CN102093173A - Method for preparing 3-ethyoxyl-1,2-propylene glycol by directly esterifying glycerol and ethanol - Google Patents
Method for preparing 3-ethyoxyl-1,2-propylene glycol by directly esterifying glycerol and ethanol Download PDFInfo
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- CN102093173A CN102093173A CN2010105986076A CN201010598607A CN102093173A CN 102093173 A CN102093173 A CN 102093173A CN 2010105986076 A CN2010105986076 A CN 2010105986076A CN 201010598607 A CN201010598607 A CN 201010598607A CN 102093173 A CN102093173 A CN 102093173A
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- propylene glycol
- glycerine
- oxyethyl group
- catalyzer
- ethanol
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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
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention relates to a method for preparing 3-ethyoxyl-1,2-propylene glycol, in particular to a catalyst and a reaction process for preparing the 3-ethyoxyl-1,2-propylene glycol from glycerol and bioethanol. In the invention, acid catalysts such as HZSM5, Beta molecular sieves, gamma-aluminum oxide, silicon dioxide, phosphotungstic acid, sulfuric acid, and the like and basic catalysts such as magnesium oxide, NaOH, La2O3, Eu2O3, Nd2O3, and the like are adopted, and the 3-ethyoxyl-1,2-propylene glycol is prepared by esterifying the glycerol and the ethanol in aqueous solutions of different concentrations in a high pressure autoclave, wherein under the action of the phosphotungstic acid as the catalyst, the conversion rate of the glycerol reaches up to 97.1 percent, and the yield of the 3-ethyoxyl-1,2-propylene glycol reaches 60.1 percent. The process provided by the invention provides a novel approach for industrially producing the 3-ethyoxyl-1,2-propylene glycol, and solid acids are used as catalysts to directly catalyze the glycerol and the ethanol to esterify.
Description
Technical field
What the present invention relates to is a kind of preparation 3-oxyethyl group-1, the method for 2-propylene glycol, and concrete must saying is a kind ofly to prepare 3-oxyethyl group-1 by glycerine and bio-ethanol, the catalyzer of 2-propylene glycol and reaction process.
Background technology
3-oxyethyl group-1,2-propylene glycol (3-ethoxy-1 2-propanediol), is a kind of thickness, stable water-absorbent liquid, no color or smell, boiling point 221-222 ℃, relative density 1.061(25/4 ℃) is with water, ethanol and multiple immiscible organic solvent.
3-oxyethyl group-1,2-propylene glycol are the important intermediate of synthetic dioxolane compounds.The dioxolane compounds is a kind of very useful Chemicals, can mix with diesel oil and do fuel, the dioxolane compounds that contains 6-8 carbon atom is that fabulous oxidation mixture and diesel oil fuel mixing can reduce solid particulate and the NO that diesel combustion brings greatly
x Discharging.
To 3-oxyethyl group-1, the production method of 2-propylene glycol is not also reported, a kind of production of reported first of the present invention 3-oxyethyl group-1, the new reaction process of 2-propylene glycol at present.
Summary of the invention
The objective of the invention is to develop an environmental friendliness, biological glycerol and bio-ethanol direct esterification efficiently prepares 3-oxyethyl group-1, the reaction process of 2-propylene glycol.
Solution of the present invention is: adopt the different Si/Al of HZSM5(), Beta molecular sieve, γ
-Aluminium sesquioxide, silicon-dioxide, phospho-wolframic acid, sulfuric acid, etc. an acidic catalyst and magnesium oxide, NaOH, La
2O
3, Eu
2O
3And Nd
2O
3Deng basic catalyst, a step realizes that glycerine and ethyl esterification prepare 3-oxyethyl group-1, the 2-propylene glycol in the solution in different concentration in autoclave.
Concrete technical scheme of the present invention is as follows:
The present invention a kind ofly prepares 3-oxyethyl group-1 by glycerine and ethanol direct esterification, and the method for 2-propylene glycol is characterized in that: with glycerine and ethanol is raw material, and under catalyst action, the intermittent type single step reaction prepares 3-oxyethyl group-1, the 2-propylene glycol, and preparation process is as follows:
(1), in being joined, a certain amount of glycerine and alcoholic acid mixing solutions be lined with in the stainless steel autoclave of a glass cylinder, control glycerine and alcoholic acid mol ratio are 1:1-1:6, add a certain amount of catalyzer of people then, the mass ratio of control glycerine and catalyzer is 10:1-5:3;
(2), with after the aforesaid reaction vessel sealing, fall air in the reactor with nitrogen replacement;
(3), heat temperature raising, the temperature of control in the reactor started stirring simultaneously at 80-160 ℃, the reaction times is controlled to be 6-20 hour;
(4), after reaction finishes,, reaction soln is carried out centrifugation, solid catalyst reclaims with the reactor cool to room temperature;
(5), centrifugation goes out after the catalyzer, just can obtain product 3-oxyethyl group-1, the 2-propylene glycol after reaction solution is distilled, isolates unreacted ethanol, glycerine.
Catalyzer of the present invention is HZSM5, HBeta, phospho-wolframic acid, sulfuric acid, Al
2O
3, SiO
2, MgO, NaOH, La
2O
3, Eu
2O
3, Nd
2O
3A kind of.
As preferably, catalyzer of the present invention is a phospho-wolframic acid.
The present invention is that a kind of glycerine and ethyl esterification prepare 3-oxyethyl group-1, the method of 2-propylene glycol is a raw material with glycerine and ethanol, under the effect of above-mentioned different acidity and basic catalyst, the catalyzing glycerol and the alcoholic acid aqueous solution obtain 3-oxyethyl group-1,2-propylene glycol in autoclave.
The pre-treatment step of catalyzer of the present invention is as follows:
A, with the different Si/Al of HZSM5(), Beta molecular sieve, γ
-Aluminium sesquioxide, silicon-dioxide, magnesium oxide, La
2O
3, Eu
2O
3And Nd
2O
3Spend pre-treatment 4 hours Deng solid catalyst 550.
B, phospho-wolframic acid, sulfuric acid and NaOH etc. need not any pre-treatments, directly add reaction system.
Beneficial effect of the present invention is as follows:
Under the effect of phosphotungstic acid catalyst, the transformation efficiency of glycerine is up to 97.1%, 3-oxyethyl group-1, the yield of 2-propylene glycol reaches 60.1%, this technology provides a kind of novel suitability for industrialized production 3-oxyethyl group-1 that can be used for, the new way of 2-propylene glycol is with direct catalyzing glycerol of solid acid as catalyst and ethyl esterification.
Embodiment
Embodiment 1
Adopting HZSM5(Si/Al is 20) be catalyzer, get the roasting 4 hours under 550 degree of 1.0 grams.Preparation glycerine and ethanol mol ratio are 1 to 6 mixing solutions (containing 5 gram glycerine), the mass ratio of glycerine and catalyzer is 5:1, then that roasting is good catalyzer is poured in the mixing solutions for preparing, the good seal autoclave, with the air in the nitrogen replacement reactor, heat temperature raising, start stirring simultaneously, the temperature in the control reactor is 160 degree, reacts 20 hours, after reaction finishes, the reactor cool to room temperature, the high speed centrifugation reaction solution makes reaction product solution and catalyst separating, reaction solution is distilled, isolate unreacted ethanol, behind the glycerine, can obtain product 3-oxyethyl group-1,2-propylene glycol (0.4 gram), the transformation efficiency of glycerine is 7.3%, 3-oxyethyl group-1, the yield of 2-propylene glycol are 6%.
Embodiment 2
The same with embodiment 1, just catalyzer becomes and adopts Si/Al to be 23 HZSM5.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol (0.26 gram), the transformation efficiency of glycerine is 5.0%, 3-oxyethyl group-1, the yield of 2-propylene glycol are 4%.
Embodiment 3
The same with embodiment 1, catalyzer employing Si/Al is 30 HZSM5.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol (0.19 gram), the transformation efficiency of glycerine is 3.9%, 3-oxyethyl group-1, the yield of 2-propylene glycol are 3%.
Embodiment 4
The same with embodiment 1, catalyzer employing Si/Al is 70 HZSM5.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol (0.1 gram), the transformation efficiency of glycerine is 1.8%, 3-oxyethyl group-1, the yield of 2-propylene glycol are 2%.
Embodiment 5
The same with embodiment 1, catalyzer employing Si/Al is 100 HZSM5.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol (0.07 gram), the transformation efficiency of glycerine is 1.1%, 3-oxyethyl group-1, the yield of 2-propylene glycol are 1%.
Embodiment 6
The same with embodiment 1, catalyzer employing Si/Al is 25 Hbeta.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol (0.3 gram), the transformation efficiency of glycerine is 5.7%, 3-oxyethyl group-1, the yield of 2-propylene glycol are 6%.
Embodiment 7
The same with embodiment 1, catalyzer adopts H
3PO
40W
12, 1.5 grams.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol (3.6 gram), glycerol conversion yield is 68.9%, 3-oxyethyl group-1, the yield of 2-propylene glycol are 54.4%.
Embodiment 8
The same with embodiment 1, catalyzer becomes the H of employing 98%
2SO
4, 0.05 milliliter.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol (2.78 gram), glycerol conversion yield is 70.0%, 3-oxyethyl group-1, the yield of 2-propylene glycol are 55.0%.
Embodiment 9
The same with embodiment 1, catalyzer adopts γ
-Aluminium sesquioxide, 1.0 grams.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol 0 gram.
Embodiment 10
The same with embodiment 1, catalyzer adopts silicon-dioxide, 1.0 grams.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol 0 gram.
Embodiment 11
The same with embodiment 1, catalyzer adopts magnesium oxide, 1.0 grams.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol 0 gram.
Embodiment 12
The same with embodiment 1, catalyzer adopts lanthanum trioxide, 1.0 grams.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol 0 gram.
Embodiment 13
The same with embodiment 1, catalyzer adopts europium sesquioxide, 1.0 grams.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol 0 gram.
Embodiment 14
The same with embodiment 1, catalyzer adopts Neodymium trioxide, 1.0 grams.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol 0 gram.
Embodiment 15
The same with embodiment 1, catalyzer adopts H
3PO
40W
12,3.3 gram, temperature of reaction change 80 degree into, obtain product 3-oxyethyl group-1 at last, 2-propylene glycol (0.65 gram), and glycerol conversion yield is 10.1%, 3-oxyethyl group-1, the yield of 2-propylene glycol are 10.0%.
Embodiment 16
The same with embodiment 1, catalyzer adopts H
3PO
40W
12,3.3 gram, temperature of reaction change 100 degree into, obtain product 3-oxyethyl group-1 at last, 2-propylene glycol (1.9 gram), and glycerol conversion yield is 30.5%, 3-oxyethyl group-1, the yield of 2-propylene glycol are 29.2%.
Embodiment 17
The same with embodiment 1, catalyzer adopts H
3PO
40W
12,3.3 gram, temperature of reaction change 120 degree into, obtain product 3-oxyethyl group-1 at last, 2-propylene glycol (2.7), and glycerol conversion yield is 49.9%, 3-oxyethyl group-1, the yield of 2-propylene glycol are 41.7%.
Embodiment 18
Configuration glycerine and ethanol mol ratio are 1 to 1 mixing solutions (containing glycerine 5 grams), get H
3PO
40W
123.3 gram is as catalyzer, the mass ratio of control glycerine and catalyzer is 5 to 3, and other conditions are the same with embodiment 1.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol (3.36 gram), the transformation efficiency of glycerine is 65.6%, 3-oxyethyl group-1, the yield of 2-propylene glycol are 51.6%.
Embodiment 19
Configuration glycerine and ethanol mol ratio are 1 to 4 mixing solutions (containing glycerine 5 grams), get H
3PO
40W
123.3 gram is as catalyzer, other conditions are the same with embodiment 1.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol (4.03 gram), the transformation efficiency of glycerine is 89.3%, 3-oxyethyl group-1, the yield of 2-propylene glycol are 62.2%.
Embodiment 20
Be that the raw glycerine of 20wt% and coarse ethanol that water content is 20wt% are raw material with the water content, the mol ratio of ethanol and glycerine is 6 to be 5 grams than the clean glycerol content of 1(in the control raw material); Add 3.3 gram H
3PO
40W
12Be catalyzer, other conditions are the same with embodiment 1.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol (2.49 gram), the transformation efficiency of glycerine is 43.2%, 3-oxyethyl group-1, the yield of 2-propylene glycol are 38.7%.
Embodiment 21
Be that the raw glycerine of 20wt% and coarse ethanol that water content is 10wt% are raw material with the water content, the mol ratio of ethanol and glycerine is 6 to be 5 grams than the clean glycerol content of 1(in the control raw material); Add 3.3 gram H
3PO
40W
12Be catalyzer, other conditions are the same with embodiment 1.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol (2.82 gram), the transformation efficiency of glycerine is 53.1%, 3-oxyethyl group-1, the yield of 2-propylene glycol are 43.9%.
Embodiment 22
Be that the raw glycerine of 9.1wt% and coarse ethanol that water content is 3.2wt% are raw material with the water content, the mol ratio of ethanol and glycerine is 6 to be 5 grams than the clean glycerol content of 1(in the control raw material); Add 3.3 gram H
3PO
40W
12Be catalyzer, other conditions are the same with embodiment 1.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol (3.67 gram), the transformation efficiency of glycerine is 78.9%, 3-oxyethyl group-1, the yield of 2-propylene glycol are 56.5%.
Embodiment 23
Get 0.5 gram H
3PO
40W
12Be catalyzer, the mass ratio 10:1 of control glycerine and catalyzer, other conditions are the same with embodiment 1.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol (1.3 gram), glycerol conversion yield is 21.2%, 3-oxyethyl group-1, the yield of 2-propylene glycol are 20.3%.
Embodiment 24
Get 1.5 gram H
3PO
40W
12Be catalyzer, the mass ratio of control glycerine and catalyzer is 10 to 3, and other conditions are the same with embodiment 1.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol (3.54 gram), glycerol conversion yield is 68.9%, 3-oxyethyl group-1, the weight yield of 2-propylene glycol are 54.4%.
Embodiment 25
Get 3.3 gram H
3PO
40W
12Be catalyzer, the reaction times is 6 hours, and other conditions are the same with embodiment 1.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol (3.57 gram), glycerol conversion yield is 60.7%, 3-oxyethyl group-1, the yield of 2-propylene glycol are 54.0%.
Embodiment 26
Get 3.3 gram H
3PO
40W
12Be catalyzer, the reaction times is 10 hours, and other conditions are the same with embodiment 1.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol (3.8 gram), glycerol conversion yield is 83.9%, 3-oxyethyl group-1, the yield of 2-propylene glycol are 58.8%.
Embodiment 27
Get 3.3 gram H
3PO
40W
12Be catalyzer, the reaction times is 15 hours, and other conditions are the same with embodiment 1.Obtain product 3-oxyethyl group-1 at last, 2-propylene glycol (3.7 gram), glycerol conversion yield is 93.7%, 3-oxyethyl group-1, the yield of 2-propylene glycol are 58.0%.
Claims (3)
1. one kind prepares 3-oxyethyl group-1 by glycerine and ethanol direct esterification, and the method for 2-propylene glycol is characterized in that: with glycerine and ethanol is raw material, and under catalyst action, the intermittent type single step reaction prepares 3-oxyethyl group-1, the 2-propylene glycol, and preparation process is as follows:
(1), a certain amount of glycerine and alcoholic acid mixing solutions are added the people in the interior stainless steel autoclave that is lined with a glass cylinder, control glycerine and alcoholic acid mol ratio are 1:1-1:6, add a certain amount of catalyzer of people then, the mass ratio of control glycerine and catalyzer is 10:1-5:3;
(2), with after the aforesaid reaction vessel sealing, fall air in the reactor with nitrogen replacement;
(3), heat temperature raising, the temperature of control in the reactor started stirring simultaneously at 80-160 ℃, the reaction times is controlled to be 6-20 hour;
(4), after reaction finishes,, reaction soln is carried out centrifugation, solid catalyst reclaims with the reactor cool to room temperature;
(5), centrifugation goes out after the catalyzer, just can obtain product 3-oxyethyl group-1, the 2-propylene glycol after reaction solution is distilled, isolates unreacted ethanol, glycerine.
2. according to claim 1ly prepare 3-oxyethyl group-1 by glycerine and ethanol direct esterification, the method for 2-propylene glycol is characterized in that: the catalyzer that is adopted is HZSM5, HBeta, phospho-wolframic acid, sulfuric acid, Al
2O
3, SiO
2, MgO, NaOH, La
2O
3, Eu
2O
3, Nd
2O
3A kind of.
3. according to claim 1 and 2ly prepare 3-oxyethyl group-1 by glycerine and ethanol direct esterification, the method for 2-propylene glycol is characterized in that: described catalyzer is a phospho-wolframic acid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105986076A CN102093173A (en) | 2010-12-21 | 2010-12-21 | Method for preparing 3-ethyoxyl-1,2-propylene glycol by directly esterifying glycerol and ethanol |
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|---|---|---|---|
| CN2010105986076A CN102093173A (en) | 2010-12-21 | 2010-12-21 | Method for preparing 3-ethyoxyl-1,2-propylene glycol by directly esterifying glycerol and ethanol |
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391076A (en) * | 2011-10-08 | 2012-03-28 | 中国科学院山西煤炭化学研究所 | Method for preparing glycerol single methanol ether by utilizing glycerol and methanol |
| CN103214402A (en) * | 2013-04-17 | 2013-07-24 | 浙江大学 | Method for directly preparing glycidol from glycerol |
| CN105732332A (en) * | 2016-02-05 | 2016-07-06 | 中北大学 | Glycerinum alkyl ether production method and device based on heterogeneous catalysis |
| CN105797787A (en) * | 2016-04-08 | 2016-07-27 | 于迎春 | Method for recovering heteropolyacid catalyst in catalytic esterification process |
| CN109704958A (en) * | 2018-12-19 | 2019-05-03 | 万华化学集团股份有限公司 | A kind of method preparing ethyl butyrate and the catalyst for this method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009141564A2 (en) * | 2008-05-05 | 2009-11-26 | Centre National De La Recherche Scientifique (C.N.R.S.) | Method for preparing a mixture of biofuels |
| BRPI0806066A2 (en) * | 2008-11-06 | 2010-09-21 | Univ Rio De Janeiro | processes for obtaining glycerine ethers by reaction with an etherifying agent |
-
2010
- 2010-12-21 CN CN2010105986076A patent/CN102093173A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009141564A2 (en) * | 2008-05-05 | 2009-11-26 | Centre National De La Recherche Scientifique (C.N.R.S.) | Method for preparing a mixture of biofuels |
| BRPI0806066A2 (en) * | 2008-11-06 | 2010-09-21 | Univ Rio De Janeiro | processes for obtaining glycerine ethers by reaction with an etherifying agent |
Non-Patent Citations (1)
| Title |
|---|
| STEPHANE PARIENTE ET AL: "Etherification of glycerol with ethanol over solid acid catalysts", 《GREEN CHEMISTRY》, vol. 11, no. 8, 8 June 2009 (2009-06-08), pages 1256 - 1261 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391076A (en) * | 2011-10-08 | 2012-03-28 | 中国科学院山西煤炭化学研究所 | Method for preparing glycerol single methanol ether by utilizing glycerol and methanol |
| CN103214402A (en) * | 2013-04-17 | 2013-07-24 | 浙江大学 | Method for directly preparing glycidol from glycerol |
| CN105732332A (en) * | 2016-02-05 | 2016-07-06 | 中北大学 | Glycerinum alkyl ether production method and device based on heterogeneous catalysis |
| CN105797787A (en) * | 2016-04-08 | 2016-07-27 | 于迎春 | Method for recovering heteropolyacid catalyst in catalytic esterification process |
| CN109704958A (en) * | 2018-12-19 | 2019-05-03 | 万华化学集团股份有限公司 | A kind of method preparing ethyl butyrate and the catalyst for this method |
| CN109704958B (en) * | 2018-12-19 | 2022-09-20 | 万华化学集团股份有限公司 | Method for preparing ethyl butyrate and catalyst used in method |
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Application publication date: 20110615 |