CN101723800A - Method for preparing 1, 3-propylene glycol - Google Patents
Method for preparing 1, 3-propylene glycol Download PDFInfo
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- CN101723800A CN101723800A CN200810155293A CN200810155293A CN101723800A CN 101723800 A CN101723800 A CN 101723800A CN 200810155293 A CN200810155293 A CN 200810155293A CN 200810155293 A CN200810155293 A CN 200810155293A CN 101723800 A CN101723800 A CN 101723800A
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Abstract
The invention relates to a method for preparing 1, 3-propylene glycol, belonging to the technical field of chemical engineering. The method comprises: first, hydrating acraldehyde to prepare 3-hydroxyaldehyde (3-HPAL), and acidic catalyst is generally used for preparation with ion exchange resin and acidic molecular sieve as the preferential catalyst; second, reducing 3-hydroxy propanal into 1, 3-PDO by hydrogenation; when reducing the 3-hydroxy propanal into the 1, 3-PDO by hydrogenation, group VIII noble metal catalyst is used as catalyst. Pt and Pd are preferentially taking as catalyst and the catalyst loads on activated carbon or aluminum oxide. The temperature on hydrogenation is controlled to be 180-260 DEG C, liquid hourly volume space velocity is 0.6-1h-1 and the pressure of a reaction pressure gage is 3-6MPa, ensuring the conversion rate of the 3-hydroxy propanal not to be less than 80%, the selectivity of the 1, 3-PDO to be 90% and the weight yield of the 1, 3-PDO to be 95%.
Description
Technical field: the invention belongs to chemical technology field, be specifically related to a kind of 1, the preparation method of ammediol.
Background technology: 1, ammediol (1,3-Propanediol, be called for short 1,3-PDO, chemical formula is: CH2OHCH2CH2OH), be a kind of important Organic Chemicals, be mainly used in industries such as printing ink, coating, makeup, pharmacy, frostproofer, its most important purposes is the monomer as polyester, polyethers and polyurethane.By its synthetic polyester unique character and excellent performance are arranged, and can make polyester plastics have the biodegradable characteristic of the natural circulation of being easy to.
In recent years, as important organic synthesis raw material and intermediate, because of its special performance and widely purposes become the focus of research and development.As far back as 1948, U.S. Shell company just applied for synthesizing 1 with the acrolein hydration route, and the patent of 3-PDO, has been carried out industrialized implementation with this patent again at the sixties in 20th century and the seventies.Enter the eighties in 20th century and the nineties, German Degussa company has developed propenal path of preparing 1, the method for 3-PDO.Afterwards, it is raw material production 1 that U.S. Shell company develops with oxyethane (EO) again, the production technique of 3-PDO, and in realization suitability for industrialized production in 1996.In recent years, China also has how tame scientific research institutions to be engaged in 1, the development research of ammediol biological process technology.Wherein Dalian University of Technology's biochemical industry institute produces 1 with German national biotech research center joint study exploitation transformation of glycerol, and the technology of ammediol obtains very big progress already.This institute once with chemical industry metallurgical institute of Chinese Academy of Sciences cooperation development glycerine continuously ferment production and glycerine and 1, the novel process research of ammediol coproduction.Chemical industry metallurgical institute of the Chinese Academy of Sciences has industrialized technology of fermentative Production glycerine and experience.In addition, Tsing-Hua University's chemical industry is that applied chemistry institute is also carrying out fermentative Production 1 a few years ago, the development research of ammediol, and this institute also had the patented technology that two-step fermenting is produced glycerine at that time.But prior preparation method all exists transformation efficiency not high, and side reaction is higher, causes the subsequent disposal difficulty to strengthen the technical problem that yield is lower.
Summary of the invention: the present invention is directed to existing 1, ammediol preparation method defect of insufficient, and the exploitation preparation 1, the method for ammediol.The inventive method is adopted as the propenal raw material and prepares 1,3-PDO by two methods.
The present invention is achieved in that
At first, generally adopt an acidic catalyst by acrolein hydration system 3-hydroxy aldehyde (3-HPAL).Preferred catalyzer is ion exchange resin, acidic molecular sieve.Secondly be 1 by the 3-hydroxy propanal through hydrogenating reduction, 3-PDO.
CH2=CHCHO+H2O → HOCH2CH2CHO 3-hydroxy propanal
HOCH2CH2CO+H2→HOCH2CH2CH2OH 1,3-PDO
The reaction conditions of propene hydrate aldehyde is: temperature of reaction 60-100 ℃, residence time 1-3 hour, this moment acrolein conversion rate 70%, 3-HPAL selectivity 80%, the weight yield of 3-HPAL is 90%.
The 3-hydroxy propanal is 1 through hydrogenating reduction, and 3-PDO, the catalyzer of employing are the noble metal catalyst of VIII family, catalyzer is preferably Bo, Palladium, catalyst cupport is on gac or aluminum oxide, and the temperature of hydrogenation is 180-260 ℃, and volume space velocity is 0.6-1h-1 during liquid, reaction pressure gauge pressure 3-6MPa, this moment, 3-hydroxy propanal transformation efficiency was not less than 80%, 1,3-PDO selectivity 90%, 1, the weight yield of 3-PDO is 95%.
Embodiment: the present invention is described in detail below in conjunction with embodiment.
Embodiment 1
In small-sized reactor, add commodity propenal 300 grams, add ion exchange resin 100 grams, under condition of stirring, add deionized water 100 grams then, be heated to temperature to 60 ℃, stop heating, stir, stopped reaction after spending 1 hour, 3-HPAL is 320 grams in the mensuration solution, isolates 3-HPAL.Isolated 3-HPAL is equipped with the tubular reactor of platinum-aluminum trioxide catalyst from the top adding, the bottom of reactor leads to hydrogen, maintain the temperature at 180 ℃, volume space velocity is 0.6-h-1 during liquid, and reaction pressure is 3MPa, and reaction finishes and measures in the product 1, the content of 3-PDO, obtain 1, the 3-PDO300 gram, yield is 95.6%.
Embodiment 2
In small-sized reactor, add commodity propenal 300 grams, add ion exchange resin 100 grams, under condition of stirring, add deionized water 100 grams then, be heated to temperature to 80 ℃, stop heating, stir, stopped reaction after spending 2 hours, 3-HPAL is 325 grams in the mensuration solution, isolates 3-HPAL.Isolated 3-HPAL is equipped with the tubular reactor of platinum-aluminum trioxide catalyst from the top adding, the bottom of reactor leads to hydrogen, maintain the temperature at 200 ℃, volume space velocity is 0.8-h-1 during liquid, and reaction pressure is 4MPa, and reaction finishes and measures in the product 1, the content of 3-PDO, obtain 1, the 3-PDO300 gram, yield is 96.8%.
Claims (5)
1. one kind prepares 1, and the method for ammediol is characterized in that comprising following consecutive steps: at first adopting an acidic catalyst hydration system 3-hydroxy aldehyde by propenal, is 1 by the 3-hydroxy propanal through hydrogenating reduction secondly, 3-PDO.
2. preparation method as claimed in claim 1 is characterized in that an acidic catalyst is ion exchange resin, property molecular sieve.
3. preparation method as claimed in claim 1 is characterized in that the reaction conditions of propene hydrate aldehyde is: temperature of reaction 60-100 ℃, and residence time 1-3 hour.
4. preparation method as claimed in claim 1 is characterized in that the 3-hydroxy propanal is 1 through hydrogenating reduction, and 3-PDO, the catalyzer of employing are the noble metal catalyst of VIII family, and the temperature of hydrogenation is 180-260 ℃, and volume space velocity is 0.6-1h during liquid
-1, reaction pressure gauge pressure 3-6MPa.
5. preparation method as claimed in claim 4 is characterized in that catalyzer is Bo, Palladium, and catalyst cupport is on gac or aluminum oxide.
Priority Applications (1)
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CN200810155293A CN101723800A (en) | 2008-10-30 | 2008-10-30 | Method for preparing 1, 3-propylene glycol |
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CN200810155293A CN101723800A (en) | 2008-10-30 | 2008-10-30 | Method for preparing 1, 3-propylene glycol |
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CN200810155293A Pending CN101723800A (en) | 2008-10-30 | 2008-10-30 | Method for preparing 1, 3-propylene glycol |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110204422A (en) * | 2019-07-01 | 2019-09-06 | 宁波环洋新材料股份有限公司 | A method of 1,3- propylene glycol is prepared by methacrylaldehyde |
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2008
- 2008-10-30 CN CN200810155293A patent/CN101723800A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110204422A (en) * | 2019-07-01 | 2019-09-06 | 宁波环洋新材料股份有限公司 | A method of 1,3- propylene glycol is prepared by methacrylaldehyde |
CN110204422B (en) * | 2019-07-01 | 2022-06-10 | 宁波环洋新材料股份有限公司 | Method for preparing 1, 3-propylene glycol from acrolein |
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Open date: 20100609 |