CN1762938A - Method for producing ethylene glycol and lower polyol using hydrocracking - Google Patents
Method for producing ethylene glycol and lower polyol using hydrocracking Download PDFInfo
- Publication number
- CN1762938A CN1762938A CN 200510094472 CN200510094472A CN1762938A CN 1762938 A CN1762938 A CN 1762938A CN 200510094472 CN200510094472 CN 200510094472 CN 200510094472 A CN200510094472 A CN 200510094472A CN 1762938 A CN1762938 A CN 1762938A
- Authority
- CN
- China
- Prior art keywords
- ethylene glycol
- hydrocracking
- lower polyol
- produced
- glycol
- 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.)
- Pending
Links
Abstract
The hydrocracking process is one process, in which saccharide or alditol is produced into ethylene glycol, propylene glycol and other lower alcohols in conditions of relatively high temperature and certain hydrogen pressure. The technological process includes two steps. In the first step, the material inside some solvent is hydroreduced into corresponding alditol at relatively low temperature of 50-150 deg.c and relatively low hydrogen pressure of 3.5-7.0 MPa. In the second step, catalyst and alkali promoter are added to perform hydrocracking reaction at temperature 150-250 deg.c and hydrogen pressure 7.0-10.5 MPa for 3-5 hr to obtain lower alcohols with ethylene glycol and propylene glycol as main components. The present invention may have sorbic alcohol as material to reach conversion rate of 80-100 %, and mixed solvent for lowered power consumption in evaporating water.
Description
Technical field
The present invention be a kind of with using hydrocracking with carbohydrate or glycitols by producing the technology that ethylene glycol and propylene glycol are product such as main under comparatively high temps and the certain hydrogen-pressure.
Background technology
Ethylene glycol is the 3rd the important chemical products that is only second to polyethylene and polyvinyl chloride in the ethylene industry derivative.It is the basic raw material of producing trevira.Its purposes is very extensive: be mainly used in and produce trevira, unsaturated polyester resin, frostproofer, lubricant, softening agent, tensio-active agent, coating and oily magnitude industry.Itself is the solvent and the medium of some organic synthesis, still produces the raw material of special solvent gylcol ether.
Propylene glycol also is important industrial chemicals.1, the 2-propylene glycol is a raw material of producing unsaturated polyester resin, urethane resin, Resins, epoxy, Synolac, also is polyester plasticizer.At essence and flavoring agent, makeup, medicine, industries such as cigarette have big consumption.Being organic synthesis intermediate, also is good nontoxic solvent.
Up to the present, each big production ethylene glycol enterprise of the world all is that to adopt with the oil be the technology of raw material basically.Some ethylene glycol production units of China also all are petrochemical systems.Introduction of foreign technology and suite of equipment are synthetic and catalytic hydration production ethylene glycol mostly by the oxyethane pressurized water.These technical process are long, and facility investment is big, the energy consumption height; Perhaps Preparation of catalysts complexity, problems such as instability or residual quantity are difficult to solve.And oil recovery, transportation and refining etc. all may cause problems such as serious environmental pollution.
Soaring along with the minimizing of petroleum resources and oil price is that the operational path of raw material obviously has been subjected to very big threat by oil.World's oilreserves sharply descends, and many chemical engineering industries are just carrying out the adjustment of raw material mix.Existing in the world at present trend thinks that the petrochemical industry route does not have competitive power, based on the raw material of biomass resource, can take from plant, and can be converted into needed product with enzymolysis process.Cereal starch is a kind of renewable raw materials, is that raw material has its very big advantage than oil gas non-renewable and resource exhaustion day by day.
Summary of the invention
Technical problem: purpose of the present invention just provides the raw material of a kind of utilization based on biomass resource, produces the method for ethylene glycol and lower polyol by using hydrocracking.
Technical scheme: using hydrocracking of the present invention is produced the method for ethylene glycol and lower polyol and is carried out in two steps: the first step, earlier raw material is added in the solvent, promptly 50 ℃-150 ℃ of lesser tempss, and the i.e. 3.5～7.0Mpa of low hydrogen pressure, the time is that to carry out hydro-reduction under 1～3 hour the condition be corresponding sugar alcohol; Second step added catalyzer and alkali promotor and carries out hydrocarbon hydrocracking reaction, and temperature of reaction is 150 ℃～250 ℃, and hydrogen pressure is 7.0～10.5Mpa, and the time is 3～5 hours, obtains ethylene glycol, and propylene glycol is the main lower polyol that waits.
The raw material that is adopted has aldose or sugar alcohol or saccharan.
Described aldose is one or more the mixture in glucose, seminose, wood sugar, pectinose and their hydro-reduction product sorbyl alcohol, mannitol, Xylitol, the arabitol.
Described sugar alcohol is to adopt cereal starch and other plant amylum or fiber hydrolysis, and the small molecular sugar that enzymolysis obtains obtains corresponding sugar alcohol through hydro-reduction again.
Used catalyzer is one or more in the following material: nickel, cobalt, rhenium, rhodium, ruthenium, osmium metal or its salt and their mixture, or the complex compound of these metals or salt and organic phosphine formation.
The carrier of described catalyzer is a gac, or aluminum oxide, or diatomite or molecular sieve.
Described alkali promotor has sodium hydroxide, or potassium hydroxide or calcium oxide or calcium hydroxide.
Described solvent is water, ethanol, Virahol, this butanols of 2-hydroxyl, N-methylformamide, N-N-methyl 2-pyrrolidone N-, N-methyl caprolactam, diox, glycol dimethyl ether, the mixed solution of one or more in the tetraethyleneglycol dimethyl ether.
Beneficial effect: the technology of having reported both at home and abroad before the present invention has improved.Advantage is:
(1) be raw material by sorbyl alcohol, can reach 80%～100% transformation efficiency, the total molal selectivity of ethylene glycol and propylene glycol is 75%～180%.
(2) be raw material by sugar, can carry out hydro-reduction and hydrocracking continuously and obtain needed lower polyol.
(3) select mixed solvent for use, can reduce the needed energy consumption of vaporize water.
Embodiment
Using hydrocracking of the present invention is produced the method for ethylene glycol and lower polyol and is carried out in two steps: the first step, earlier raw material is added in the solvent, promptly 50 ℃-150 ℃ of lesser tempss, and the i.e. 3.5～7.0Mpa of low hydrogen pressure, the time is that to carry out hydro-reduction under 1～3 hour the condition be corresponding sugar alcohol; Second step added catalyzer and alkali promotor and carries out hydrocarbon hydrocracking reaction, and temperature of reaction is 150 ℃～250 ℃, and hydrogen pressure is 7.0～10.5Mpa, and the time is 3～5 hours, obtains ethylene glycol, and propylene glycol is the main lower polyol that waits.
The raw material that the present invention adopts has cereal starch and other plant amylum or fiber hydrolysis, and the small molecular sugar that enzymolysis obtains obtains corresponding sugar alcohol through hydro-reduction again.Glucose, seminose, wood sugar, arabitol etc. are arranged.Raw material can be pure, thick, blended, or hydrolysis enzymolysis solution.Also can use low molecular polylol.With Xylitol or arabitol is raw material, can obtain highly selective ethylene glycol.
Catalyst system is selected for use from the solid catalyst system of transition metal on some carrier.Metal is nickel, cobalt, rhenium, rhodium, ruthenium, osmium etc. or its salt, and their mixture, or the complex compound that forms with organic phosphine.Carrier has gac, aluminum oxide, diatomite and molecular sieve etc.
Reaction can be carried out in the aqueous solution, also can non-aqueous solution in or carry out in the mixed solvent.Non-aqueous solution has the mixed solvent of ethanol, Virahol, 2-hydroxyl butanols, tetrahydrofuran (THF), diox, N-methylformamide, N-methyl caprolactam, N-methyl solution, and is capable of reducing energy consumption.
Some catalyst system need add alkali promotor, can strengthen catalyst activity, promotes reaction to carry out smoothly, improves selectivity.
Embodiment 1:40 restrains sorbyl alcohol, is dissolved in 40 gram water and 40 gram tetrahydrofuran (THF)s; Add 5 gram 5%Ru/c3 gram calcium oxide; Logical hydrogen reaches 10.5Mpa, is heated to 220 ℃～250 ℃, and after four hours, transformation efficiency can reach 100%, and the molal selectivity of ethylene glycol and propylene glycol is 75%, and by product is 12% methane, 3% methyl alcohol, and 1% ethanol also has a small amount of C
4With C
5Composition.
Embodiment 2:40 restrains glucose, is dissolved in the 80 gram water processing 5 grams " Raney Ni ", hydro-reduction is 2 hours under 150 ℃ and 6.0Mpal, hydrocracking 4 hours under 250 ℃ and 10.5Mpa then, the molal selectivity of ethylene glycol and propylene glycol reaches 140%, and the selectivity of glycerine is 5%.
Embodiment 3:50 kilogram starch hydrolyzate (60%W/V), add 5 kilograms " Raney Ni " logical hydrogen, maintained 140 ℃/9.5Mpa about 85 minutes, cooling elimination catalyzer, add 5 kilograms of 5%Ru/c, maintain 250 ℃/10.5Mpa, 4 hours, the molal selectivity of ethylene glycol and propylene glycol was about 110%.
Claims (8)
1. a using hydrocracking is produced the method for ethylene glycol and lower polyol, it is characterized in that this method carries out in two steps: the first step, earlier raw material is added in the solvent, promptly 50 ℃-150 ℃ of lesser tempss, and the i.e. 3.5～7.0Mpa of low hydrogen pressure, the time is that to carry out hydro-reduction under 1～3 hour the condition be corresponding sugar alcohol; Second step added catalyzer and alkali promotor and carries out hydrocarbon hydrocracking reaction, and temperature of reaction is 150 ℃～250 ℃, and hydrogen pressure is 7.0～10.5Mpa, and the time is 3～5 hours, obtains ethylene glycol, and propylene glycol is main lower polyol.
2. using hydrocracking according to claim 1 is produced the method for ethylene glycol and lower polyol, it is characterized in that the raw material that is adopted has aldose or sugar alcohol or saccharan.
3. using hydrocracking according to claim 2 is produced the method for ethylene glycol and lower polyol, it is characterized in that described aldose is one or more the mixture in glucose, seminose, wood sugar, pectinose and their hydro-reduction product sorbyl alcohol, mannitol, Xylitol, the arabitol.
4. the method for producing ethylene glycol and lower polyol according to claim 2 or 3 described using hydrocrackings, it is characterized in that described sugar alcohol is to adopt cereal starch and other plant amylum or fiber hydrolysis, the small molecular sugar that enzymolysis obtains obtains corresponding sugar alcohol through hydro-reduction again.
5. using hydrocracking according to claim 1 is produced the method for ethylene glycol and lower polyol, it is characterized in that used catalyzer is one or more in the following material: nickel, cobalt, rhenium, rhodium, ruthenium, osmium metal or its salt and their mixture, or the complex compound of these metals or salt and organic phosphine formation.
6. the using hydrocracking method of producing ethylene glycol and lower polyol according to claim 1 or 5, the carrier that it is characterized in that described catalyzer is a gac, or aluminum oxide, or diatomite or molecular sieve.
7. using hydrocracking according to claim 1 is produced the method for ethylene glycol and lower polyol, it is characterized in that described alkali promotor has sodium hydroxide, or potassium hydroxide or calcium oxide or calcium hydroxide.
8. using hydrocracking according to claim 1 is produced the method for ethylene glycol and lower polyol, it is characterized in that described solvent is water, ethanol, Virahol, this butanols of 2-hydroxyl, the N-methylformamide, the N-N-methyl 2-pyrrolidone N-, N-methyl caprolactam, diox, glycol dimethyl ether, the mixed solution of one or more in the tetraethyl-glycol dimethyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510094472 CN1762938A (en) | 2005-09-21 | 2005-09-21 | Method for producing ethylene glycol and lower polyol using hydrocracking |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510094472 CN1762938A (en) | 2005-09-21 | 2005-09-21 | Method for producing ethylene glycol and lower polyol using hydrocracking |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1762938A true CN1762938A (en) | 2006-04-26 |
Family
ID=36747297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510094472 Pending CN1762938A (en) | 2005-09-21 | 2005-09-21 | Method for producing ethylene glycol and lower polyol using hydrocracking |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1762938A (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781167A (en) * | 2010-03-18 | 2010-07-21 | 西安近代化学研究所 | Method for synthesizing dihydric alcohol and polyhydric alcohol |
| CN101781166A (en) * | 2010-03-18 | 2010-07-21 | 西安近代化学研究所 | Preparation method of dihydric alcohol |
| CN101781171A (en) * | 2010-03-18 | 2010-07-21 | 西安近代化学研究所 | Preparation method of dihydric alcohol |
| CN101781170A (en) * | 2010-03-18 | 2010-07-21 | 西安近代化学研究所 | Preparation method of dihydric alcohol |
| 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 |
| CN102391066A (en) * | 2011-08-09 | 2012-03-28 | 山东省鲁洲食品集团有限公司 | Method for carrying out one-step method to produce low-molecular-weight polyalcohols by utilizing glucose |
| CN103130612A (en) * | 2011-11-24 | 2013-06-05 | 中国科学院青岛生物能源与过程研究所 | Method for applying skeleton metal catalyst in polyhydroxy compound hydrogenolysis |
| CN104292071A (en) * | 2014-09-19 | 2015-01-21 | 浙江科技学院 | Method for preparing low-grade polyols |
| CN104370692A (en) * | 2013-08-13 | 2015-02-25 | 北京化工大学 | Polyol preparation method through glucose hydrogenolysis |
| CN104557451A (en) * | 2015-01-04 | 2015-04-29 | 南京工业大学 | Method for catalyzing sugar and sugar alcohol hydrocracking reaction through nickel-based catalyst |
| CN104860800A (en) * | 2014-02-21 | 2015-08-26 | 中国科学院大连化学物理研究所 | Method used for preparing ethylene glycol monomethyl ether from sugar alcohols |
| CN104961625A (en) * | 2015-04-27 | 2015-10-07 | 大连理工大学 | Method for synthesizing 1,2-propylene glycol using glucose |
| WO2016001169A1 (en) * | 2014-06-30 | 2016-01-07 | Haldor Topsøe A/S | Process for the preparation of ethylene glycol from sugars |
| WO2017001382A1 (en) * | 2015-06-30 | 2017-01-05 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of glycols |
| CN106866374A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | It is a kind of by xylose or the method for xylooligosaccharides production 1,2- propane diols and ethylene glycol |
| CN109692687A (en) * | 2018-12-28 | 2019-04-30 | 浙江工业大学 | A kind of platinum nickel/active carbon is total to loaded catalyst and its preparation and application |
| CN111054337A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing ethylene glycol from biomass |
-
2005
- 2005-09-21 CN CN 200510094472 patent/CN1762938A/en active Pending
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781167B (en) * | 2010-03-18 | 2013-04-17 | 西安近代化学研究所 | Method for synthesizing dihydric alcohol and polyhydric alcohol |
| CN101781166A (en) * | 2010-03-18 | 2010-07-21 | 西安近代化学研究所 | Preparation method of dihydric alcohol |
| CN101781171A (en) * | 2010-03-18 | 2010-07-21 | 西安近代化学研究所 | Preparation method of dihydric alcohol |
| CN101781170A (en) * | 2010-03-18 | 2010-07-21 | 西安近代化学研究所 | Preparation method of dihydric alcohol |
| CN101781167A (en) * | 2010-03-18 | 2010-07-21 | 西安近代化学研究所 | Method for synthesizing dihydric alcohol and polyhydric alcohol |
| CN101781166B (en) * | 2010-03-18 | 2013-06-05 | 西安近代化学研究所 | Preparation method of dihydric alcohol |
| 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 |
| CN102391066A (en) * | 2011-08-09 | 2012-03-28 | 山东省鲁洲食品集团有限公司 | Method for carrying out one-step method to produce low-molecular-weight polyalcohols by utilizing glucose |
| CN103130612A (en) * | 2011-11-24 | 2013-06-05 | 中国科学院青岛生物能源与过程研究所 | Method for applying skeleton metal catalyst in polyhydroxy compound hydrogenolysis |
| CN104370692B (en) * | 2013-08-13 | 2017-02-15 | 北京化工大学 | Polyol preparation method through glucose hydrogenolysis |
| CN104370692A (en) * | 2013-08-13 | 2015-02-25 | 北京化工大学 | Polyol preparation method through glucose hydrogenolysis |
| CN104860800B (en) * | 2014-02-21 | 2016-09-14 | 中国科学院大连化学物理研究所 | A kind of method being prepared glycol monoethyl ether by sugar alcohol |
| CN104860800A (en) * | 2014-02-21 | 2015-08-26 | 中国科学院大连化学物理研究所 | Method used for preparing ethylene glycol monomethyl ether from sugar alcohols |
| WO2016001169A1 (en) * | 2014-06-30 | 2016-01-07 | Haldor Topsøe A/S | Process for the preparation of ethylene glycol from sugars |
| US10077222B2 (en) | 2014-06-30 | 2018-09-18 | Haldor Topsoe A/S | Process for the preparation of ethylene glycol from sugars |
| CN104292071B (en) * | 2014-09-19 | 2016-01-20 | 浙江科技学院 | A kind of method preparing lower polyol |
| CN104292071A (en) * | 2014-09-19 | 2015-01-21 | 浙江科技学院 | Method for preparing low-grade polyols |
| CN104557451A (en) * | 2015-01-04 | 2015-04-29 | 南京工业大学 | Method for catalyzing sugar and sugar alcohol hydrocracking reaction through nickel-based catalyst |
| CN104557451B (en) * | 2015-01-04 | 2017-02-08 | 南京工业大学 | Method for catalyzing sugar and sugar alcohol hydrocracking reaction through nickel-based catalyst |
| CN104961625A (en) * | 2015-04-27 | 2015-10-07 | 大连理工大学 | Method for synthesizing 1,2-propylene glycol using glucose |
| CN107787312B (en) * | 2015-06-30 | 2021-03-05 | 国际壳牌研究有限公司 | Process for the preparation of diols |
| WO2017001382A1 (en) * | 2015-06-30 | 2017-01-05 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of glycols |
| CN107787312A (en) * | 2015-06-30 | 2018-03-09 | 国际壳牌研究有限公司 | method for preparing glycol |
| CN106866374A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | It is a kind of by xylose or the method for xylooligosaccharides production 1,2- propane diols and ethylene glycol |
| CN106866374B (en) * | 2015-12-12 | 2020-08-04 | 中国科学院大连化学物理研究所 | Method for producing 1, 2-propylene glycol and ethylene glycol from xylose or xylo-oligosaccharide |
| CN111054337A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing ethylene glycol from biomass |
| CN111054337B (en) * | 2018-10-16 | 2023-01-31 | 中国石油化工股份有限公司 | Catalyst for preparing ethylene glycol from biomass |
| CN109692687A (en) * | 2018-12-28 | 2019-04-30 | 浙江工业大学 | A kind of platinum nickel/active carbon is total to loaded catalyst and its preparation and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1762938A (en) | Method for producing ethylene glycol and lower polyol using hydrocracking | |
| Yu et al. | Synthesis of γ-valerolactone from different biomass-derived feedstocks: Recent advances on reaction mechanisms and catalytic systems | |
| CN101475442B (en) | Method for preparing ethylene glycol from oxalic ester | |
| CN101475441A (en) | Method for preparing ethylene glycol from oxalic ester | |
| CN1683293A (en) | Process for producing diatomic alcohol and polyol from cracking sorbierite | |
| CN103209950A (en) | Method for catalytically producing formic acid | |
| CN102850157B (en) | Novel technique for preparing long-chain alkane efficiently through multifunctional catalyst in one-step method | |
| CN101475443A (en) | Method for preparing ethylene glycol | |
| CN103193623A (en) | Method for catalytic preparation of acetylpropionic acid in one step by using waste residues obtained by producing xylose | |
| CN113877583B (en) | Catalyst in process for producing 1, 5-pentanediol by hydrofuran alcohol hydro-ring opening, preparation and application | |
| CN109608304B (en) | Method for directly producing 1, 2-pentanediol by furfural hydrogenation | |
| CN103420817B (en) | By the method for dimethoxym ethane and paraformaldehyde synthesizing polyoxymethylene dimethyl ether | |
| CN101781167B (en) | Method for synthesizing dihydric alcohol and polyhydric alcohol | |
| CN101544537A (en) | Method for producing low carbon chemical ethanol from C6 sugar alcohol | |
| CN102219641A (en) | Method for purifying ethylene glycol | |
| CN110102343B (en) | Composite acid catalyst and method for preparing 5-hydroxymethylfurfural by catalyzing saccharides through composite acid catalyst | |
| CN102372598A (en) | Method for separating glycol from butanediol | |
| CN101830774A (en) | Method for preparing C2-4 dihydric alcohol and polyalcohol from starch raw materials | |
| CN103896703A (en) | Method of preparing C5 and C6 alkanes by catalytically converting lignocelluloses by virtue of one-step method | |
| CN110590860B (en) | Method for preparing lignin oligomer by selective reductive degradation | |
| CN1915962A (en) | Method for preparing 1,4 - cyclohexanedicarboxylate | |
| CN106881102A (en) | A kind of method by cobalt base amorphous state catalyst ethyl lactate hydrogenation synthesis 1,2- propane diols | |
| CN114230429B (en) | Method for synthesizing methyl cyclopentadiene from 3-hydroxymethyl cyclopentanone | |
| CN102276418B (en) | Ethylene glycol purification method | |
| CN1275689C (en) | Catalyzer synthesized from ethyl lactate and hydrogen in use for 1, 2 propylene glycol, and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |