CN110028393B

CN110028393B - Method for preparing acetol and hydroxy butanone by cellulose catalytic hydrogenation

Info

Publication number: CN110028393B
Application number: CN201910414720.5A
Authority: CN
Inventors: 马隆龙; 王海永; 刘琪英; 王晨光; 张琦; 谈金; 朱长辉; 刘竞
Original assignee: Guangzhou Institute of Energy Conversion of CAS
Current assignee: Guangzhou Institute of Energy Conversion of CAS
Priority date: 2019-05-17
Filing date: 2019-05-17
Publication date: 2021-12-10
Anticipated expiration: 2039-05-17
Also published as: CN110028393A

Abstract

The invention discloses a method for preparing acetol and hydroxy butanone by catalytic hydrogenation of cellulose, which utilizes Ni-W/C as a catalyst to convert cellulose into the acetol and the hydroxy butanone. The catalyst has the advantages of rich raw materials, low price, mild preparation conditions, simple preparation method, no need of hydrogenation reduction, low cost, high efficiency and large-scale popularization and application.

Description

Method for preparing acetol and hydroxy butanone by cellulose catalytic hydrogenation

The technical field is as follows:

the invention relates to a method for preparing acetol and hydroxy butanone by catalytic hydrogenation of cellulose.

Background art:

cellulose is the main component of biomass, is a polysaccharide which is most widely distributed and contained in nature, and accounts for more than 50% of the carbon content in plants. Generally, conversion of cellulose to hydrocarbon fuels or chemicals can be achieved by catalytic depolymerization hydrogenation to obtain polyols, followed by further hydrodeoxygenation.

The general preparation method of acetol is to use 1, 2-propylene glycol as raw material, alkaline earth metal as catalyst, carry out reaction at 350-700 ℃, and prepare acetol through dehydrogenation. Or the glycerol is taken as a raw material and is subjected to dehydrogenation reaction under certain pressure condition under the catalytic action of a nickel-based catalyst to prepare the catalyst. In addition to chemical methods, they can also be prepared by the action of microorganisms. The biological method is to convert glycerol into acetone alcohol by using glycerol as a raw material under the action of a strain.

The 3-hydroxy butanone can be used as spice, and is mainly used as food additive. Mainly prepared by processes of partial hydrogenation reduction of butanedione, selective reduction oxidation of 2, 3-butanediol, chlorination hydrolysis of butanone and the like. However, the three methods have the defects of low product yield and yield, serious environmental pollution, and difficulty in meeting the requirement of the product quality as the edible spice, thereby greatly limiting the large-scale development and application of the product.

Both chemical and biological methods for preparing acetol use C3 polyhydric alcohols such as propylene glycol and glycerol as raw materials, and the sources of glycerol and propylene glycol greatly limit the capacity and price of acetol.

The invention content is as follows:

the invention aims to provide a method for preparing acetol and hydroxy butanone by catalytic hydrogenation of cellulose, which utilizes Ni-W/C as a catalyst to convert cellulose into the acetol and the hydroxy butanone, has wide sources of used raw materials, is cheap and easy to obtain, can obtain chemicals with high added values, and solves the environmental problem caused by agricultural and forestry wastes. The catalyst has the advantages of rich raw materials, low price, mild preparation conditions, simple preparation method, no need of hydrogenation reduction, low cost, high efficiency and large-scale popularization and application.

The invention is realized by the following technical scheme:

a method for preparing acetol and hydroxy butanone by cellulose catalytic hydrogenation takes cellulose as a raw material and Ni-W/C as a catalyst to prepare the acetol and the hydroxy butanone by aqueous phase hydrogenation, the reaction temperature is 180-260 ℃, the reaction temperature is preferably 220-260 ℃, the reaction time is 1-3h, the reaction time is preferably 0.5-2h, and the hydrogen pressure in the reaction system is 1-5 MPa, the reaction pressure is preferably 2-5 MPa; the specific preparation method of the Ni-W/C catalyst is as follows: nickel salt, organic matter, ammonium tungstate or/and ammonium metatungstate and deionized water, and stirring for 6-12 hours at 0-100 ℃, preferably 70 ℃; raising the temperature to 100-160 ℃, preferably 100 ℃, and keeping for 12 hours to obtain a powder sample, and roasting the powder sample for 3 hours at the temperature of 600-800 ℃, preferably 700-800 ℃ under the protection of inert atmosphere to obtain the target catalyst; the mol ratio of tungsten, organic matters and nickel salt in the ammonium tungstate or/and ammonium metatungstate is (1-5): 3: 1.

the nickel salt is preferably any one of nickel chloride, nickel nitrate, nickel sulfate and nickel acetate.

The organic substance is preferably more than one of glucose, tartaric acid, sorbitol, citric acid and malic acid.

The invention has the following beneficial effects: the Ni-W/C catalyst has the advantages of rich raw materials, low price, mild preparation conditions, simple preparation method, excellent catalytic activity, high hydrodeoxygenation efficiency and reusability, and can efficiently catalyze lignocellulose to be converted into acetol and hydroxy butanone.

Description of the drawings:

FIG. 1 is a TEM image of the catalyst obtained in example 1.

The specific implementation mode is as follows:

the following is a further description of the invention and is not intended to be limiting.

Example 1: preparation of the catalyst

10mL of deionized water, 0.01mol of nickel salt, 0.03mol of organic matter, and 0.0008mol of ammonium tungstate ((NH) were added to a beaker₄)₁₀W₁₂O₄₁～xH₂O), stirring at 70 ℃ for 6 hours, heating to 100 ℃ and keeping for 12 hours. The obtained green powder is mixed with N₂And raising the temperature to 600 ℃ in the atmosphere, and keeping the temperature for 3 hours to obtain the target catalyst.

In a TEM image as shown in FIG. 1, both the metal Ni and the metal oxide WOx are wrapped by the carbon layer, the WOx mainly has a rod-like structure, the length is about 7.9nm, and the average particle size of the Ni metal particles is about 3.4 nm.

Example 2:

0.05gNi-W/C catalyst prepared in example 1, 0.2g of cellulose and 20.0ml of deionized water were placed in a 50ml autoclave, which was sealed and charged with H₂Replacing gas in the kettle for 6 times, and charging H₂Pressurizing to 4 MPa. The stirring paddle (800rpm) was turned on, and the reaction kettle was heated to 240 ℃ at a heating rate of 3 ℃/min, to start the timed reaction. The reaction time was 1 h. The yield of acetol is 35 percent, and the yield of hydroxy butanone is 35 percent.

Examples 3 to 15:

referring to example 2, except that the catalyst tungsten-nickel atomic ratio, the catalyst calcination temperature, the reaction temperature, the pressure and the time were different, see table 1 specifically:

TABLE 1

Examples 16 to 22: and (3) a repeatability experiment of the Ni-W catalyst on the preparation of the acetol and hydroxy butanone products by the catalytic conversion of the cellulose.

Referring to example 2, the number of times of catalyst reuse and the reaction results are shown in Table 2.

TABLE 2

Examples	Number of times of catalyst utilization	Product yield (%)
			16	1	91
17	2	90
			18	3	91
19	4	87
			20	5	89
21	6	90
			22	7	89

Claims

1. A method for preparing acetone alcohol and hydroxy butanone by cellulose catalytic hydrogenation is characterized in that cellulose is used as a raw material, Ni-W/C is used as a catalyst, water phase hydrogenation is carried out to prepare acetone alcohol and hydroxy butanone, the reaction temperature is 180-; the specific preparation method of the Ni-W/C catalyst is as follows: stirring nickel salt, organic matter, ammonium tungstate or/and ammonium metatungstate and deionized water at 70 ℃ for 6-12 hours; heating to 100-160 ℃, keeping for 12 hours, and roasting the obtained powder sample for 3 hours in the range of 600-800 ℃ under the protection of inert atmosphere to obtain the target catalyst; the mol ratio of tungsten, organic matters and nickel salt in the ammonium tungstate or/and ammonium metatungstate is (1-5): 3: 1; the organic matter is selected from more than one of glucose, tartaric acid, sorbitol, citric acid and malic acid.

2. The method according to claim 1, wherein the Ni-W/C catalyst is prepared by the following method: stirring nickel salt, organic matters, ammonium tungstate and deionized water at 70 ℃ for 6 hours; heating to 100 ℃, keeping for 12 hours, and obtaining a powder sample within the range of 700-800 ℃ and N₂Roasting for 3 hours under the protection of atmosphere to obtain a target catalyst; the mol ratio of tungsten, organic matters and nickel salt in the ammonium tungstate or/and ammonium metatungstate is (1-5): 3: 1.

3. the method as claimed in claim 1 or 2, wherein cellulose is used as raw material, Ni-W/C is used as catalyst, water phase hydrogenation is carried out to prepare the acetol and the hydroxy butanone, the reaction temperature is 220-260 ℃, and the hydrogen pressure in the reaction system is 2-5 MPa.

4. The method according to claim 1 or 2, wherein the nickel salt is selected from any one of nickel chloride, nickel nitrate, nickel sulfate and nickel acetate.