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Supported catalyst for catalytic hydrogenolysis of glycerol to prepare dihydric alcohol and preparation method thereof

A supported catalyst, a technology for catalytic hydrogenolysis, applied in metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, chemical instruments and methods, etc., can solve the problem of low utilization rate of catalyst metal components and stable Unsatisfactory performance and other problems, to achieve the effect of high metal utilization rate, low cost and good stability

Inactive Publication Date: 2011-12-14
DALIAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Most of the non-precious metal catalysts currently developed are catalysts with copper as the active component prepared by coprecipitation method, which has better selectivity than noble metals, but the utilization rate of catalyst metal components is low.
In addition, this kind of catalyst needs reduction pretreatment to obtain higher activity, and the stability is not ideal during the reaction process.

Method used

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  • Supported catalyst for catalytic hydrogenolysis of glycerol to prepare dihydric alcohol and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] CuAg / Al 2 o 3 Batch reaction of supported cocatalyst (without reduction pretreatment) at 200 °C.

[0031] Catalyst preparation: Take 0.014mol copper nitrate, 0.006mol copper nitrate and 7.5g activated alumina powder, prepare a supported catalyst by equal volume impregnation method, dry at 110°C, and pre-calcine at 400°C in air.

[0032] Reaction conditions: adopt batch reaction, get 60mL of 50% (mass) glycerol aqueous solution, add 5.1g pretreated catalyst, now the molar ratio of catalyst metal component (Cu and Ag sum) and glycerin is 3: 100, The reaction pressure is 3.6Mpa, the reaction temperature is 200°C, and the reaction time is 10 hours.

[0033] Reaction result: the propylene glycol selectivity of above-mentioned reaction is 96%, and propylene glycol productive rate is 25.4%, is under the similar conditions (metal component and glycerol molar ratio 3: 100, reaction temperature, pressure, time etc. are identical) commercial chromous acid Copper (requires reduc...

Embodiment 2

[0035] CuAg / Al 2 o 3Batch Reaction of Supported Cocatalyst (Reducing Pretreatment) at 200℃

[0036] Catalyst preparation: take 0.014mol copper nitrate and 0.006mol copper nitrate and 7.5g activated alumina powder, prepare a supported catalyst by equal volume impregnation method, dry at 110°C, roast at 350°C, and reduce the pre- deal with.

[0037] Reaction conditions: adopt batch reaction, get 60mL of 50% (mass) glycerol aqueous solution, add 5.1g pretreated catalyst, at this moment the molar ratio of catalyst metal component (Cu and Ag sum) and glycerol is 3: 100, The reaction pressure is 3.6MPa, the reaction temperature is 200°C, and the reaction time is 10 hours.

[0038] Reaction result: the propylene glycol selectivity of above-mentioned reaction is 96%, and propylene glycol productive rate is 35.0%, is (metal and glycerol mol ratio 3: 100, reaction temperature, pressure, time etc. are identical) commercial copper chromite ( Reduction pretreatment) more than 3 times o...

Embodiment 3

[0040] Cu / Al 2 o 3 Batch Reaction of Supported Catalyst (Reduction Pretreatment) at 200℃

[0041] Catalyst preparation: Take 0.02mol of copper nitrate and 7.5g of activated alumina powder, prepare a supported catalyst by equal volume impregnation method, dry at 110°C, roast at 350°C, and perform reduction pretreatment in hydrogen at 350°C.

[0042] Reaction conditions: adopt batch reaction, get 60mL of 50% (mass) glycerol aqueous solution, add the good catalyst of 5.0g pretreatment, now the mol ratio of catalyst metal component and glycerin is 3: 100, reaction pressure 3.6MPa, reaction temperature 200°C, the reaction time is 10 hours.

[0043] Reaction result: the propylene glycol selectivity of above-mentioned reaction is 94%, and propylene glycol productive rate is 31.8%, is (Cu and glycerol mol ratio 3: 100, reaction temperature, pressure, time etc. are identical) on commercial copper chromite ( Reduction pretreatment is required) 3 times of the propylene glycol yield (1...

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Abstract

The invention relates to a supported catalyst for catalyzing the hydrogenolysis of glycerol to prepare dihydric alcohol and a preparation method thereof. The catalyst consists of active components, auxiliary agents and carriers. The catalyst introduces Ag as a key component into the catalyst formula, and the catalyst prepared by Ag and Cu together as active components can obtain better activity under milder reaction conditions without reduction pretreatment, and is stable during the reaction process. Good performance; compared with the catalyst prepared by industrial co-precipitation method, the use efficiency of the metal component of the CuAg / Al2O3 catalyst is significantly improved, and the selectivity of propylene glycol is above 90%, which is higher than the selectivity of Ru-based supported noble metal catalysts . The catalyst of the present invention has the advantages of high selectivity, mild reaction conditions, low cost and good stability in the reaction of catalyzing the hydrogenolysis of glycerol to produce propylene glycol, and can be used for the reaction of catalyzing the hydrogenolysis of glycerol to prepare small molecular glycols, and can also be used It is used in the reaction of sugar hydrogenolysis to produce lower alcohols.

Description

technical field [0001] The invention relates to a supported catalyst for catalyzing the hydrogenolysis of glycerin to prepare dihydric alcohol and a preparation method thereof. Background technique [0002] Small molecule diols (1,2-propanediol, 1,3-propanediol and ethylene glycol) are important organic chemical raw materials. They are widely used in chemical production and daily life, and their demand is increasing day by day. However, the current production of diols (PDO) is almost entirely obtained from the petrochemical industry, and its production methods are under the pressure of production costs. It is urgent to develop new raw material sources and synthetic routes to achieve sustainable development. On the other hand, the rapid development of the biodiesel industry has led to a sharp increase in the world's glycerin production, making it a relatively cheap renewable industrial raw material with sufficient supply. In this situation, many researchers continue to explo...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/89B01J23/72B01J23/50C07C31/20C07C29/132
Inventor 周锦霞张曙光郭丽媛
Owner DALIAN UNIV