CN104292071A - Method for preparing low-grade polyols - Google Patents
Method for preparing low-grade polyols Download PDFInfo
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- CN104292071A CN104292071A CN201410480801.2A CN201410480801A CN104292071A CN 104292071 A CN104292071 A CN 104292071A CN 201410480801 A CN201410480801 A CN 201410480801A CN 104292071 A CN104292071 A CN 104292071A
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- Prior art keywords
- sugar alcohol
- alcohol
- calcium oxide
- polyols
- hydrogenolysis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing low-grade polyols. The method comprises the following steps: 1) preparing sugar alcohol serving as raw material into a water solution with mass concentration of 10-60%, adding a catalyst and calcium oxide, and reacting for 1-2 hours at 100-200DEG C under nitrogen protection, wherein the mass ratio of sugar alcohol to the catalyst is (50-100):1, and the mass ratio of sugar alcohol to calcium oxide is (100-200):1; introducing hydrogen gas into the solution and reacting at the temperature of 180-200DEG C under the pressure of 10-20MPa for 1-4 hours; filtering the catalyst; and concentrating the filtrate to obtain low-grade polyols. The low-grade polyols are prepared by adopting a method in which dehydrogenation is carried out before hydrogenolysis, and the sugar alcohol is hydrolyzed into polyols, the selectivity is good, and the yield is high; therefore, the method is suitable for industrial production.
Description
Technical field
The present invention relates to the synthesis technique of compound, especially relate to a kind of method preparing lower polyol.
Background technology
Sugar alcohol is a kind of polyvalent alcohol, containing plural hydroxyl, mainly contains Sorbitol Powder, mannitol, erythrose alcohol, maltose alcohol, Saccharum lactis, Xylitol etc.These sugar alcohols can adopt the renewable carbohydrate in 1 year all one's life to be raw material, originate inexhaustible, particularly mixing sugar alcohol, are the by products producing the product such as sorbyl alcohol, Xylitol, with low cost.The small molecules that sugar alcohol hydrogenation cracking generates mainly comprises the lower polyols such as ethylene glycol, propylene glycol, glycerol, butyleneglycol.These lower polyols can be applicable to polyester industrial, Fine Chemical.
Sugar alcohol hydrogenolysis technique can be divided into interval or continuous print mode, as shown in Figure 1:
Directly squeeze in hydrogenolysis system add sugar alcohol, water, additive dissolving mixing in feed proportioning system after, carry out hydrogenolysis at high temperature under high pressure, after reaction terminates, pressure release, vapor-liquid separation, hydrogen is purified reenters hydrogenolysis system, liquid enters separation, recovery system, and be separated and obtain product ethylene glycol, propylene glycol, glycerol, high boiling bed material reenters feed proportioning system and prepares burden.
Hydrogenolysis adopts single stage method usually.Li Zhongliang (hydrogenolysis of sorbitol prepares the research [D] of C4 ~ C6 polyvalent alcohol CuO-ZnO catalyzer. Hangzhou: Zhejiang Polytechnical University, 2006.) and employing CuO-ZnO is catalyzer, prepared by C4-C6 polyvalent alcohol to hydrogenolysis of sorbitol and studies.Result shows, when Cu/Zn is 1, the selectivity of C4 ~ C6 polyvalent alcohol is 68.48%, and in product, the selectivity of ethylene glycol, propylene glycol and glycerol is 11.52%.
Hanford(Hanford W E. Process for cleaving monosaccharides and preparation of lower polhydric alcohols therefrom:US, 2209055 [P]. 1940-07-23.)] with Raney Ni for catalyzer, organic bases pyridine or xylidine are catalyzer, at 100-150 DEG C, 14-21MPa hydrogenolysis sugar alcohol, the yield of alcohol mixture is 31.6%, wherein the yield of propylene glycol and ethylene glycol alcohol mixture is 14.1%, and the yield of glycerol is 17.5%.Bottoms(Bottoms R R. Hydrogenolysis of polyhydric alcohols:US, 2335731 [P]. 1943-11-30.) with Raney Ni for catalyzer, salt such as Repone K, the sodium sulfate of metal are promotor, at 235 DEG C, 10MPa hydrogenolysis Xylitol, the transformation efficiency of Xylitol reaches 80%, and ethylene glycol and glycerol selectivity reach 85-90%.Arena(Arena B J. Hydrocracking of polyols:US, 4496780 [P]. 1985-01-29.) change the carrier of Ru, use Al
2o
3-TiO
2-BaO is carrier, carrying out hydrogenolysis on sorbierite, and the transformation efficiency of sorbyl alcohol is 57.6%, and the yield of ethylene glycol is 3.1%, and glycerol is 21.5%, and 1,2-PD is 18.3%.Zhao Long (L. Zhao, J. H. Zho, Z. J. Sui, et al. Hydrogenolysis of sorbitol to glycols over carbon nanofiber supported ruthenium catalyst [J] .Chemical Engineering Scienc
e. 2010,65,30-35.; Zhao Long. low-carbon (LC) dibasic alcohol [D] prepared by carbon nano fiber load Ru catalytic hydrogenolysis sorbyl alcohol. Shanghai: East China University of Science, 2010) etc. with new carbon-carbon nano fiber (CNFs) for carrier, take Ru as active ingredient, prepare hydrogenolysis of sorbitol Ru/ CNFs fine catalyst, at 220 DEG C, 8MPa reacts, and the transformation efficiency of sorbyl alcohol is 85.73%, the selectivity of ethylene glycol, glycerol and 1,2-PD alcohol mixture is 51.3%.In existing single stage method hydrogenolysis, there is polyvalent alcohol and be degraded to small molecules C further
1, there is the deficiencies such as sugar alcohol hydrogenolysis poor selectivity, yield be low in compound.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of two-step approach to prepare the method for polyvalent alcohol.
Technical scheme of the present invention is as follows:
A kind of method preparing lower polyol comprises the steps:
1) take sugar alcohol as raw material, be mixed with the aqueous solution of 10-60% mass concentration, add catalyzer, calcium oxide, under nitrogen protection, in 100-200 DEG C of reaction 1-2 hour, the mass ratio of sugar alcohol and catalyzer is 50-100:1; The mass ratio of sugar alcohol and calcium oxide is 100-200:1.
2) in above-mentioned solution, pass into hydrogen, pressure is to 10-20MPa, and temperature is 180-200 DEG C, reaction 1-4 hour, filtering catalyst, and filtrate is concentrated obtains lower polyol.
Described sugar alcohol is Sorbitol Powder, maltose alcohol or Xylitol;
Described catalyzer is Ru/C, Ru/Al
2o
3or Raney Ni.
The present invention adopts first dehydrogenation, the method for rear hydrogenolysis prepares polyvalent alcohol, and sugar alcohol hydrogenolysis is that polyvalent alcohol selectivity is good, and yield is high, is suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is sugar alcohol hydrogenolysis process flow sheet.
embodiment
Be reaction raw materials with sugar alcohol, be mixed with the aqueous solution of 10-60% mass concentration, add catalyzer, calcium oxide, under nitrogen protection, in 100-200 DEG C of reaction 1-2 hour.The mass ratio of sugar alcohol and catalyzer is 50-100:1; The mass ratio of sugar alcohol and calcium oxide is for being 100-200:1.In above-mentioned solution, pass into hydrogen, pressure is to 10-20MPa, and temperature is 180-200 DEG C, reaction 1-4 hour, filtering catalyst, and filtrate is concentrated obtains polyvalent alcohol.Described sugar alcohol is Sorbitol Powder, maltose alcohol or Xylitol; Described catalyzer is Ru/C, Ru/Al
2o
3or Raney Ni.Described Ru/C is the Ru/C of 5% mass content, described Ru/Al
2o
3be the Ru/Al of 5% mass content
2o
3.
embodiment 1
The Ru/C of 50 grams sorbitol, 450 grams of water, 1 gram of 5% content is added in the autoclave of 1 L, 0.5 gram of calcium oxide, with nitrogen replacement three times, maintenance nitrogen pressure is 0.1MPa, is warmed up to 100 DEG C, react 1 hour, pass into hydrogen after reaction to pressure 10 MPa, be warmed up to 180 DEG C, react 1 hour, cool to room temperature, filtering catalyst, filtrate concentrates, and obtains 43.0 grams of mixtures, liquid-phase chromatographic analysis, sorbyl alcohol 28.6%, ethylene glycol 43.2%, propylene glycol 10.1%, glycerol 15.1%, other is unknown product.
embodiment 2
The Ru/Al of 50 grams of maltose alcohols, 450 grams of water, 0.5 gram of 5% content is added in the autoclave of 1 L
2o
3, 0.25 gram of calcium oxide, with nitrogen replacement three times, maintenance nitrogen pressure is 0.1MPa, be warmed up to 200 DEG C, react 2 hours, pass into hydrogen after reaction to pressure 20 MPa, be warmed up to 200 DEG C, react 4 hours, cool to room temperature, filtering catalyst, filtrate concentrates, and obtains 38.7 grams of mixtures, liquid-phase chromatographic analysis, sorbyl alcohol 12.3%, ethylene glycol 41.3%, propylene glycol 12.5%, glycerol 14.9, other is unknown product.
embodiment 3
120 grams of Xylitols, 80 grams of water, 3.0 grams of Raney Ni are added in the autoclave of 1 L, 1.0 grams of calcium oxide, with nitrogen replacement three times, maintenance nitrogen pressure is 0.1MPa, is warmed up to 150 DEG C, react 2 hours, pass into hydrogen after reaction to pressure 15 MPa, be warmed up to 200 DEG C, react 3 hours, cool to room temperature, filtering catalyst, filtrate concentrates, and obtains 98.7 grams of mixtures, liquid-phase chromatographic analysis, sorbyl alcohol 22.3%, ethylene glycol 41.3%, propylene glycol 12.5%, glycerol 14.9, other is unknown product.
Claims (3)
1. prepare a method for lower polyol, it is characterized in that comprising the steps:
1) take sugar alcohol as raw material, be mixed with the aqueous solution of 10-60% mass concentration, add catalyzer, calcium oxide, under nitrogen protection, in 100-200 DEG C of reaction 1-2 hour, the mass ratio of sugar alcohol and catalyzer is 50-100:1; The mass ratio of sugar alcohol and calcium oxide is 100-200:1;
2) in above-mentioned solution, pass into hydrogen, pressure is to 10-20MPa, and temperature is 180-200 DEG C, reaction 1-4 hour, filtering catalyst, and filtrate is concentrated obtains lower polyol.
2. a kind of method preparing polyvalent alcohol according to claim 1, is characterized in that described sugar alcohol is Sorbitol Powder, maltose alcohol or Xylitol.
3. a kind of method preparing polyvalent alcohol according to claim 1, is characterized in that described catalyzer is Ru/C, Ru/Al
2o
3or Raney Ni.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410480801.2A CN104292071B (en) | 2014-09-19 | 2014-09-19 | A kind of method preparing lower polyol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410480801.2A CN104292071B (en) | 2014-09-19 | 2014-09-19 | A kind of method preparing lower polyol |
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| Publication Number | Publication Date |
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| CN104292071A true CN104292071A (en) | 2015-01-21 |
| CN104292071B CN104292071B (en) | 2016-01-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410480801.2A Expired - Fee Related CN104292071B (en) | 2014-09-19 | 2014-09-19 | A kind of method preparing lower polyol |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2335731A (en) * | 1938-10-03 | 1943-11-30 | Robert R Bottoms | Hydrogenolysis of polyhydric alcohols |
| US4496780A (en) * | 1983-06-22 | 1985-01-29 | Uop Inc. | Hydrocracking of polyols |
| CN1762938A (en) * | 2005-09-21 | 2006-04-26 | 徐昌洪 | Method for producing ethylene glycol and lower polyol using hydrocracking |
-
2014
- 2014-09-19 CN CN201410480801.2A patent/CN104292071B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2335731A (en) * | 1938-10-03 | 1943-11-30 | Robert R Bottoms | Hydrogenolysis of polyhydric alcohols |
| US4496780A (en) * | 1983-06-22 | 1985-01-29 | Uop Inc. | Hydrocracking of polyols |
| CN1762938A (en) * | 2005-09-21 | 2006-04-26 | 徐昌洪 | Method for producing ethylene glycol and lower polyol using hydrocracking |
Non-Patent Citations (2)
| Title |
|---|
| JINGHONG ZHOU ET AL.: "Hydrogenolysis of sorbitol to glycols over carbon nanofibers-supported ruthenium catalyst : The role of base promoter", 《CHINESE JOURNAL OF CATALYSIS》, vol. 35, no. 5, 20 May 2014 (2014-05-20), pages 692 - 702 * |
| 蒋成君等: "糖醇催化氢解制低级多元醇研究进展", 《化工进展》, vol. 31, no. 10, 31 December 2012 (2012-12-31), pages 2270 - 2276 * |
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| CN104292071B (en) | 2016-01-20 |
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Granted publication date: 20160120 Termination date: 20160919 |