CN101781166B - Preparation method of dihydric alcohol - Google Patents
Preparation method of dihydric alcohol Download PDFInfo
- Publication number
- CN101781166B CN101781166B CN 201010126759 CN201010126759A CN101781166B CN 101781166 B CN101781166 B CN 101781166B CN 201010126759 CN201010126759 CN 201010126759 CN 201010126759 A CN201010126759 A CN 201010126759A CN 101781166 B CN101781166 B CN 101781166B
- Authority
- CN
- China
- Prior art keywords
- reaction
- glucose
- dihydric alcohol
- dibasic alcohol
- preparation
- 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.)
- Expired - Fee Related
Links
Abstract
The invention discloses a preparation method of dihydric alcohol, comprising the following steps of: reacting dextrose water with the pH value of 12-14 and the weight percentage content of 10-50 percent for 0.5-2 hours in the presence of a hydrogenolysis catalyst at the reaction temperature of 130-150 DEG C and the hydrogen pressure of 6-8 MPa, wherein glucose is used as a raw material; then raising the temperature to 220-250 DEG C, and reacting for 0.5-2 hours at the hydrogen pressure of 10-13 MPa; and cooling, filtering and rectifying a reaction product to obtain the dihydric alcohol, wherein the hydrogenolysis catalyst is Raney nickel, ruthenium/carbon, nickel/ruthenium or CuO-ZnO, the usage amount of the hydrogenolysis catalyst is 15-30 percent relative to the mass of the glucose, and the dihydric alcohol is a dihydric alcohol which has a carbon number of 2-4. The invention is mainly used for preparing the dihydric alcohol and especially used for preparing the dihydric alcohol which has the carbon number of 2-4.
Description
Technical field
The present invention relates to a kind of preparation method of dibasic alcohol, particularly relate to carbon number and be the preparation method of 2～4 dibasic alcohol.
Background technology
At present, industrial mainly take oil as the raw material production dibasic alcohol, for example take oxyethane as raw material production ethylene glycol, take propylene oxide as the raw material production propylene glycol.Yet oil is a kind of Nonrenewable resources, and faces more and more serious short situation, therefore needs to seek a kind of method of new raw material, novel process production dibasic alcohol.For example Chinese patent ZL 200610068869.5 discloses a kind of ethylene glycol production technique, the method is take starch as raw material, comprise DX value glucose syrup preparation, hydrogenation, Sorbitol Solution USP refining, sorbyl alcohol hydrogenolysis, polyol blends refining with the process such as separate, concrete steps are as follows:
(1) starch milk enters chromatographic fractionation system through liquefaction, saccharification, filtration, decolouring, after the order of handing over and separates the glucose slurries that obtain DX99～99.7%;
(2) evaporation glucose slurries are 50% to dry, and under the existence of nickel or ruthenium catalyst, 140 ℃～150 ℃, pH value 7.5～8.5 is carried out hydrogenation reaction under pressure 3.5MPa～5.5MPa, obtain Sorbitol Solution USP;
(3) sorbyl alcohol after hydrogenation by cooling, sedimentation, filtration, from hand over, after decolouring, evaporation dry to 50%;
(4) sorbyl alcohol is under the effect of catalyzer, and hydrogenolysis obtains the mixture of ethylene glycol, propylene glycol and glycerol;
(5) with polyol blends by cooling, sedimentation, filtration, from handing over, after decolouring, separating obtaining ethylene glycol, propylene glycol and glycerol.
The reaction raw materials starch of the method can be that raw material makes by corn, belong to renewable resources, compare with the method for dibasic alcohol take oil as raw material production, has certain advantage, but the method processing step is more, and the reacted sorbyl alcohol product of glucose hydrogenation need to carry out sedimentation, filtration, from hand over, the decolouring treatment step, complex process.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and the preparation method of the dibasic alcohol that a kind of technique is simple, step is few is provided.
in order to solve the problems of the technologies described above, the invention provides a kind of preparation method of dibasic alcohol, take glucose as raw material, comprise the following steps: under hydrogenolysis catalyst exists, pH value 12～14, the quality percentage composition is that 10%～50% D/W is 130 ℃～150 ℃ of temperature of reaction, under hydrogen pressure 6MPa～8MPa, reaction is 0.5 hour～2 hours, then be warming up to 220 ℃～250 ℃, reaction is 0.5 hour～2 hours under hydrogen pressure 10MPa～13MPa, reaction product is through cooling, filter, obtain dibasic alcohol after rectifying, wherein hydrogenolysis catalyst is Raney's nickel, ruthenium/carbon, nickel/ruthenium or CuO-ZnO, consumption is 15%～30% of glucose quality, it is 2～4 dibasic alcohol that dibasic alcohol is mainly carbon number.
The present invention is under hydrogenolysis catalyst exists, and glucose is reaction generation sorbyl alcohol under lower temperature of reaction and hydrogen pressure first; Then the temperature of reaction that raises and hydrogen pressure, make the dibasic alcohol such as the further hydrogenolysis generating glycol of sorbyl alcohol, propylene glycol of generation, simplified technological process, reduced operation steps, avoided simultaneously cooling, the sedimentation, filtration of the treating process of sorbyl alcohol, from the energy consumption of the intermediate treatment processes such as friendship, decolouring, reduce facility investment, reduced cost.
In D/W of the present invention, the quality percentage composition of glucose is preferred 20%～40%, and more preferably 30%.
The reaction of the standby dibasic alcohol of G/W phase hydrogenation cracking of the present invention and polyvalent alcohol is preferably carried out for 13～14 times in the pH value, and more preferably the pH value 13～13.5.Before the reaction beginning, with NaOH, KOH, Na
2CO
3Or Ca (OH)
2Regulate pH value to 13～13.5 in alkali, can make the organic acids such as by product lactic acid of G/W phase hydrogenation scission reaction further generate organic salt under alkaline condition, avoided itself and catalyst reaction to cause the problem of catalyst loss.
The preferred catalyzer of the present invention is Raney's nickel, and its consumption is 25% of glucose quality.
Method for preparing catalyst of the present invention is those skilled in the art's technology in common knowledge, is not further described.
Catalyzer is different, and the reaction conditions of the standby dibasic alcohol of G/W phase hydrogenation cracking and polyvalent alcohol is different.Be catalyzer when adopting Raney's nickel, the preferred reactions steps of the present invention is as follows: pH value 13.5, at first the D/W of quality percentage composition 30% reacted 1 hour under the reaction conditions of 140 ℃ of temperature of reaction, hydrogen pressure 7MPa, then be warming up to 240 ℃, reaction is 1 hour under the 12MPa hydrogen pressure, and reaction product obtains dibasic alcohol after cooling, filtration, rectifying.
Dibasic alcohol of the present invention comprises ethylene glycol, propylene glycol and butyleneglycol.Except dibasic alcohol, also contain the polyvalent alcohols such as glycerol, sorbyl alcohol in reaction product.
Beneficial effect of the present invention is mainly reflected in: glucose is reaction generation sorbyl alcohol under lower temperature of reaction and hydrogen pressure first; Then the temperature of reaction that raises and hydrogen pressure make the dibasic alcohol such as the further hydrogenolysis generating glycol of sorbyl alcohol, propylene glycol of generation, have simplified technological process, have reduced operation steps.The transformation efficiency of glucose of the present invention can reach 100%, and the selectivity of different products is: ethylene glycol 15%～20%, propylene glycol 40%～60%, butyleneglycol (comprising all isomer) 5%～10%, glycerol 7%～14%, sorbyl alcohol 1%～15%, other 2%～10%.
Embodiment
Below by specific embodiment, the present invention is described in further detail, but protection scope of the present invention is not limited to this.
Embodiment 1
A certain amount of glucose is dissolved in is mixed with 30% D/W in water, getting this solution 300g joins in the autoclave of 500mL, the Raney's nickel catalyst that adds 22.5g to activate, regulating pH with sodium hydroxide is 13.5, closes autoclave, and nitrogen vacuumizes after suppressing leak test, and with hydrogen exchange 3 times, then heat temperature raising, after the question response temperature was increased to 140 ℃, to be filled with hydrogen to pressure be 7MPa and reacted 1 hour; Then, rising temperature of reaction to 240 ℃, being filled with hydrogen to pressure is 12MPa, reacts after 1 hour, and high pressure liquid chromatographic analysis is used in sampling, and result is as follows:
The transformation efficiency of glucose is 100%, and the selectivity of different products is: ethylene glycol 19%, propylene glycol 58%, butyleneglycol (comprising all isomer) 5%, glycerol 9%, sorbyl alcohol 5%, other 4%.
Embodiment 2
Operate substantially the same manner as Example 1ly, difference is that catalyzer is CuO-ZnO, and reaction result is as follows:
The transformation efficiency of glucose is 100%, and the selectivity of different products is: ethylene glycol 15%, propylene glycol 42%, butyleneglycol (comprising all isomer) 10%, glycerol 12%, sorbyl alcohol 15%, other 6%.
Embodiment 3
Operate substantially the same manner as Example 1ly, difference is that catalyzer is ruthenium/carbon, and reaction result is as follows:
The transformation efficiency of glucose is 100%, and the selectivity of different products is: ethylene glycol 16%, propylene glycol 47%, butyleneglycol (comprising all isomer) 9%, glycerol 12%, sorbyl alcohol 6%, other 10%.
Embodiment 4
Operate substantially the same manner as Example 1ly, difference is that catalyzer is nickel/ruthenium, and reaction result is as follows:
The transformation efficiency of glucose is 100%, and the selectivity of different products is: ethylene glycol 20%, propylene glycol 45%, butyleneglycol (comprising all isomer) 8%, glycerol 13%, sorbyl alcohol 5%, other 9%.
Embodiment 5
Operate substantially the same manner as Example 1, difference be the reaction Initial pH be 12, reaction result is as follows:
The transformation efficiency of glucose is 100%, and the selectivity of different products is: ethylene glycol 16%, propylene glycol 50%, butyleneglycol (comprising all isomer) 7%, glycerol 10%, sorbyl alcohol 9%, other 8%.
Embodiment 6
Operate substantially the same manner as Example 1ly, difference is that reaction conditions is: at first 130 ℃ of temperature of reaction, under the reaction conditions of reaction pressure 8MPa, reaction is 1 hour; Then, 220 ℃ of temperature of reaction, under the reaction conditions of reaction pressure 13MPa, reaction is 1 hour, and reaction result is as follows:
The transformation efficiency of glucose is 100%, and the selectivity of different products is: ethylene glycol 15%, propylene glycol 49%, butyleneglycol (comprising all isomer) 8%, glycerol 10%, sorbyl alcohol 10%, other 8%.
Embodiment 7
Operate substantially the same manner as Example 1ly, difference is that reaction conditions is: at first 150 ℃ of temperature of reaction, under the reaction conditions of reaction pressure 6MPa, reaction is 1 hour; Then, 250 ℃ of temperature of reaction, under the reaction conditions of reaction pressure 10MPa, reaction is 1 hour, and reaction result is as follows:
The transformation efficiency of glucose is 100%, and the selectivity of different products is: ethylene glycol 16%, propylene glycol 55%, butyleneglycol (comprising all isomer) 6%, glycerol 8%, sorbyl alcohol 5%, other 10%.
Embodiment 8
Operate substantially the same manner as Example 1ly, difference is that the concentration of aqueous phase glucose is 10%, and catalyst levels is 9g, and reaction result is as follows:
The transformation efficiency of glucose is 100%, and the selectivity of different products is: ethylene glycol 20%, propylene glycol 60%, butyleneglycol (comprising all isomer) 8%, glycerol 9%, sorbyl alcohol 1%, other 2%.
Embodiment 9
Operate substantially the same manner as Example 1ly, difference is that the concentration of aqueous phase glucose is 50%, and the Initial pH of reaction is 14, and reaction result is as follows:
The transformation efficiency of glucose is 100%, and the selectivity of different products is: ethylene glycol 16%, propylene glycol 50%, butyleneglycol (comprising all isomer) 9%, glycerol 7%, sorbyl alcohol 13%, other 5%.
Embodiment 10
Operate substantially the same manner as Example 1ly, difference is at first reaction 0.5 hour under 140 ℃, 7MPa reaction conditions, then reaction 0.5 hour under 240 ℃, 12MPa reaction conditions, and reaction result is as follows:
The transformation efficiency of glucose is 100%, and the selectivity of different products is: ethylene glycol 15%, propylene glycol 40%, butyleneglycol (comprising all isomer) 10%, glycerol 14%, sorbyl alcohol 15%, other 6%.
Embodiment 11
Operate substantially the same manner as Example 1ly, difference is at first reaction 2 hours under 140 ℃, 7MPa reaction conditions, then reaction 2 hours under 240 ℃, 12MPa reaction conditions, and reaction result is as follows:
The transformation efficiency of glucose is 100%, and the selectivity of different products is: ethylene glycol 18%, propylene glycol 50%, butyleneglycol (comprising all isomer) 9%, glycerol 10%, sorbyl alcohol 3%, other 10%.
Embodiment 12
Operate substantially the same manner as Example 1ly, difference is at first reaction 0.5 hour under 140 ℃, 7MPa reaction conditions, then reaction 2 hours under 240 ℃, 12MPa reaction conditions, and reaction result is as follows:
The transformation efficiency of glucose is 100%, and the selectivity of different products is: ethylene glycol 17%, propylene glycol 56%, butyleneglycol (comprising all isomer) 5%, glycerol 9%, sorbyl alcohol 5%, other 8%.
Claims (3)
1. the preparation method of a dibasic alcohol, take glucose as raw material, comprise the following steps: under hydrogenolysis catalyst exists, pH value 12～14, the quality percentage composition is that 10%～50% D/W is 130 ℃～150 ℃ of temperature of reaction, under hydrogen pressure 6MPa～8Mpa, reaction is 0.5 hour～2 hours, then be warming up to 220 ℃～250 ℃, reaction is 0.5 hour～2 hours under hydrogen pressure 10MPa～13MPa, reaction product is through cooling, filter, obtain dibasic alcohol after rectifying, wherein hydrogenolysis catalyst is CuO-ZnO, consumption is 15%～30% of glucose quality, it is 2～4 dibasic alcohol that dibasic alcohol is mainly carbon number.
2. the preparation method of dibasic alcohol according to claim 1, the quality percentage composition that it is characterized in that glucose in described D/W is 30%.
3. the preparation method of dibasic alcohol according to claim 2, is characterized in that described pH value is 13～14.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010126759 CN101781166B (en) | 2010-03-18 | 2010-03-18 | Preparation method of dihydric alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010126759 CN101781166B (en) | 2010-03-18 | 2010-03-18 | Preparation method of dihydric alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101781166A CN101781166A (en) | 2010-07-21 |
| CN101781166B true CN101781166B (en) | 2013-06-05 |
Family
ID=42521333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010126759 Expired - Fee Related CN101781166B (en) | 2010-03-18 | 2010-03-18 | Preparation method of dihydric alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101781166B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830774A (en) * | 2010-04-13 | 2010-09-15 | 郸城财鑫糖业有限责任公司 | Method for preparing C2-4 dihydric alcohol and polyalcohol from starch raw materials |
| CN102464572B (en) * | 2010-11-04 | 2015-08-12 | 中国石油化工股份有限公司 | A kind of method of hydrogenolysis of sorbitol |
| CN104119207B (en) * | 2013-04-26 | 2016-08-10 | 中国科学院大连化学物理研究所 | A kind of method that carbohydrate catalyzed conversion prepares ethylene glycol |
| CN105523890B (en) | 2014-09-28 | 2021-04-16 | 长春美禾科技发展有限公司 | Method for preparing dihydric alcohol |
| CN109107581A (en) | 2017-06-22 | 2019-01-01 | 长春美禾科技发展有限公司 | A kind of acid resisting alloy catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4380678A (en) * | 1981-01-21 | 1983-04-19 | Hydrocarbon Research, Inc. | Multi-stage aldoses to polyols process |
| CN1762938A (en) * | 2005-09-21 | 2006-04-26 | 徐昌洪 | Method for producing ethylene glycol and lower polyol using hydrocracking |
-
2010
- 2010-03-18 CN CN 201010126759 patent/CN101781166B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4380678A (en) * | 1981-01-21 | 1983-04-19 | Hydrocarbon Research, Inc. | Multi-stage aldoses to polyols process |
| 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 |
|---|
| Jyrki Kuusisto et al..Kinetics of the catalytic hydrogenation of D-fructose over a CuO-ZnO catalyst.《Chemical Engineering Journal》.2005,第115卷93–102. |
| Kinetics of the catalytic hydrogenation of D-fructose over a CuO-ZnO catalyst;Jyrki Kuusisto et al.;《Chemical Engineering Journal》;20051231;第115卷;93–102 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101781166A (en) | 2010-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101781166B (en) | Preparation method of dihydric alcohol | |
| CN102286548A (en) | Method for preparing dihydric alcohol from lignocellulosic biomass | |
| CN103502258A (en) | Cellulose hydrolysis with ph adjustment | |
| CN101659606A (en) | Method for producing calcium formate by using industrial waste liquid | |
| CN101781167B (en) | Method for synthesizing dihydric alcohol and polyhydric alcohol | |
| CN103449970A (en) | Preparation method of neopentyl glycol | |
| RU2608999C2 (en) | Multistage cellulose hydrolysis and quench with or without acid | |
| CN101781171A (en) | Preparation method of dihydric alcohol | |
| CN101684065A (en) | Efficient energy-saving process for continuously processing dihydromyrcenol | |
| CN102417445B (en) | Method for synthesizing succinic acid from maleic acid | |
| CN101544537A (en) | Method for producing low carbon chemical ethanol from C6 sugar alcohol | |
| CN104788408B (en) | A kind of method that γ valerolactones are produced by hemicellulose | |
| CN103896703B (en) | One-step catalytic converts lignocellulose and produces C5, C6the method of alkane | |
| CN101830774A (en) | Method for preparing C2-4 dihydric alcohol and polyalcohol from starch raw materials | |
| CN111393260A (en) | Preparation process of neopentyl glycol and equipment used in process | |
| CN101434547B (en) | Method for preparing aniline from nitrobenzene | |
| Wang et al. | One-pot synthesis of 5-hydroxymethylfurfural directly from cottonseed hull biomass using chromium (III) chloride in ionic liquid | |
| CN100381412C (en) | Novel technique for preparing ethylene glycol | |
| CN101434550A (en) | Method for preparing 1-naphthylamine from 1-nitronaphthalene | |
| CN101434549B (en) | Method for preparing 1,4-3 diaminonaphthalene from 1,4-dinitronaphthalene | |
| CN101781168A (en) | Method for synthesizing dihydric alcohol and polyhydric alcohol | |
| CN103012065A (en) | Method for preparing high-concentration polyhydric alcohol by circularly hydrolyzing and hydrogenating biomass | |
| CN102391065B (en) | Method for producing dihydric alcohol and low molecular polyalcohol by taking corn husk as raw material | |
| CN107778151B (en) | Method for preparing methyl ethyl ketone by sec-butyl alcohol dehydrogenation | |
| CN105418555A (en) | Method for hydrolytically preparing furfural |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130605 Termination date: 20180318 |