3) mixture of step (2) gained is dried 3 ~ 12h in 80 ~ 120 DEG C, obtain white solid product;
(4) by step (3) gained solid product in 450 ~ 700 DEG C of roasting 2 ~ 6h, namely obtain catalyst of the present invention.
The described application process for carbon dioxide and glycerine synthesis of glycerol carbonate catalyst is as follows: carbon dioxide and reacting in autoclave of glycerine synthesis of glycerol carbonate are carried out, the mol ratio of reaction raw materials glycerine and epoxide is 1: 1 ~ 10, catalyst charge is 1 ~ 10% of qualities of glycerin, carbon dioxide initial pressure is 0.5 ~ 20MPa, reaction temperature is 80 ~ 200 DEG C, and the reaction time is 1 ~ 24h.
Described epoxide is expoxy propane or oxirane.
Beneficial effect of the present invention is as follows:
Prepare glycerol carbonate with carbon dioxide and glycerine for raw material to have broad application prospects, both make use of the glycerine of biodiesel byproduct, also effectively make use of " greenhouse gases " carbon dioxide simultaneously.And product and catalyst are easy to be separated, and catalyst is reusable, and production cost is low.Therefore, the present invention has good prospects for commercial application.
Detailed description of the invention
The present invention is further illustrated below in conjunction with embodiment.It is noted that these embodiments are only in order to demonstrate the invention, in office where face does not form limitation of the scope of the invention.
Embodiment 1
Take the K of KI, 0.2g of 1.0g
2cO
3be dissolved in the deionized water of 8.0g, then the meso-porous alumina taking 6.0g adds in this solution, floods 24h under room temperature condition, dry 12h in the baking oven of 80 DEG C, finally roasting 4h in the Muffle furnace of 500 DEG C, can obtain KI-K
2cO
3/ Al
2o
3catalyst.
In autoclave, add 9.2g glycerine, 17.5g expoxy propane, the above-mentioned catalyst of 0.3g, pass into carbon dioxide, initial pressure 3.0MPa, 130 DEG C of reaction 3h.After reaction terminates, isolate catalyst, liquid product gas chromatographic analysis.Result is as follows: the conversion ratio of glycerine is 58.5%, and the productive rate of glycerol carbonate is 54.6%.
Embodiment 2
Take the Na of KF, 1.0g of 0.5g
2cO
3be dissolved in the deionized water of 9.0g, then the meso-porous alumina taking 6.0g adds in this solution, floods 12h under room temperature condition, dry 6h in the baking oven of 100 DEG C, finally roasting 3h in the Muffle furnace of 600 DEG C, can obtain KF-Na
2cO
3/ Al
2o
3catalyst.
In autoclave, add 9.2g glycerine, 35g expoxy propane, the above-mentioned catalyst of 0.5g, pass into carbon dioxide, initial pressure 5.0MPa, 150 DEG C of reaction 6h.After reaction terminates, isolate catalyst, liquid product gas chromatographic analysis.Result is as follows: the conversion ratio of glycerine is 68.5%, and the productive rate of glycerol carbonate is 24.6%.
Embodiment 3
The NaOH taking KCl, 0.5g of 0.5g is dissolved in the deionized water of 7.0g, the meso-porous alumina taking 6.0g again adds in this solution, floods 24h under room temperature condition, dry 3h in the baking oven of 120 DEG C, finally roasting 2h in the Muffle furnace of 700 DEG C, can obtain KCl-NaOH/Al
2o
3catalyst.
In autoclave, add 9.2g glycerine, 8.8g oxirane, the above-mentioned catalyst of 0.6g, pass into carbon dioxide, initial pressure 8.0MPa, 120 DEG C of reaction 4h.After reaction terminates, isolate catalyst, liquid product gas chromatographic analysis.Result is as follows: the conversion ratio of glycerine is 24.5%, and the productive rate of glycerol carbonate is 18.6%.
Embodiment 4
Take the Cs of KF, 0.1g of KI, 0.5g of 1.0g
2cO
3be dissolved in the deionized water of 9.0g, then the meso-porous alumina taking 6.0g adds in this solution, floods 12h under room temperature condition, dry 10h in the baking oven of 80 DEG C, finally roasting 3h in the Muffle furnace of 550 DEG C, can obtain KI-KF-Cs
2cO
3/ Al
2o
3catalyst.
In autoclave, add 9.2g glycerine, 17.6g oxirane, the above-mentioned catalyst of 0.2g, pass into carbon dioxide, initial pressure 2.0MPa, 100 DEG C of reaction 12h.After reaction terminates, isolate catalyst, liquid product gas chromatographic analysis.Result is as follows: the conversion ratio of glycerine is 18.5%, and the productive rate of glycerol carbonate is 14.6%.
Embodiment 5
Take the Na of KOH, 0.5g of KBr, 0.5g of 1.0g
2cO
3be dissolved in the deionized water of 8.0g, then the meso-porous alumina taking 6.0g adds in this solution, floods 8h under room temperature condition, dry 6h in the baking oven of 100 DEG C, finally roasting 5h in the Muffle furnace of 500 DEG C, can obtain KBr-KOH-Na
2cO
3/ Al
2o
3catalyst.
In autoclave, add 9.2g glycerine, 23.6g expoxy propane, the above-mentioned catalyst of 0.6g, pass into carbon dioxide, initial pressure 15.0MPa, 180 DEG C of reaction 2h.After reaction terminates, isolate catalyst, liquid product gas chromatographic analysis.Result is as follows: the conversion ratio of glycerine is 63.5%, and the productive rate of glycerol carbonate is 42.6%.
Embodiment 6
The NaOH taking CsI, 0.5g of KI, 1.0g of 1.5g is dissolved in the deionized water of 9.0g, the meso-porous alumina taking 6.0g again adds in this solution, 10h is flooded under room temperature condition, dry 8h in the baking oven of 90 DEG C, finally roasting 5h in the Muffle furnace of 500 DEG C, can obtain KI-CsI-NaOH/Al
2o
3catalyst.
In autoclave, add 9.2g glycerine, 5.8g expoxy propane, the above-mentioned catalyst of 0.2g, pass into carbon dioxide, initial pressure 10.0MPa, 110 DEG C of reaction 10h.After reaction terminates, isolate catalyst, liquid product gas chromatographic analysis.Result is as follows: the conversion ratio of glycerine is 31.5%, and the productive rate of glycerol carbonate is 22.6%.
Embodiment 7
The NaCl taking KI, 0.2g of 0.2g is dissolved in the deionized water of 6.0g, the meso-porous alumina taking 6.0g again adds in this solution, floods 16h under room temperature condition, dry 12h in the baking oven of 80 DEG C, finally roasting 6h in the Muffle furnace of 450 DEG C, can obtain KI-NaCl/Al
2o
3catalyst.
In autoclave, add 9.2g glycerine, 17.5g expoxy propane, the above-mentioned catalyst of 0.9g, pass into carbon dioxide, initial pressure 8.0MPa, 130 DEG C of reaction 6h.After reaction terminates, isolate catalyst, liquid product gas chromatographic analysis.Result is as follows: the conversion ratio of glycerine is 43.5%, and the productive rate of glycerol carbonate is 38.6%.
Embodiment 8
The CsBr taking NaI, 0.5g of 1.5g is dissolved in the deionized water of 9.0g, the meso-porous alumina taking 6.0g again adds in this solution, floods 20h under room temperature condition, dry 4h in the baking oven of 110 DEG C, finally roasting 3h in the Muffle furnace of 600 DEG C, can obtain NaI-CsBr/Al
2o
3catalyst.
In autoclave, add 9.2g glycerine, 22g oxirane, the above-mentioned catalyst of 0.5g, pass into carbon dioxide, initial pressure 6.0MPa, 140 DEG C of reaction 3h.After reaction terminates, isolate catalyst, liquid product gas chromatographic analysis.Result is as follows: the conversion ratio of glycerine is 46.8%, and the productive rate of glycerol carbonate is 39.5%.
Claims (4)
1. the catalyst for carbon dioxide and glycerine synthesis of glycerol carbonate, it is characterized in that: this catalyst is using meso-porous alumina as carrier, using one or more in alkali halide, alkali metal hydroxide or alkali carbonate as active component, infusion process is adopted to obtain;
Described activity component load quantity is 5 ~ 50wt%;
Described mesoporous alumina carrier is using aluminium isopropoxide as aluminium source, with non-ionic surface active agent P123 (EO
20pO
70eO
20) the mesoporous Ordered Materials prepared as template;
Alkali metal in described alkali halide, alkali metal hydroxide or alkali carbonate is Cs, K or Na.
2. a kind of preparation method for carbon dioxide and glycerine synthesis of glycerol carbonate catalyst as claimed in claim 1, is characterized in that: preparation process is made up of following each step:
(1) get a certain amount of mesoporous alumina carrier, measure its water absorption rate.
(2) according to the water absorption rate that step (1) records, by catalyst composition, one or more in alkali halide, alkali metal hydroxide or alkali carbonate are dissolved in appropriate amount of deionized water, are mixed with maceration extract;
(3) get appropriate mesoporous alumina carrier to join in maceration extract prepared by step (2), under room temperature, carry out incipient impregnation 8 ~ 24h;
(4) mixture of step (3) gained is dried 3 ~ 12h in 80 ~ 120 DEG C, obtain white solid product;
(5) by step (4) gained solid product in 450 ~ 700 DEG C of roasting 2 ~ 6h, namely obtain catalyst of the present invention.
3. the reaction method of a carbon dioxide and glycerine synthesis of glycerol carbonate, it is characterized in that: apply catalyst as claimed in claim 1, comprise the following steps: carbon dioxide and reacting in autoclave of glycerine synthesis of glycerol carbonate are carried out, the mol ratio of reaction raw materials glycerine and epoxide is 1: 1 ~ 10, catalyst charge is 1 ~ 10% of qualities of glycerin, carbon dioxide initial pressure is 0.5 ~ 20MPa, and reaction temperature is 80 ~ 200 DEG C, and the reaction time is 1 ~ 24h.
4. the reaction method of carbon dioxide as claimed in claim 3 and glycerine synthesis of glycerol carbonate, is characterized in that: described epoxide is expoxy propane or oxirane.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017077494A1 (en) * | 2015-11-05 | 2017-05-11 | Reliance Industries Limited | Metal hydroxide based ionic liquid composition |
| CN108855038A (en) * | 2018-05-25 | 2018-11-23 | 东南大学 | A kind of method for preparing catalyst of carbonate synthesis glyceride |
| US11602737B2 (en) | 2015-11-05 | 2023-03-14 | Reliance Industries Limited | Metal hydroxide based ionic liquid composition |
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| US6316641B1 (en) * | 1997-03-12 | 2001-11-13 | Organisation Nationale Interprofessionelle Des Oleagineux (O.N.I.D.Ol.) | Method for producing an epoxide, in particular of glycidol, and installation for implementation |
| CN101822992A (en) * | 2010-05-26 | 2010-09-08 | 华中科技大学 | Catalyst for synthesis of glycerol carbonate and preparation method thereof |
| CN102794189A (en) * | 2011-05-23 | 2012-11-28 | 华中科技大学 | Catalyst for synthesizing glycerol carbonate by urea method |
| CN102962044A (en) * | 2012-11-26 | 2013-03-13 | 中国科学院山西煤炭化学研究所 | Solid base catalyst for synthetizing carbonic acid glyceride by transesterification method, and preparation method and application thereof |
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2015
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Patent Citations (4)
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| US6316641B1 (en) * | 1997-03-12 | 2001-11-13 | Organisation Nationale Interprofessionelle Des Oleagineux (O.N.I.D.Ol.) | Method for producing an epoxide, in particular of glycidol, and installation for implementation |
| CN101822992A (en) * | 2010-05-26 | 2010-09-08 | 华中科技大学 | Catalyst for synthesis of glycerol carbonate and preparation method thereof |
| CN102794189A (en) * | 2011-05-23 | 2012-11-28 | 华中科技大学 | Catalyst for synthesizing glycerol carbonate by urea method |
| CN102962044A (en) * | 2012-11-26 | 2013-03-13 | 中国科学院山西煤炭化学研究所 | Solid base catalyst for synthetizing carbonic acid glyceride by transesterification method, and preparation method and application thereof |
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| WEI WU,ET AL: "Ordered mesoporous alumina supported potassium carbonate as solid base catalysts for biodiesel production", 《CHEMECA 2013: CHALLENGING TOMORROW》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017077494A1 (en) * | 2015-11-05 | 2017-05-11 | Reliance Industries Limited | Metal hydroxide based ionic liquid composition |
| US11602737B2 (en) | 2015-11-05 | 2023-03-14 | Reliance Industries Limited | Metal hydroxide based ionic liquid composition |
| CN108855038A (en) * | 2018-05-25 | 2018-11-23 | 东南大学 | A kind of method for preparing catalyst of carbonate synthesis glyceride |
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Application publication date: 20150805 |