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Method for preparing glycolate from carbohydrates

A technology for carbohydrates and glycolic acid esters, which is applied in the field of one-step catalytic production of glycolic acid esters from carbohydrates in an alcohol solution through a vanadium-containing or molybdenum-containing catalyst, and can solve problems such as unfavorable large-scale industrial production, unfavorable industrialized production, and inconvenient operation. , to achieve good catalytic cycle performance, abundant and renewable resources, and good industrial application prospects.

Inactive Publication Date: 2018-06-08
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] (1) One-step synthesis method of glyoxal and methanol, which was developed by Mitsui East Asia Chemical Co., Ltd. [Document 1: Qingpu, Zhongguang. Manufacturing method of glycolic acid ester [P].1996, JP: 08-104], Using glyoxal or other acetals and alcohols as raw materials, this method has mild reaction conditions, high reaction conversion and selectivity, but the glyoxal used as raw materials is toxic and expensive, which is not conducive to large-scale industrial production ;
[0005] (2) Formaldehyde carbonylation-esterification synthesis method, under high temperature and high pressure, formaldehyde aqueous solution and CO are condensed under the action of catalysts such as concentrated sulfuric acid or boron trifluoride to generate glycolic acid, and then esterified with alcohol to obtain glycolic acid Esters [Document 2: Soumay SanoH. Carbonylation of formaldehydecatalyzed by Cu(I), Ag(I) carbonyls at 1 atm [J]. Nippon Kagaku Kashi, 1982, (2): 163-166] [Document 3: Wei Wende. Organic Chemical Industry Encyclopedia of Raw Materials (Second Edition) Volume [M]. Beijing: Chemical Industry Press, 1999: 913-914], after the 1980s, this method had a major breakthrough, catalyst performance and reaction pressure were improved, and the product The selectivity has also been improved [Document 4: Li Jinchun. Synthesis and development prospects of methyl glycolate [J]. Sichuan Chemical Industry and Corrosion Control, 1998,1(6):24-27]. The disadvantage of this method is that the strong acid catalyst Severe corrosion of reaction equipment, and high pressure reaction, higher requirements for equipment
[0006] (3) Methylal and formic acid method, adopted by E.L.Yeakey et al. (CH 3 O) 2 CH 2 (methylal) and HCOOH are raw materials, under the situation that a kind of organic peroxide exists, and prepare glycolic acid alkyl ester under non-acidic condition, but reaction needs segmental to carry out, and product is difficult to separate [document 5: Production of Alkylglycolates, Patent No. US 4602102]
[0007] (4) Coupling method, this method mainly adopts methyl formate and acetaldehyde (or polyoxymethylene etc.) as raw material, adopts acid catalyzed method to synthesize methyl glycolate [document 6: Qi Weidong. Methyl glycolate coupling reaction The research progress of Yunnan Chemical Industry, 2002,29(4):33-35], this method is very corrosive to equipment, serious environmental pollution, not conducive to industrial production
[0008] (5) Chloroacetic acid method, chloroacetic acid method is to use chloroacetic acid and caustic soda to mix, heat reaction, reaction process is complicated, inconvenient to operate, and needs to neutralize acid-base strong acid [document 7: Duan Xingxin. Practical Fine Organic Synthesis Handbook [M] ]. Beijing: Chemical Industry Press, 2000:129] [Document 8: Xu Kexun. Handbook of Fine Organic Chemical Raw Materials and Intermediates [M]. Beijing: Chemical Industry Press, 1998: 1-268]
[0010] (7) Hydrogenation reduction of dimethyl oxalate. This reaction adopts a relatively novel C1 synthesis route, synthesizes oxalate from synthesis gas, and prepares glycolate by controlling the hydrogenation process [Document 9: Catalyst for hydrogenation of dimethyloxalate tomethylglycolate, comprises copper as active component, auxiliary active component and aluminum as structural carrier, in specifiedweight ratio.patent No.CN103801303-A] [Document 10: Zhang Xu. Research on Catalysts for Gas Phase Hydrogenation of Diethyl Oxalate [D]. Tianjin University, 2008 ], but it is easy to over-hydrogenate to ethylene glycol, resulting in a decrease in selectivity
At present, there is no report on the efficient and selective catalytic degradation of carbohydrates to produce glycolate

Method used

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  • Method for preparing glycolate from carbohydrates
  • Method for preparing glycolate from carbohydrates
  • Method for preparing glycolate from carbohydrates

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] h 10 PMo 5 V 7 o 40 Catalyst preparation

[0031] First put the 3.18g V 2 o 5 Add dropwise 30 mL of cold 10% H 2 o 2 solution to form a deep red vanadium peroxide (V) compound; gradually heated to room temperature, the solution decomposes and releases oxygen to form 0.0125mol / L orange H 6 V 10 o 28 Solution, then add excess concentrated phosphoric acid to solidify, forming dark brown H9 PV 14 o 42 solution;

[0032] The freshly prepared H 9 PV 14 o 42 The solution was gradually added dropwise to the boiling water containing 3.60g MoO 3 in the phosphoric acid suspension, stirred for 30min, MoO 3 Slowly dissolve into the mixed solution to form a solution, and obtain the heteropolyacid H 10 PMo 5 V 7 o 40 .

[0033] The obtained solid was filtered, washed, dried at about 110°C, and roasted at 300°C for 2 hours before use.

Embodiment 2

[0035] Preparation of V / AC: Weigh 50g of activated carbon (AC), 250mL of 33wt% nitric acid, place in a 500mL three-neck flask, treat in a water bath at 80°C for 24h, wash until neutral, and dry at 120°C for 24h. Pour 1g of pretreated AC into 0.23g of ammonium metavanadate (NH 4 VO 3 ) in an aqueous solution of 120°C after being dried in an oven, the catalyst precursor was subjected to temperature-programmed reduction in hydrogen. The heating rate of min was raised to 900 ° C and maintained for 1 h, and the hydrogen flow rate was 120 mL / min. The theoretical loading of V in the prepared catalyst was 10wt%.

Embodiment 3

[0037] Preparation of V / CMK-3: The preparation process was similar to Example 2, except that the AC carrier was replaced by CMK-3. The preparation process of CMK-3 is as follows: dissolve 1.25g sucrose in 5g deionized water, add 0.14g concentrated sulfuric acid, add 1g SBA-15 to the obtained mixed solution, soak at room temperature for 6h, and then dry at 100°C and 160°C for 6h respectively . The obtained beige powder was dipped again in a solution consisting of 0.8 g of sucrose, 0.09 g of concentrated sulfuric acid and 5 g of deionized water, and the drying step was repeated. Transfer to a tube furnace at a constant temperature of 900°C for 6 hours under a nitrogen atmosphere to completely carbonize the sucrose. Add 50ml of 4wt% hydrofluoric acid to the obtained black powder, stir at room temperature for 2h, filter / wash, repeat this process three times to completely remove silica, and finally dry overnight in an oven at 120°C to obtain ordered mesoporous carbon CMK -3.

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Abstract

The invention provides a method for efficiently preparing glycolate from carbohydrates as a raw material. Raw materials comprise carbohydrates and natural wood fiber containing carbohydrates, whereincarbohydrates contain cellulose, starch, hemicellulose, sucrose, glucose, fructose, fructan, xylose and soluble xylo-oligosaccharide. The method has the following advantages: carbohydrates or the natural wood fiber raw material containing carbohydrates is used, a catalyst is a compound containing vanadium or molybdenum, the reaction temperature is 100-450 DEG C in air atmosphere, the catalytic conversion process is completed in one step in an alcohol solvent, glycolate is prepared from carbohydrates with high conversion rate, high selectivity and high yield, raw materials used in the preparation process are renewable, and glycolate has the significant advantages of being natural, environmentally friendly, widely sourced and high in atom economy.

Description

technical field [0001] The invention relates to a preparation method of chemical product glycolic acid ester, in particular to a method for preparing glycolic acidic acid ester by one-step catalysis of carbohydrate in alcohol solution through a catalyst containing vanadium or molybdenum. Background technique [0002] Glycolate has its unique molecular structure: it has α-H, hydroxyl and ester functional groups at the same time, which makes it have the chemical properties of both alcohols and esters, and can undergo carbonylation reactions, hydrolysis reactions, oxidation reactions, etc., and can be widely used It has become an important chemical raw material in many fields such as chemical industry, medicine, pesticide, feed, spices and dyes. As a chemical intermediate, glycolic acid ester has the following uses: hydrogenation reduction to produce ethylene glycol, hydrolysis to produce glycolic acid, which can be used to produce polyester fiber and used as a cleaning agent, ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C69/675C07C67/00B01J31/18B01J27/199B01J23/22
CPCB01J23/22B01J27/199C07C67/00C07C69/675
Inventor 郑明远赵宇姜宇庞纪峰张涛
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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