阅读说明：本技术 葡萄糖氢解反应目标产物为二元醇的催化剂的制备方法 (Preparation method of catalyst with target product of glucose hydrogenolysis reaction being dihydric alcohol ) 是由 张燚 徐莹 刘意 吉嘉铖 于 2019-03-15 设计创作，主要内容包括：本发明公开了葡萄糖氢解反应目标产物为二元醇的催化剂的制备方法,包括如下步骤：1)称取乙酸钴和钼酸铵,溶解于去离子水中,搅拌使之完全溶解至形成澄清透明的红色混合溶液；2)在搅拌条件下,将乙醇逐滴加入到红色混合溶液中,并在水浴条件下保温,逐渐生成紫色沉淀物；3)将紫色沉淀物分别用去离子水和无水乙醇洗涤2-3次；4)将沉淀物转移至烘箱,在空气氛围中干燥；5)将干燥后沉淀物转移至马弗炉,在空气氛围中焙烧,即可得到棒状形貌的钼酸钴催化剂。该制备方法制得的催化剂为钼酸钴催化剂,呈棒状形貌,使用该催化剂,可以使得葡萄糖的转化率达到100％,总二元醇的选择性≥80％,目标产物丙二醇的选择性≥60％。(The invention discloses a preparation method of a catalyst with a target product of a glucose hydrogenolysis reaction being dihydric alcohol, which comprises the following steps: 1) weighing cobalt acetate and ammonium molybdate, dissolving the cobalt acetate and the ammonium molybdate in deionized water, and stirring to completely dissolve the cobalt acetate and the ammonium molybdate until a clear and transparent red mixed solution is formed; 2) under the condition of stirring, dropwise adding ethanol into the red mixed solution, and preserving heat under the condition of water bath to gradually generate purple precipitates; 3) washing the purple precipitate with deionized water and anhydrous ethanol for 2-3 times; 4) transferring the precipitate to an oven, and drying in an air atmosphere; 5) and transferring the dried precipitate to a muffle furnace, and roasting in the air atmosphere to obtain the rod-shaped cobalt molybdate catalyst. The catalyst prepared by the preparation method is a cobalt molybdate catalyst and is in a rod-like shape, and by using the catalyst, the conversion rate of glucose can reach 100%, the selectivity of total dihydric alcohol is more than or equal to 80%, and the selectivity of a target product, namely propylene glycol is more than or equal to 60%.)

1. The preparation method of the catalyst with the target product of the hydrogenolysis reaction of glucose being dihydric alcohol is characterized by comprising the following steps:

1) weighing cobalt acetate and ammonium molybdate, dissolving the cobalt acetate and the ammonium molybdate in deionized water, and stirring to completely dissolve the cobalt acetate and the ammonium molybdate until a clear and transparent red mixed solution is formed;

2) under the condition of stirring, dropwise adding ethanol into the red mixed solution, and preserving heat under the condition of water bath to gradually generate purple precipitates;

3) washing the purple precipitate with deionized water and anhydrous ethanol for 2-3 times;

4) transferring the precipitate to an oven, and drying in an air atmosphere;

5) and transferring the dried precipitate to a muffle furnace, and roasting in the air atmosphere to obtain the rod-shaped cobalt molybdate catalyst.

2. The method for preparing the catalyst according to claim 1, wherein: in the step 1), the ratio of the amount of cobalt in the cobalt acetate to the amount of molybdenum in the ammonium molybdate is 0.8-1: 0.8-1.

3. The method for preparing the catalyst according to claim 2, wherein: in step 1), the ratio of the amount of cobalt species in the cobalt acetate to the amount of molybdenum species in the ammonium molybdate used was 1: 1.

4. The method for preparing the catalyst according to claim 1, wherein: in the step 2), the water bath condition is maintained for 3-5h at 80-90 ℃.

5. The method for preparing the catalyst according to claim 4, wherein: in the step 2), the water bath condition is maintained for 4 hours at 85 ℃.

6. The method for preparing the catalyst according to claim 1, wherein: in the step 4), the drying condition is that the heat preservation time is 10-15h under the air condition of 70-90 ℃.

7. The method for preparing the catalyst according to claim 6, wherein: in the step 4), the drying condition is that the heat preservation time is 12 hours under the air condition of 80 ℃.

8. The method for preparing the catalyst according to claim 1, wherein: in the step 4), the roasting condition is that the heat preservation time is 2-4h under the air condition of 450-550 ℃.

9. The method for preparing the catalyst according to claim 8, wherein: in the step 4), the roasting condition is that the heat preservation time is 3 hours under the air condition of 500 ℃.

Technical Field

The invention relates to a preparation method of a catalyst, in particular to a preparation method of a catalyst with a target product of a glucose hydrogenolysis reaction being dihydric alcohol.

Background

With the large consumption of energy in the world, fossil fuels are increasingly scarce, the problem of environmental pollution is becoming more severe, and a new energy source capable of replacing the traditional fossil energy source needs to be found, so that renewable energy sources are widely regarded by society. The biomass as the only renewable organic carbon on the earth can be converted into various fuel components and basic chemicals, and has extremely high environmental and economic benefits. Glucose is the most abundant monosaccharide in biomass, is a high-efficiency biomass clean energy source, and is recognized as a potential energy source for replacing petrochemical energy sources. The hydrogenolysis of glucose refers to the hydrocracking of glucose at a certain temperature and pressure to produce lower alcohols. However, the reaction conditions of the process route are harsh, and the selectivity of the low-carbon dihydric alcohol is not high.

Disclosure of Invention

The invention aims to provide a preparation method of a catalyst with a target product of a glucose hydrogenolysis reaction being dihydric alcohol. The catalyst prepared by the preparation method is a cobalt molybdate catalyst and is in a rod-shaped shape, and by using the catalyst, the conversion rate of glucose in the reaction of preparing dihydric alcohol by glucose hydrogenolysis can reach 100%, the selectivity of the total dihydric alcohol is more than or equal to 80%, and the selectivity of the target product propylene glycol is more than or equal to 60%; the method has the advantages of simple process, mild conditions and low cost.

In order to solve the technical problems, the invention adopts the following technical scheme:

a preparation method of a catalyst with a target product of a glucose hydrogenolysis reaction being dihydric alcohol comprises the following specific steps:

1) weighing cobalt acetate and ammonium molybdate, dissolving the cobalt acetate and the ammonium molybdate in deionized water, and stirring to completely dissolve the cobalt acetate and the ammonium molybdate until a clear and transparent red mixed solution is formed;

2) under the condition of stirring, dropwise adding ethanol into the red mixed solution, and preserving heat under the condition of water bath to gradually generate purple precipitates;

3) washing the purple precipitate with deionized water and anhydrous ethanol for 2-3 times;

4) transferring the precipitate to an oven, and drying in an air atmosphere;

5) and transferring the dried precipitate to a muffle furnace, and roasting in the air atmosphere to obtain the rod-shaped cobalt molybdate catalyst.

As a further improvement of the technical scheme, in the step 1), the ratio of the amount of cobalt substances in the cobalt acetate to the amount of molybdenum substances in the ammonium molybdate is 0.8-1: 0.8-1.

Preferably, in step 1), the amount of cobalt species in the cobalt acetate to molybdenum species in the ammonium molybdate used is 1: 1.

As a further improvement of the technical scheme, in the step 2), the water bath condition is maintained for 3-5h at 80-90 ℃.

Preferably, in step 2), the water bath conditions are maintained at 85 ℃ for 4 h.

As a further improvement of the technical scheme, in the step 4), the drying condition is that the heat preservation time is 10-15h under the air condition of 70-90 ℃.

Preferably, in the step 4), the drying condition is that the heat preservation time is 12 hours under the air condition of 80 ℃.

As a further improvement of the technical scheme, in the step 4), the roasting condition is that the heat preservation time is 2-4h under the air condition of 450-550 ℃.

Preferably, in the step 4), the roasting condition is that the heat preservation time is 3 hours under the air condition of 500 ℃.

Any range recited herein is intended to include the endpoints and any number between the endpoints and any subrange subsumed therein or defined therein.

The starting materials of the present invention are commercially available, unless otherwise specified, and the equipment used in the present invention may be any equipment conventionally used in the art or may be any equipment known in the art.

Compared with the prior art, the invention has the following beneficial effects:

the catalyst prepared by the preparation method is a cobalt molybdate catalyst and is in a rod-like shape; by using the catalyst, the conversion rate of glucose in the reaction of preparing dihydric alcohol by hydrogenolysis of glucose can reach 100 percent, the selectivity of the total dihydric alcohol is more than or equal to 80 percent, and the selectivity of a target product, namely propylene glycol is more than or equal to 60 percent; the method has the advantages of simple process, mild conditions and low cost.

Drawings

The following detailed description of embodiments of the invention is provided in connection with the accompanying drawings

FIG. 1 is an X-ray diffraction (XRD) pattern of the product shown in example 1;

FIG. 2 is a Scanning Electron Microscope (SEM) morphology photograph of the product shown in example 1 at different magnifications.

Detailed Description

In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.

As one aspect of the present invention, the preparation method of the catalyst with the target product of the hydrogenolysis reaction of glucose being dihydric alcohol of the present invention comprises the following specific steps:

1) weighing cobalt acetate and ammonium molybdate, dissolving the cobalt acetate and the ammonium molybdate in deionized water, and stirring to completely dissolve the cobalt acetate and the ammonium molybdate until a clear and transparent red mixed solution is formed;

2) under the condition of stirring, dropwise adding ethanol into the red mixed solution, and preserving heat under the condition of water bath to gradually generate purple precipitates;

3) washing the purple precipitate with deionized water and anhydrous ethanol for 2-3 times;

4) transferring the precipitate to an oven, and drying in an air atmosphere;

5) and transferring the dried precipitate to a muffle furnace, and roasting in the air atmosphere to obtain the rod-shaped cobalt molybdate catalyst.

In certain embodiments of the invention, the amount of cobalt species in the cobalt acetate to the amount of molybdenum species in the ammonium molybdate used in step 1) is in the range of 0.8-1: 0.8-1.

In certain preferred embodiments of the present invention, in step 1), a 1:1 ratio of the amount of cobalt species in the cobalt acetate to the amount of molybdenum species in the ammonium molybdate is used.

In certain embodiments of the invention, in step 2), the water bath conditions are maintained at 80-90 ℃ for 3-5 h.

In certain preferred embodiments of the present invention, in step 2), the water bath conditions are maintained at 85 ℃ for 4 h.

In certain embodiments of the present invention, in step 4), the drying is performed under the condition of 70-90 ℃ and the heat preservation time is 10-15h under the air condition.

In certain preferred embodiments of the present invention, in step 4), the drying is carried out under the condition of 80 ℃ and the holding time under the air condition is 12 h.

In some embodiments of the invention, in the step 4), the roasting condition is 450-.

In certain preferred embodiments of the present invention, in the step 4), the roasting condition is 500 ℃ and the holding time under the air condition is 3 hours.