CN101781170B - Preparation method of dihydric alcohol - Google Patents
Preparation method of dihydric alcohol Download PDFInfo
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- CN101781170B CN101781170B CN2010101267581A CN201010126758A CN101781170B CN 101781170 B CN101781170 B CN 101781170B CN 2010101267581 A CN2010101267581 A CN 2010101267581A CN 201010126758 A CN201010126758 A CN 201010126758A CN 101781170 B CN101781170 B CN 101781170B
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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 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 must seek a kind of method of new raw material, novel process production dibasic alcohol.For example Chinese patent CN 1683293A discloses a kind of technique of being produced dibasic alcohol by cracking sorbierite, under the existence of sodium hydroxide and nickel/ruthenium catalyst, massfraction is 5%～30% sorbitol aqueous solution hydrocracking generating glycol and propylene glycol under high temperature, high pressure.This raw material that adopts is pure sorbitol aqueous solution, need to obtain by separating-purifying, and the method nickel used/the ruthenium catalyst price is more expensive.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that overcomes 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, take hexabasic alcohol as raw material, under the existence of hydrogenolysis catalyst, 180 ℃～260 ℃ of temperature of reaction, hydrogen pressure 8MPa～15MPa, pH value 11～14, the water hydrogenolysis makes dibasic alcohol, wherein hexabasic alcohol is 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 is 3%～10% of water gross weight, 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 separating-purifying, can be directly used in the present invention, select cheap, nickel-the molybdenum of chromium-doped, iron, tin or zinc-copper catalyst, its mass ratio is 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, the isomer such as 3-butyleneglycol, BDO, 2,3-butanediol.In addition, also comprise a small amount of glycerol, methyl alcohol, ethanol and unreacted sorbyl alcohol and N.F,USP MANNITOL etc. in reaction product of the present invention.
The present invention is under different catalysts and reaction conditions, and 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 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 reactor.Dropwise rear continuation and stir 1h, pour out liquid.Catalyst solid washing three times, 300 ℃, cooling after reduction 5h in water or alcoholic solvent in nitrogen atmosphere, obtain nickel-molybdenum-copper-chromium (or nickel-molybdenum-copper-Xi or nickel-molybdenum-copper-iron or nickel-molybdenum-copper-zinc) catalyzer.By the reaction of hydrochloric acid and aluminium and the replacement(metathesis)reaction of metal salt solution and aluminium, the 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 affect catalytic performance, the present invention does not do strict restriction to the content of aluminium.
Beneficial effect of the present invention is mainly reflected in: the raw material of selecting 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 separating-purifying; Select the nickel-molybdenum of chromium-doped or iron, tin, zinc-copper catalyst as the hydrogenolysis catalyst of the mixture of sorbyl alcohol and N.F,USP MANNITOL, low price.
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 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, then heat temperature raising, after the question response temperature is increased to 240 ℃, being filled with hydrogen to reaction pressure is that 11MPa begins the shortening scission reaction, react sampling after 1 hour, high pressure liquid chromatographic analysis, product composition and being distributed as: ethylene glycol 22.7%, propylene glycol 62%, butyleneglycol 7.8%, other is 5.2% years old, 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 difference is that the catalyzer that adopts is different with reaction conditions, and products distribution also has different, 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 take hexabasic alcohol as raw material, under the existence of hydrogenolysis catalyst, 180 ℃～260 ℃ of temperature of reaction, hydrogen pressure 8MPa～15MPa, pH value 11～14, 1 hour reaction times, the water hydrogenolysis makes dibasic alcohol, its Raw hexabasic alcohol is the mixture of sorbyl alcohol and 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 the nickel-molybdenum-copper catalyst of chromium-doped or iron, catalyst levels is 3%～10% of water gross weight, 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 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%.
According to claim 1 to 3 arbitrary described dibasic alcohol the preparation method, 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 |
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| CN2010101267581A CN101781170B (en) | 2010-03-18 | 2010-03-18 | Preparation method of dihydric alcohol |
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| CN2010101267581A CN101781170B (en) | 2010-03-18 | 2010-03-18 | Preparation method of dihydric alcohol |
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| CN101781170A CN101781170A (en) | 2010-07-21 |
| CN101781170B true CN101781170B (en) | 2013-06-26 |
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| JPH03109338A (en) * | 1989-09-22 | 1991-05-09 | Agency Of Ind Science & Technol | Production of alcohol using hydrocarbon as raw material |
| CN1762938A (en) * | 2005-09-21 | 2006-04-26 | 徐昌洪 | Method for producing ethylene glycol and lower polyol using hydrocracking |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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