CN101781171A - Preparation method of dihydric alcohol - Google Patents
Preparation method of dihydric alcohol Download PDFInfo
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- CN101781171A CN101781171A CN201010126760A CN201010126760A CN101781171A CN 101781171 A CN101781171 A CN 101781171A CN 201010126760 A CN201010126760 A CN 201010126760A CN 201010126760 A CN201010126760 A CN 201010126760A CN 101781171 A CN101781171 A CN 101781171A
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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 a nickel-molybdenum-copper catalyst doping chromium or ferrum, stannum and zinc, 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, belong to and particularly to relate to the preparation method that carbon number is 2～4 dibasic alcohol.
Background technology
At present, industrial mainly is the raw material production dibasic alcohol with the oil, is raw material production ethylene glycol with oxyethane for example, is the raw material production propylene glycol with the propylene oxide.Yet oil is a kind of Nonrenewable resources, and faces more and more serious short situation, therefore needs to seek the method for a kind of new raw material, novel process production dibasic alcohol.For example Chinese patent ZL 200610068869.5 discloses a kind of ethylene glycol production technique, this method is raw material with starch, comprise DX value glucose syrup preparation, hydrogenation, Sorbitol Solution USP refining, sorbyl alcohol hydrogenolysis, polyol blends refining with process such as separate, concrete steps are as follows:
(1) starch milk through liquefaction, saccharification, filtration, decolouring, after the preface of handing over, enter chromatographic fractionation system and separate the glucose slurries that obtain DX99～99.7%;
(2) evaporation glucose slurries are 50% to dry, and in the presence 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 behind the hydrogenation by cooling, sedimentation, filtration, from hand over, after the 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 the decolouring, separating obtaining ethylene glycol, propylene glycol and glycerol.
The reaction raw materials starch of this method can be that raw material makes by corn, belong to renewable resources, compare with the method that with the oil is the dibasic alcohol of raw material production, has certain advantage, but this method processing step is more, and the reacted sorbyl alcohol product of glucose hydrogenation need 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 technology 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, with glucose is raw material, may further comprise the steps: in the presence of hydrogenolysis catalyst, pH value 12～14, the D/W of quality percentage composition 10%～50% is 130 ℃～150 ℃ of temperature of reaction, hydrogen pressure 6MPa～8MPa reacted 0.5 hour～2 hours down, be warming up to 220 ℃～250 ℃ then, reaction is 0.5 hour～2 hours under hydrogen pressure 10MPa～13MPa, reaction product is through cooling, filter, obtain dibasic alcohol after the rectifying, wherein hydrogenolysis catalyst is chromium-doped or iron, tin, nickel-the molybdenum of zinc-copper catalyst, consumption is 15%～30% of a glucose quality, and dibasic alcohol is that carbon number is 2～4 dibasic alcohol.
The present invention is in the presence of hydrogenolysis catalyst, and glucose is reaction generation sorbyl alcohol under lower temperature of reaction and hydrogen pressure earlier; The temperature of reaction that raises then and hydrogen pressure, make the further hydrogenolysis of sorbyl alcohol of generation generate dibasic alcohol such as ethylene glycol, propylene glycol, simplified technological process, reduced operation steps, avoided the cooling, sedimentation, filtration of the treating process of sorbyl alcohol simultaneously, from the energy consumption of intermediate treatment processes such as friendship, decolouring, reduce facility investment, reduced cost.
The quality percentage composition of glucose is preferred 20%～40% in the D/W of the present invention, and more preferably 30%.
G/W phase of the present invention hydrocracking prepares the reaction of dibasic alcohol and polyvalent alcohol preferably reacts 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 under alkaline condition, further generate organic salt, avoided itself and catalyst reaction to cause the problem of catalyst loss.
Nickel in the catalyzer of the present invention: molybdenum: copper: chromium (or iron, zinc)=100: 2: 5: 5, nickel: molybdenum: copper: tin=100: 2: 5: 10.Preferred catalyzer is nickel-molybdenum-copper-chromium, and its consumption is 25% of a glucose quality.
Method for preparing catalyst:
Alumino nickel is added in the reaction vessel, adds entry, is heated to 50 ℃.To be dissolved with ammonium molybdate, cupric chloride, 15% hydrochloric acid soln of chromium trichloride (or tin protochloride or iron trichloride or zinc chloride) drops in the reactor.1h is stirred in continuation after dropwising, and topples over liquid.Catalyst solid washing three times, 300 ℃, reduction 5h postcooling in water or the alcoholic solvent obtains nickel-molybdenum-copper-chromium (or nickel-molybdenum-copper-Xi or nickel-molybdenum-copper-iron or nickel-molybdenum-copper-zinc) catalyzer in the nitrogen atmosphere.By the reaction of hydrochloric acid and aluminium and the replacement(metathesis)reaction of metal salt solution and aluminium, metals such as copper, chromium, tin, iron, zinc enter the alloy duct.May contain the aluminium that traces of unreacted is fallen in the catalyzer of present method preparation, but its existence does not influence catalytic performance, the present invention does not do strict the qualification to the content of aluminium.
The catalyzer difference, it is different that the hydrocracking of G/W phase prepares the reaction conditions of dibasic alcohol and polyvalent alcohol.When adopting nickel-molybdenum-copper-chromium is catalyzer, the preferred reactions steps of the present invention is as follows: pH value 13.5, the D/W of quality percentage composition 30% at first reacted 1 hour under the reaction conditions of 140 ℃ of temperature of reaction, hydrogen pressure 7MPa, be warming up to 240 ℃ then, 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 that dibasic alcohol, also contain polyvalent alcohols such as glycerol, sorbyl alcohol in the 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 earlier; The temperature of reaction that raises then and hydrogen pressure make the further hydrogenolysis of sorbyl alcohol of generation generate dibasic alcohol such as ethylene glycol, propylene glycol, have simplified technological process, have reduced operation steps.The transformation efficiency of glucose of the present invention can reach 100%, and different product selectivity are: 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 the water, getting this solution 300g joins in the autoclave of 500mL, add 22.5g nickel-molybdenum-copper-chromium catalyst, regulating pH with sodium hydroxide is 13.5, closes autoclave, and nitrogen vacuumizes after suppressing leak test, and with hydrogen exchange 3 times, heat temperature raising then, after the question response temperature was increased to 140 ℃, to charge into hydrogen to pressure be 7MPa and reacted 1 hour; Then, rising temperature of reaction to 240 ℃, charging into hydrogen to pressure is 12MPa, reacts after 1 hour, and high pressure liquid chromatographic analysis is used in sampling, and the result is as follows:
The transformation efficiency of glucose is 100%, and different product selectivity are: 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, different is that catalyzer is nickel-molybdenum-copper-Xi, and reaction result is as follows:
The transformation efficiency of glucose is 100%, and different product selectivity are: 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, different is that catalyzer is nickel-molybdenum-copper-iron, and reaction result is as follows:
The transformation efficiency of glucose is 100%, and different product selectivity are: 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, different is that catalyzer is nickel-molybdenum-copper-zinc, and reaction result is as follows:
The transformation efficiency of glucose is 100%, and different product selectivity are: 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 1ly, the initial pH value of reaction that different is is 12, and reaction result is as follows:
The transformation efficiency of glucose is 100%, and different product selectivity are: 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, different is that reaction conditions is: at first 130 ℃ of temperature of reaction, and the reaction 1 hour down of the reaction conditions of reaction pressure 8MPa; Then, 220 ℃ of temperature of reaction, the reaction conditions of reaction pressure 13MPa reacted 1 hour down, and reaction result is as follows:
The transformation efficiency of glucose is 100%, and different product selectivity are: 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, different is that reaction conditions is: at first 150 ℃ of temperature of reaction, and the reaction 1 hour down of the reaction conditions of reaction pressure 6MPa; Then, 250 ℃ of temperature of reaction, the reaction conditions of reaction pressure 10MPa reacted 1 hour down, and reaction result is as follows:
The transformation efficiency of glucose is 100%, and different product selectivity are: 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, the concentration of different is aqueous phase glucose is 10%, and catalyst levels is 9g, and reaction result is as follows:
The transformation efficiency of glucose is 100%, and different product selectivity are: 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, the concentration of different is aqueous phase glucose is 50%, and the initial pH value of reaction is 14, and reaction result is as follows:
The transformation efficiency of glucose is 100%, and different product selectivity are: 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 1, at first reaction 0.5 hour under 140 ℃, 7MPa reaction conditions that different is, reaction 0.5 hour under 240 ℃, 12MPa reaction conditions then, reaction result is as follows:
The transformation efficiency of glucose is 100%, and different product selectivity are: 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 1, at first reaction 2 hours under 140 ℃, 7MPa reaction conditions that different is, reaction 2 hours under 240 ℃, 12MPa reaction conditions then, reaction result is as follows:
The transformation efficiency of glucose is 100%, and different product selectivity are: 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 1, at first reaction 0.5 hour under 140 ℃, 7MPa reaction conditions that different is, reaction 2 hours under 240 ℃, 12MPa reaction conditions then, reaction result is as follows:
The transformation efficiency of glucose is 100%, and different product selectivity are: ethylene glycol 17%, propylene glycol 56%, butyleneglycol (comprising all isomer) 5%, glycerol 9%, sorbyl alcohol 5%, other 8%.
Claims (5)
1. the preparation method of a dibasic alcohol, with glucose is raw material, may further comprise the steps: in the presence of hydrogenolysis catalyst, pH value 12～14, the D/W of quality percentage composition 10%～50% is 130 ℃～150 ℃ of temperature of reaction, hydrogen pressure 6MPa～8MPa reacted 0.5 hour～2 hours down, be warming up to 220 ℃～250 ℃ then, reaction is 0.5 hour～2 hours under hydrogen pressure 10MPa～13MPa, reaction product is through cooling, filter, obtain dibasic alcohol after the rectifying, wherein hydrogenolysis catalyst is chromium-doped or iron, tin, nickel-the molybdenum of zinc-copper catalyst, consumption is 15%～30% of a glucose quality, and dibasic alcohol is that carbon number is 2～4 dibasic alcohol.
2. the preparation method of dibasic alcohol according to claim 1, the quality percentage composition that it is characterized in that glucose in the 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.
4. the preparation method of dibasic alcohol according to claim 3 is characterized in that described hydrogenolysis catalyst is nickel-molybdenum-copper-chromium, nickel: molybdenum: copper: chromium=100: 2: 5: 5, and consumption is 25% of a glucose quality.
5. according to the preparation method of the arbitrary described dibasic alcohol of claim 1 to 4, it is characterized in that described reactions steps is as follows: in the presence of nickel-molybdenum-copper-chromium catalyst, pH value 13.5, under 140 ℃ of temperature of reaction, hydrogen pressure 7MPa, reacted 1 hour under the D/W of quality percentage composition 30%, be warming up to 240 ℃ then, reaction is 1 hour under hydrogen pressure 12MPa, and reaction product obtains dibasic alcohol after cooling, filtration, rectifying.
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| CN201010126760A CN101781171A (en) | 2010-03-18 | 2010-03-18 | Preparation method of dihydric alcohol |
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| CN201010126760A CN101781171A (en) | 2010-03-18 | 2010-03-18 | Preparation method of dihydric alcohol |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119207A (en) * | 2013-04-26 | 2014-10-29 | 中国科学院大连化学物理研究所 | Method for preparation of ethylene glycol by catalytic conversion of carbohydrate |
| WO2018233677A1 (en) | 2017-06-22 | 2018-12-27 | 长春美禾科技发展有限公司 | Acid-resistant alloy catalyst |
| EP3653595A1 (en) | 2014-09-28 | 2020-05-20 | Changchun Meihe Science and Technology Development Co., Ltd. | Method for preparing diol |
| CN111686747A (en) * | 2019-03-15 | 2020-09-22 | 北京化工大学 | Preparation method of catalyst with target product of glucose hydrogenolysis reaction being dihydric alcohol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5104504A (en) * | 1989-09-22 | 1992-04-14 | Agency Of Industrial Science And Technology | Method for the preparation of an alcohol from hydrocarbon |
| CN1762938A (en) * | 2005-09-21 | 2006-04-26 | 徐昌洪 | Method for producing ethylene glycol and lower polyol using hydrocracking |
| CN101613253A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | The catalytic cracking method of a kind of sugar and sugar alcohol |
-
2010
- 2010-03-18 CN CN201010126760A patent/CN101781171A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5104504A (en) * | 1989-09-22 | 1992-04-14 | Agency Of Industrial Science And Technology | Method for the preparation of an alcohol from hydrocarbon |
| CN1762938A (en) * | 2005-09-21 | 2006-04-26 | 徐昌洪 | Method for producing ethylene glycol and lower polyol using hydrocracking |
| CN101613253A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | The catalytic cracking method of a kind of sugar and sugar alcohol |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119207A (en) * | 2013-04-26 | 2014-10-29 | 中国科学院大连化学物理研究所 | Method for preparation of ethylene glycol by catalytic conversion of carbohydrate |
| 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 |
| EP3653595A1 (en) | 2014-09-28 | 2020-05-20 | Changchun Meihe Science and Technology Development Co., Ltd. | Method for preparing diol |
| WO2018233677A1 (en) | 2017-06-22 | 2018-12-27 | 长春美禾科技发展有限公司 | Acid-resistant alloy catalyst |
| CN111686747A (en) * | 2019-03-15 | 2020-09-22 | 北京化工大学 | Preparation method of catalyst with target product of glucose hydrogenolysis reaction being dihydric alcohol |
| CN111686747B (en) * | 2019-03-15 | 2023-03-21 | 北京化工大学 | Preparation method of catalyst with target product of glucose hydrogenolysis reaction being dihydric alcohol |
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Application publication date: 20100721 |