Method for synthesizing 1,2-propylene glycol using glucose

A technology of propylene glycol and glucose, which is applied in the field of glucose hydrogenolysis to prepare polyols, to avoid corrosion, solve equipment corrosion, and operate easily

Inactive Publication Date: 2015-10-07
DALIAN UNIV OF TECH +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] The invention provides a method for preparing polyalcohols by hydrogenolysis of glucose. Aiming at the problems of low glucose concentration and the requirement of corrosion resistance of equipment due to the addition of alkali, 1,2-propanediol is used as the target product to realize the directional resource utilization of glucose.

Method used

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  • Method for synthesizing 1,2-propylene glycol using glucose
  • Method for synthesizing 1,2-propylene glycol using glucose

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Experimental program
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Embodiment 1

[0018] The hydrogenolysis catalyst is a supported Cu, Ni, CuNi metal catalyst, the carrier is MgO, ZnO, and the specific surface area of ​​the catalyst is 200-300m 2 / g, the pore volume is 0.4-0.7cm 3 / g, the average pore size distribution is 3-6nm. The metal precursors are respectively nickel nitrate, copper nitrate, magnesium nitrate or zinc nitrate. The supported metal catalyst is prepared by a co-precipitation method through the steps of precipitation-drying-roasting and the like. The total molar loading of metal Cu and Ni is 30%, and the metal loading of Mg / Zn is 70%.

[0019] Glucose reaction results on different catalysts in the following table 1

[0020]

[0021]

[0022] Reaction conditions: 10wt% glucose aqueous solution 30g, catalyst 0.3g, Ca(OH) 2 0.08g, reaction pressure 6MPa, reaction temperature 140°C, reaction 2h, temperature raised to 220°C, reaction 3h. (EG in the table is ethylene glycol; 1,2-PD is 1,2-propanediol; GLY is glycerin)

[0023] It ca...

Embodiment 2

[0025] Based on the basicity of MgO, the basicity of the support in the Cu / MgO and Ni / MgO catalysts was respectively investigated instead of the solid base Ca(OH) 2 Effect on C-C Fragmentation. The following table 2 sees the impact of not adding solid base on the reaction result.

[0026]

[0027] a Ca(OH) 2 0.08g; b No Ca(OH) added 2 . Other reaction conditions: 10wt% glucose aqueous solution 30g, catalyst 0.3g, reaction pressure 6MPa, reaction temperature 140°C, reaction for 2h, temperature raised to 220°C, reaction for 3h. (EG in the table is ethylene glycol; 1,2-PD is 1,2-propanediol; GLY is glycerin)

[0028] It can be seen from Table 2 that in the low-concentration glucose hydrogenolysis reaction, the yield of 1,2-propanediol is slightly reduced, and the alkalinity of MgO can replace part of the solid base Ca(OH) 2 It plays a role in promoting C-C cleavage, and improves the yield of 1,2-propanediol by changing the reaction conditions.

Embodiment 3

[0030] Based on the fact that Cu / MgO and Ni / MgO catalysts have high selectivity in catalyzing the hydrogenolysis of glucose, the influence of CuNi / MgO with different metal ratios on the hydrogenolysis of glucose was considered. Table 3 below shows the reaction results of CuNi / MgO catalyzed hydrogenolysis of glucose with different metal ratios.

[0031]

[0032] Reaction conditions: 30g of 10wt% glucose aqueous solution, 0.3g of catalyst, no addition of Ca(OH) 2 , Reaction pressure 6MPa, reaction temperature 140°C, react for 2h, heat up to 220°C, react for 3h. (EG in the table is ethylene glycol; 1,2-PD is 1,2-propanediol; GLY is glycerol)

[0033] As can be seen from Table 3, with respect to other catalysts, the catalytic activity of 1Ni4Cu / MgO catalyst is relatively high, and the yield of 1,2-propanediol reaches 46.7%. Preliminary results show that 1Ni4Cu / MgO catalyst has certain potential for glucose conversion.

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Abstract

The invention discloses a method for synthesizing 1,2-propylene glycol using glucose, and belongs to the fields of environment protection and energy technology. The method is the technology which is characterized in that glucose of high density is used as a raw material, CuNi/MgO is used as a catalyst, and a two-stage intermittent reaction is used for producing 1,2-propylene glycol. A glucose solution is injected into a high pressure reaction vessel, and a hydrogenolysis catalyst is added for initiating a reaction; a carrier MgO with alkalescence is used for replacing the added solid alkali, so that the reaction is carried out under a neutral condition; the two-stage intermittent reaction is carried out, thereby avoiding influence of the high temperature polymerization on the reaction, a hydrogenolysis/hydrogenation reaction of glucose is carried out at low temperature for generating an intermediate product; after heating, the intermediate product is reacted further; after cooling, filtering and separating of the product, a low carbon polyhydric alcohol whose main component is 1,2-propylene glycol is obtained. According to the invention, the concentration and the reaction selectivity of the reaction raw material are increased, and the requirement of the reaction equipment is reduced, and the operation safety coefficient of the apparatus is increased.

Description

technical field [0001] The invention belongs to the technical field of environmental protection and energy, and relates to a method for preparing polyalcohol by hydrogenolysis of glucose. Background technique [0002] With the increasingly severe supply of fossil resources and the increasingly serious environmental problems, the development of new renewable carbon resources has become a very urgent issue. Biomass, as an abundant renewable resource, has attracted extensive attention for its conversion into high value-added chemicals. The two main forms of carbohydrates in nature are cellulose and starch. Through heterogeneous catalysis, it is of great practical significance to use biomass-derived carbohydrates as raw materials to prepare chemicals to reduce the dependence on traditional fossil raw materials. The process of producing glucose from starch has long been industrialized, and the hydrolysis technology of cellulose has also made great progress in recent years. The ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C29/00C07C31/20
CPCC07C29/00C07C31/205
Inventor 梁长海狄艳冰肖子辉徐彬高斌
Owner DALIAN UNIV OF TECH
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