CN-117443389-B - Composition, preparation method and application thereof in catalysis field

Abstract

The invention belongs to the technical field of catalyst research and development, and particularly relates to a composition, a preparation method and application thereof in the field of catalysis. The invention provides a composition, which comprises active components, an auxiliary agent and a carrier, wherein the active components are copper salts, and the carrier is aluminum nitride. The invention also provides a preparation method of the composition, and the invention also provides an application of the composition or a product obtained by the preparation method in a formaldehyde hydration dehydrogenation catalyst. According to the technical scheme, the aluminum nitride carrier is used, so that the stability of the catalyst in an aqueous environment is effectively improved, most of hydrated formaldehyde can be catalytically reformed into H 2 and CO 2 under the condition that an alkaline medium is not additionally introduced, meanwhile, the generation of by-product formic acid is effectively inhibited, and thirdly, catalytic dehydrogenation can be performed under the heating condition, so that the reaction efficiency is improved.

Inventors

• CHEN HONGLIN
• ZHOU RUOYU
• Deng Conger

Assignees

• 中国科学院成都有机化学有限公司
• 成都中科凯特科技有限公司

Dates

Publication Date

20260508

Application Date

20231009

Claims (5)

1. 1. The preparation method of the composition is characterized by comprising, by mass, 10-30 parts of active components, 5-10 parts of auxiliary agents and 20-40 parts of carriers, wherein the active components are copper salts, the carriers are aluminum nitride, the particle size of the carriers is 1-10 mu m, and the auxiliary agents are selected from any one or more of salt solutions containing Zn, zr, ce, ni; the preparation method comprises the following steps: Dissolving active components and auxiliary agents in water, mixing with a carrier washed by ethanol and dried, and dissolving to obtain a first product; Step two, dropwise adding an alkali solution into the first product and the middle product until the pH value is 6-8, continuously stirring to obtain a second product, wherein the dropwise adding temperature is 50-70 ℃, the stirring time is 1-3 h, and the stirring temperature is 50-70 ℃; And thirdly, washing, filtering and drying the second product, and roasting to obtain the product.
2. 2. The method according to claim 1, wherein the copper salt is selected from any one or more of copper nitrate, copper acetate and copper sulfate.
3. 3. The method according to claim 1, wherein the alkaline solution is an ammonium bicarbonate solution and/or an ammonium carbonate solution.
4. 4. The method according to claim 1, wherein in the third step, the drying temperature is 65-120 ℃, the drying time is 8-12 hours, the baking temperature is 350-550 ℃, and the baking time is 4-8 hours.
5. 5. Use of a product comprising the process of any one of claims 1 to 4 in a formaldehyde hydration dehydrogenation catalyst.

Description

Composition, preparation method and application thereof in catalysis field Technical Field The invention belongs to the technical field of catalyst research and development, and particularly relates to a composition, a preparation method and application thereof in the field of catalysis. Background In recent years, as formaldehyde aqueous solution has higher theoretical hydrogen weight percentage (8.4 wt%) and formaldehyde dehydrogenation reaction has attracted great interest (i.e. HCHO+H 2O→H2+CO2), the formaldehyde aqueous solution can be used for preparing hydrogen from formaldehyde aqueous phase, and a potential purification treatment method can be provided for wastewater containing formaldehyde impurities, so that the formaldehyde aqueous solution has general attention in the industry. In the formaldehyde dehydrogenation reaction application, the copper-based catalyst is low in cost and easy to obtain due to high catalytic activity, and is more beneficial to industrialized popularization. However, the application research of formaldehyde dehydrogenation in formaldehyde water phase hydrogen production is still in a preliminary exploration stage, most of the reported patents need to react under the condition of strong alkali, the formaldehyde activity is high, the side reaction is more, particularly, the Canniza Luo Qihua side reaction (Cannizzaro disproportionation) of formaldehyde is promoted in an alkaline environment, methanol and formate are generated, the formaldehyde water phase hydrogen production efficiency is low, and a large amount of formate and unreacted strong alkali medium also increase the subsequent treatment cost and the risk of secondary pollution to the water environment. In addition, in the prior art, partial heterogeneous catalyst carriers, such as Al 2O3, can generate hydration phenomena under the conditions of high temperature and water vapor to lead to the pulverization and inactivation of the catalyst, and the catalyst particles are extremely easy to grow, leach and oxidize in a high-water-content reaction system, so that the catalyst conversion rate and selectivity are reduced, even the service life is shortened, and the like, which is not beneficial to industrial production. In view of the above shortcomings, the method has a plurality of limitations for industrial application of formaldehyde water phase hydrogen production, and particularly includes a more serious challenge for cleaning formaldehyde byproducts. Particularly, the large-scale introduction of alkaline medium and the improvement of the hydrothermal stability of the catalyst in a high-water-content reaction system are key problems to be solved urgently. In addition, it should be noted that the high activity of formaldehyde in the absence of an alkaline medium may also cause a cannizzard Luo Qihua side reaction to form formic acid. Due to the lack of alkali for neutralization, formic acid formation can lead to deactivation of the catalyst and corrosion of the metal reaction equipment. In the application of the cleaning treatment of a plurality of formaldehyde byproducts, the catalytic removal of formaldehyde from the crude trioxymethylene product is significant for reducing the refining cost of the trioxymethylene. Trioxymethylene is an organic compound, is mainly used as an intermediate of engineering plastic polyformaldehyde and other chemicals, and can also be used as a disinfectant and colorless flameless fuel. The crude trioxymethylene contains formaldehyde, is difficult to remove by rectification in the refining process, is extremely easy to self-polymerize or generate formic acid, blocks corrosion equipment and needs to be subjected to necessary refining treatment. Therefore, a composition, a preparation method and application thereof in the field of catalysis are developed to solve the technical defects of easy inactivation, low reaction efficiency, formic acid generation inhibition and the like in the prior art, and the problems to be solved by the technicians in the field are urgent. Disclosure of Invention Based on the above, it is necessary to provide a composition, a preparation method and application thereof in the field of catalysis, aiming at the technical defects of easy deactivation, low reaction efficiency and easy pollution of copper-based catalysts for formaldehyde dehydrogenation in the prior art. The invention provides a composition, which comprises active components, an auxiliary agent and a carrier, wherein the active components are copper salts, and the carrier is aluminum nitride. In one embodiment, the composition comprises, by mass, 10-30 parts of an active component, 5-10 parts of an auxiliary agent and 20-40 parts of a carrier. In one embodiment, the particle size of the carrier is 40nm to 50 μm. In one embodiment, the copper salt is selected from any one or more of copper nitrate, copper acetate and copper sulfate. In one embodiment, the auxiliary agent is selected from any one or mo