Method for preparing 1,3 propylene glycol by using glycerol method

A technology of propylene glycol and glycerol, applied in chemical instruments and methods, preparation of hydroxyl compounds, preparation of organic compounds, etc., can solve the problems of high equipment investment, high reaction pressure, harsh production process, etc., and achieve good economic benefits and mild reaction conditions. , the effect of large market competitiveness

Inactive Publication Date: 2007-07-25
INST OF CHEM IND OF FOREST PROD CHINESE ACAD OF FORESTRY +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Acrolein hydration is an industrialized route to produce 1,3-PD with acrolein as raw material. The disadvantage is that acrolein itself is also an important organic intermediate, and it is highly toxic, flammable and explosive, and difficult to store and transport.
The ethylene oxide carbonylation method uses ethylene oxide (referred to as EO) as a raw material, undergoes hydroformylation to obtain 3-hydroxypropionaldehyde, and then hydrogenates to obtain 1,3-PD. The disadvantage of this process is that the equipment investment is high At the same time, the high-efficiency catalyst system is complex, the production process is harsh and unstable, the selection and improvement of the highly toxic ligand, and the reaction pressure is relatively high. The hydroformylation reaction pressure is about 10MPa, and the reactor structure is quite complicated.
The condensation of formaldehyde and acetaldehyde to prepare 1,3-PD is a process in which formaldehyde and acetaldehyde are condensed into 3-HPA by catalyst KOH. After removing KOH with ion exchange resin, it is reduced with aluminum isopropoxide to obtain 1,3-PD. -PD, this method has the advantage of easy access to raw materials, but the consumption of aluminum isopropoxide is large, and the cost of producing 1,3-PD is relatively high
With the large excess of glycerin, the by-product of oleochemicals, the preparation of 1,3-propanediol by the glycerol method, that is, the preparation of 1,3-propanediol with glycerol as a raw material, becomes an ideal method for preparing 1,3-propanediol. At present, the glycerol method prepares 1, At present, 3-propanediol is generally used by biological enzyme method, but the production cost of biological enzyme method is expensive, the activity and life of the enzyme are limited, the requirements for raw materials are harsh, and the requirements for the reaction environment are also high to ensure the activity of the enzyme, so it is necessary to develop glycerol A new method for the preparation of 1,3-propanediol

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Add 100ml of aqueous solution (prepared by dissolving the corresponding salt in water at 70°C) containing chromium nitrate hydrate (1.0M Cr), potassium tungstate (0.5M W) and copper acetate (0.25M Cu) into a 500ml flask . An aqueous solution of sodium hydroxide (0.5M) was then added dropwise. A reddish-brown gel formed within 15-30 minutes. The gel material was repeatedly washed with ammonium nitrate solution (1mol / L) to pH=8-9. After removing the water by using a rotary evaporator, the solid material was further dried overnight in a vacuum oven at 25°C, and then calcined. (Calcination is carried out in this way, the solid matter is placed in an air atmosphere, then heated to 275° C. at a rate of 10° C. / min and kept in an air atmosphere of 275° C. for 1 hour; then the air atmosphere is changed to argon and The material was heated from 275°C to 600°C at a rate of 2°C / min and the material was kept at 600°C under argon for 2 hours.) The nominal composition of the final ...

Embodiment 2

[0032]Add 100ml of aqueous solution (prepared by dissolving the corresponding salt in water at 70°C) containing chromium nitrate hydrate (1.0M Cr), potassium tungstate (0.5M W) and copper acetate (0.25M Cu) into a 500ml flask . An aqueous solution of sodium hydroxide (0.5M) was then added dropwise. A reddish-brown gel formed within 15-30 minutes. Stand in a dark place at 20°C for 72 hours. The gel material was repeatedly washed with ammonium nitrate solution (1mol / L) to pH=8-9. After removing water by using a rotary evaporator, the solid matter was further dried overnight in a vacuum oven at 25° C., and 34 g of a solid catalyst precursor were recovered. 17 g of this solid catalyst precursor were then calcined. Calcination is carried out by placing the solid substance in an air atmosphere, then heating it to 275°C at a rate of 10°C / min and maintaining it in an air atmosphere at 275°C for 1 hour; then changing the air atmosphere to argon and drying the substance Heat from 2...

Embodiment 3

[0035] An additional 17 g of solid catalyst precursor prepared in Example 2 was calcined in the following manner: the solid material was placed in an air atmosphere, then heated to 275° C. at a rate of 10° C. / min and held in an air atmosphere at 275° C. for 1 hours; the air atmosphere was then changed to argon and the mass was heated from 275°C to 600°C at a rate of 2°C / min and the mass was maintained at 600°C under argon for 5 hours. The nominal composition of the final catalyst is Cr 1 W 0.5 Cu 0.25 o x .

[0036] 10 grams of glycerol with a purity of 95% and 30 milliliters of hydrogen peroxide with a concentration of 30 percent were added to a 200 milliliter round-bottomed flask respectively, a condenser tube and a drying tube were installed, and the temperature was raised to 100° C. for 2 hours under stirring, and the reaction was stopped to obtain 9.0 grams Acetol. Add it into a 500 ml autoclave with 0.25 g of the catalyst prepared in advance, and continuously feed h...

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PUM

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Abstract

This invention discloses a method for preparing 1, 3-propylene glycol from glycerol. The method has such advantages as high catalytic activity, mild reaction conditions, high product selectivity, high product purity, simple process. The method comprises: (1) adding 95% glycerol and 30% oxydol into a round bottom flask, setting condensing tube and drying tube, heating to 100 deg.C under stirring, and reacting for 1-3 h to obtain acetone alcohol; (2) adding acetone alcohol into a pressure reaction kettle loaded with transition oxometalate catalyst, introducing hydrogen for 4-6 h at 100-200 deg.C and 10 MPa, reacting, and rectifying to obtain 1,3-propylene glycol.

Description

technical field [0001] The present invention relates to a kind of preparation 1,3-propanediol, more specifically relate to a kind of method of glycerol method preparation 1,3-propanediol. Background technique [0002] Glycerin is an important raw material for military industry, light industry, and chemical industry. In recent years, with the continuous expansion of oleochemicals, especially biodiesel, the by-product glycerin has been seriously oversupplied and its price has fallen sharply. It is important to develop downstream products using glycerin as a raw material. It is a good method to solve the excess of glycerin, if a suitable production method of downstream products can be developed, the production cost of downstream products can be reduced. 1,3-propanediol (1,3-propanediol is called for short 1,3-PD) is a kind of important chemical raw material, and its most important use is exactly as one of the monomers of synthesizing novel polyester (such as PTT). PTT has bett...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C29/145C07C31/20
Inventor 蒋剑春罗振扬顾晓利何明李书龙聂小安李翔宇
Owner INST OF CHEM IND OF FOREST PROD CHINESE ACAD OF FORESTRY
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