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A kind of cu/mgo catalyst that catalyzes the hydrogenolysis of glucose and its preparation method

A technology of glucose and catalyst is applied in the field of Cu/MgO catalyst and preparation of catalyzing the hydrogenolysis of glucose to produce high value-added chemicals, which can solve the problem of high local concentration of active components, low single product selectivity, small specific surface area of ​​catalyst, etc. problems, to achieve broad industrial application prospects, to solve the effects of poor selectivity and excellent catalytic performance

Active Publication Date: 2017-03-29
DALIAN UNIV OF TECH +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The reaction pressure required by the process is high, and the single selectivity to the product is not high
Chinese patent, publication number: CN101921174A, introduces a method for preparing 1,2-PD and EG by catalyzing the hydrogenolysis of sorbitol supported by nano-carbon fiber with ruthenium. The catalyst used is a noble metal catalyst, which is expensive, and NaOH needs to be added to adjust the concentration of the solution. P H is between 11 and 13, and the conversion rate of sorbitol and the selectivity of products are not high
B.C.Miranda et al. (Appl.Catal.B:Environ., 2015,166–167,166–180) introduced the use of a bimetallic catalyst prepared by an equal volume impregnation method for the hydrogenolysis of glycerol. When the impregnation method was used to prepare the catalyst, it was The supported components are distributed on the surface of the carrier, and the utilization rate is high. A catalyst with good dispersion, large specific surface area and good activity is prepared. However, in the preparation process, the reduction temperature of the catalyst is high, and waste gas is generated when the precursor is decomposed. cause environmental pollution
Chinese patent, publication number: CN102924233A, introduces that the catalyst prepared by the co-precipitation method is used in the hydrogenolysis of glycerol to prepare propylene glycol. The preparation steps of the catalyst are many, and the influencing factors are complicated. If the operating conditions are not properly controlled, the active component may be partially Concentration is too high, resulting in agglomeration
X.C.Wang et al. (GreenChem., 2012, 14, 758-765) introduced the method of loading nickel-catalyzed hydrogenolysis of cellulose into 1,2-alkanediol. In this process, the specific surface area of ​​the catalyst prepared by co-precipitation method is relatively small (about 20m 2 g -1 ), and the hydrogenolysis reaction produces more types of products, and the single selectivity is poor
[0004] In view of the high production cost of catalysts used in glucose hydrogenolysis, the reaction solution often needs to add alkaline substances as accelerators and low production efficiency, we have successfully developed a basic magnesium oxide-supported copper-based catalyst prepared by MOCVD method. Good dispersion, large specific surface area, high catalytic activity, used in glucose hydrogenolysis reaction, no need to add alkaline accelerator, and glucose can be completely converted, the selectivity to 1,2-PD is 60% to 72%

Method used

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  • A kind of cu/mgo catalyst that catalyzes the hydrogenolysis of glucose and its preparation method
  • A kind of cu/mgo catalyst that catalyzes the hydrogenolysis of glucose and its preparation method
  • A kind of cu/mgo catalyst that catalyzes the hydrogenolysis of glucose and its preparation method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1~3

[0017] Add magnesium acetate tetrahydrate to a mixed solution of 60ML deionized water and absolute ethanol (volume ratio: 2:1, 1:1, 1:2 respectively) and stir the reaction, then add the solution to the stainless steel high pressure placed in an oven at 180°C to continue the reaction, and then the reaction solution was centrifuged, washed with corresponding proportions of deionized water and absolute ethanol, and finally dried in an oven to obtain Mg(OH) 2 , and placed in a tubular resistance furnace, calcined at 500°C in an atmosphere of argon and oxygen to obtain the MgO carrier. Considering the morphology and yield of MgO, deionized water and absolute ethanol with a volume ratio of 1:2 were selected for the reaction. The scanning electron microscope photographs of the obtained samples are shown in figure 1 .

[0018] Magnesium acetate tetrahydrate / g V 去离子水 :V 无水乙醇

Embodiment 4

[0020] Will Cu 2 O was added to a three-neck round bottom flask, 1,5-cyclooctadiene and THF were added under an argon atmosphere to stir the reaction, and then 1,1,1,5,5 , 5-hexafluoro-2,4-pentanedione and THF continue to stir and react, and filter unreacted Cu after the reaction 2 O, the resulting filtrate is distilled under reduced pressure to remove the solvent, and then the solid powder is purified by sublimation to obtain the corresponding metal organic precursor hexafluoroacetylacetone-cyclooctadiene copper (I), which is obtained by thermogravimetric analysis, The loading temperature of the monovalent copper precursor was selected to be 100°C.

Embodiment 5

[0022] Basically the same as in Example 4, except that 1,5-cyclooctadiene is not added, the corresponding metal organic precursor copper hexafluoroacetylacetonate can be obtained. According to thermogravimetric analysis, the loading temperature of the divalent copper precursor was selected as 60°C.

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Abstract

The invention discloses a glucose hydrogenolysis catalysis Cu / MgO catalyst and a preparation method thereof, and belongs to the technical field of heterogeneous catalysis. In anhydrous anaerobic conditions, by filtering, vacuum distillation and sublimation and purification of a liquid obtained by reaction of cuprous oxide, 1, 5-cyclooctadiene, and hexafluoro-acetylacetone, metal organic precursor hexafluoro-acetylacetone-cyclooctadiene copper and hexafluoro-acetylacetone copper relatively stable to air is produced. Petal shaped Mg (OH) 2 is synthesized by solvothermal method from magnesium acetate tetrahydrate as a raw material by use of a mixture of ethanol and deionized water solution as solvent, and the petal shaped Mg (OH) 2 is calcined to obtain an alkaline mesoporous MgO carrier with high specific surface area. By MOCVD (metal organic chemical vapor deposition) method, the two metal organic precursors are supported onto the MgO carrier for hydrogen reduction to obtain the copper base catalyst Cu / MgO used for glucose hydrogenolysis reaction. The glucose hydrogenolysis catalysis Cu / MgO catalyst has the advantages of simple operation process, mild reaction condition, good catalyst activity and stability, and good prospects of industrial application.

Description

technical field [0001] The invention belongs to the technical field of heterogeneous catalysis, and relates to a Cu / MgO catalyst and a preparation method for catalyzing glucose hydrogenolysis to produce high value-added chemicals. Background technique [0002] With the increasing shortage of fossil fuels, the increasing world population, and the increasing human demand for energy, it is of great significance to research and develop catalysts for the conversion of renewable resources (biomass) into high value-added chemicals. Biomass has a wide range of sources and is cheap. Among them, glucose is the most widely distributed and most important monosaccharide in nature. It is a polyhydroxy aldehyde. The natural form of glucose belongs to the D configuration. Fran configuration. At present, most of the catalytic hydrogenolysis of glucose to produce low-carbon polyols uses noble metal catalysts, the production cost is high, and it is often necessary to add alkaline substances a...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/72C07C31/20C07C29/00
Inventor 梁长海翟雪娇肖子辉徐彬高斌
Owner DALIAN UNIV OF TECH
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