CN101781170A - Preparation method of dihydric alcohol - Google Patents
Preparation method of dihydric alcohol Download PDFInfo
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- CN101781170A CN101781170A CN201010126758A CN201010126758A CN101781170A CN 101781170 A CN101781170 A CN 101781170A CN 201010126758 A CN201010126758 A CN 201010126758A CN 201010126758 A CN201010126758 A CN 201010126758A CN 101781170 A CN101781170 A CN 101781170A
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a preparation method of dihydric alcohol, comprising the following step of: carrying out aqueous phase hydrogenolysis to obtain the dihydric alcohol by using hexabasic alcohol as a raw material in the presence of a hydrogenolysis catalyst and at the reaction temperature of 180 DEG C-260 DEG C, the hydrogen pressure of 8 MPa-15 MPa and the pH value of 11-14, wherein the hexabasic alcohol is a mixture of sorbierite and mannite; the weight percentage content of the sorbierite in an aqueous phase is 10-30 percent; the weight percentage content of the mannite is 2-10 percent; the hydrogenolysis catalyst is a nickel-molybdenum-copper catalyst doping chromium, ferrum and stannum or zinc, and the usage amount of the catalyst is 3-10 percent relative to the total weight of the aqueous phase; and the dihydric alcohol comprises ethylene glycol, propylene glycol and butanediol. The invention is mainly used for preparing the dihydric alcohol.
Description
Technical field
The present invention relates to a kind of preparation method of 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 must seek the method for a kind of new raw material, novel process production dibasic alcohol.For example Chinese patent CN 1683293A discloses a kind of technology of being produced dibasic alcohol by cracking sorbierite, in the presence of sodium hydroxide and nickel/ruthenium catalyst, massfraction is 5%～30% sorbitol aqueous solution hydrocracking generation ethylene glycol and propylene glycol under high temperature, high pressure.The raw material that this adopted is pure sorbitol aqueous solution, need obtain by separating to purify, and the used nickel of this method/ruthenium catalyst price is expensive.
Summary of the invention
Technical problem to be solved by this invention is to overcome disadvantages of background technology, and the production method of the dibasic alcohol that a kind of raw material sources are extensive, the catalyzer price is cheaper is provided.
In order to solve the problems of the technologies described above, the preparation method of dibasic alcohol of the present invention, with hexa-atomic sugar alcohol is raw material, in the presence of hydrogenolysis catalyst, 180 ℃～260 ℃ of temperature of reaction, hydrogen pressure 8MPa～15MPa, pH value 11～14, the water hydrogenolysis makes dibasic alcohol, and wherein hexa-atomic sugar alcohol is a sorbyl alcohol, the mixture of N.F,USP MANNITOL, the quality percentage composition of aqueous phase sorbyl alcohol is 10%～30%, the quality percentage composition of N.F,USP MANNITOL is 2%～10%, hydrogenolysis catalyst is chromium-doped, iron, nickel-the molybdenum of tin or zinc-copper catalyst, catalyst levels are 3%～10% of water gross weight, and dibasic alcohol is that carbon number is 2～4 dibasic alcohol.
It is raw material that the present invention adopts the mixture of sorbyl alcohol and N.F,USP MANNITOL, this raw material can be from the hydrolysis hydrogenation products of sugar or starch, Mierocrystalline cellulose etc., need not to separate and purify, can be directly used in the present invention, select for use cheap, nickel-molybdenum-the copper catalyst of chromium-doped, iron, tin or zinc, its mass ratio is a nickel: molybdenum: copper: chromium (or iron, zinc)=100: 2: 5: 5, nickel: molybdenum: copper: tin=100: 2: 5: 10.
Hydrogenolysis catalyst of the present invention is preferably nickel-molybdenum-copper-chromium or nickel-molybdenum-copper-tin catalyst, more preferably nickel-molybdenum-copper-chromium.
Aqueous phase sorbyl alcohol quality percentage composition of the present invention is preferably 15%～25%, and more preferably 20%; The quality percentage composition of N.F,USP MANNITOL is preferably 2%～8%, and more preferably 5%.
The reaction conditions that the mixture water hydrocracking of sorbyl alcohol of the present invention and N.F,USP MANNITOL prepares dibasic alcohol is preferably: 240 ℃ of temperature of reaction, hydrogen pressure 11MPa, pH value 13.
The dibasic alcohol that the mixture water hydrogenolysis of sorbyl alcohol and N.F,USP MANNITOL makes is that carbon number is 2～4 dibasic alcohol, mainly comprises ethylene glycol, propylene glycol and butyleneglycol, and wherein butyleneglycol comprises 1,2-butyleneglycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 2, isomer such as 3-butyleneglycol.In addition, also comprise a small amount of glycerol, methyl alcohol, ethanol and unreacted sorbyl alcohol and N.F,USP MANNITOL etc. in the reaction product of the present invention.
The present invention is under different catalysts and reaction conditions, and the mixture water hydrogenolysis product and the percentage composition of sorbyl alcohol and N.F,USP MANNITOL are different, and its scope is: ethylene glycol 20%～35%; Propylene glycol 40%～65%; Butyleneglycol (comprising all isomer) 5%～10%; Sorbyl alcohol and N.F,USP MANNITOL 1%～5%; Other is 4%～15% years old.
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.
Beneficial effect of the present invention is mainly reflected in: the raw material of selecting for use is the mixture of sorbyl alcohol and N.F,USP MANNITOL, can be from hydrolysis hydrogenation products such as sugar or starch, Mierocrystalline celluloses, and raw material sources are wide, restriction is little, and need not to separate purification; Select the hydrogenolysis catalyst of the nickel-molybdenum-copper catalyst of chromium-doped or iron, tin, zinc for use, low price as the mixture of sorbyl alcohol and N.F,USP MANNITOL.
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 sorbyl alcohol and N.F,USP MANNITOL are dissolved in the water, be mixed with contain that sorbyl alcohol quality percentage composition is 20%, N.F,USP MANNITOL quality percentage composition is 5% the aqueous solution.Getting this solution 300g joins in the autoclave of 500mL, add 25g nickel-molybdenum-copper-chromium catalyst, regulating pH with sodium hydroxide is 13, close autoclave, nitrogen vacuumizes after suppressing leak test, and with hydrogen exchange 3 times, heat temperature raising then is after the question response temperature is increased to 240 ℃, charging into hydrogen to reaction pressure is that 11MPa begins the shortening scission reaction, react sampling after 1 hour, high pressure liquid chromatographic analysis, product is formed and is distributed as: ethylene glycol 22.7%, propylene glycol 62%, butyleneglycol 7.8%, other 5.2%, residue sorbyl alcohol and N.F,USP MANNITOL totally 2.3%.
Embodiment 2～embodiment 8
Experimental technique is substantially the same manner as Example 1, and different is that the catalyzer that adopts is different with reaction conditions, and products distribution also has certain difference, sees Table 1.
Reaction conditions and the result of table 1 embodiment 2～embodiment 8
Claims (4)
1. the preparation method of a dibasic alcohol, it is characterized in that with hexa-atomic sugar alcohol be raw material, in the presence of hydrogenolysis catalyst, 180 ℃～260 ℃ of temperature of reaction, hydrogen pressure 8MPa～15MPa, pH value 11～14, the water hydrogenolysis makes dibasic alcohol, wherein the hexa-atomic sugar alcohol of raw material is the mixture of sorbyl alcohol and N.F,USP MANNITOL, the quality percentage composition of aqueous phase sorbyl alcohol is 10%～30%, and the quality percentage composition of N.F,USP MANNITOL is 2%～10%, and hydrogenolysis catalyst is chromium-doped or iron, tin, nickel-the molybdenum of zinc-copper catalyst, catalyst levels is 3%～10% of a water gross weight, and dibasic alcohol is that carbon number is 2～4 dibasic alcohol.
2. the preparation method of dibasic alcohol according to claim 1 is characterized in that described hydrogenolysis catalyst is nickel-molybdenum-copper-chromium, and its mass ratio is a nickel: molybdenum: copper: chromium=100: 2: 5: 5.
3. the preparation method of dibasic alcohol according to claim 2, the quality percentage composition that it is characterized in that described aqueous phase sorbyl alcohol is 20%, the quality percentage composition of N.F,USP MANNITOL is 5%.
4. according to the preparation method of the arbitrary described dibasic alcohol of claim 1 to 3, it is characterized in that described water hydrocracking 240 ℃ of temperature of reaction, hydrogen pressure 11MPa, the pH value is carried out for 13 times.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101267581A CN101781170B (en) | 2010-03-18 | 2010-03-18 | Preparation method of dihydric alcohol |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010101267581A CN101781170B (en) | 2010-03-18 | 2010-03-18 | Preparation method of dihydric alcohol |
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| CN101781170A true CN101781170A (en) | 2010-07-21 |
| CN101781170B CN101781170B (en) | 2013-06-26 |
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| CN2010101267581A Expired - Fee Related CN101781170B (en) | 2010-03-18 | 2010-03-18 | Preparation method of dihydric alcohol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119203A (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 dihydric alcohols by catalytic cracking of high carbon polyols under nitrogen atmosphere |
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 CN2010101267581A patent/CN101781170B/en not_active Expired - Fee Related
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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119203A (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 dihydric alcohols by catalytic cracking of high carbon polyols under nitrogen atmosphere |
| CN104119203B (en) * | 2013-04-26 | 2015-07-22 | 中国科学院大连化学物理研究所 | Method for preparation of dihydric alcohols by catalytic cracking of high carbon polyols under nitrogen atmosphere |
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| CN101781170B (en) | 2013-06-26 |
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