Preparation method and application of carbon-phosphorus-boron ternary co-doped copper/nickel-based catalyst

Abstract

The invention discloses a preparation method and application of a carbon-phosphorus-boron ternary co-doped copper / nickel-based catalyst, and the preparation method comprises the following steps: S1, dissolving a copper salt and a nickel salt in deionized water, and magnetically stirring at 50-80 DEG C for 3-5 hours to obtain a mixed solution; s2, adding a catalyst carrier into the mixed solution, performing pressurized impregnation adsorption for 1-3 hours under the pressure condition of 0.5-1.5 MPa, then dropwise adding a 0.02-0.03 mol / L sodium citrate solution, performing stirring reaction for 6-12 hours at the temperature of 20-100 DEG C, filtering, and drying to obtain a composite precursor; s3, placing the composite precursor in a tubular furnace, carrying out heat treatment at 500-600 DEG C for 1-3 hours, then introducing mixed gas of CH4 and PH3 at a flow rate of 250-500 sccm, and carrying out vapor deposition for 2-4 hours to obtain solid particles; and S4, adding the solid particles into a 0.02-0.1 mol / L H3BO3 solution, stirring for 10-20 minutes, controlling the solid-to-liquid ratio to be 1g / 10mL, carrying out solid-liquid separation, washing with deionized water for 3 times, and drying, so as to obtain the carbon-phosphorus-boron ternary co-doped copper / nickel-based catalyst. The ZSM-5 molecular sieve is used as a carrier, sodium citrate is used as a metal complexing agent, Cu < 2 + > and Ni < 2 + > grow in situ, non-metallic elements of carbon, phosphorus and boron are deposited, and the selectivity and catalytic activity of the catalyst are improved.

Description

Technical field [0001] The present invention belongs to the field of catalyst synthesis, and more particularly to the preparation method of carbonophosphate ternate co-doped copper / nickel based catalyst. Background technique [0002] Hydrogenation refers to a reaction from the organic compound to molecular hydrogen, which is divided into hydrogenation and hydrogenolysis, wherein the hydrogenation reaction is an organic compound which increases the number of hydrogen atoms in the unsaturated organic compound molecule and makes it more saturated. Organic compound. Process, such as olefins, alkynes, aldehyde, ketones, imine, and the like having high economic performance, simple operation, clean green, etc., extensive applications in fine chemical production. Hydrogenation reactions generally need to occur in the presence of catalysts, and the copper / nickel-based metal catalyst has high activity, high selectivity, and has a wide range of applications in catalytic hydrogenation re...

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Problems solved by technology

For example, the patent application number CN201310414930.7 discloses a method for catalytic hydrogenation of p-nitrophenol with nano-nickel / copper composite catalyst, using polystyrene / polymethacrylic acid microspheres as a template, copper nitrate, oxalic acid Nickel is used as a raw material to prepare nano-nickel / copper composite catalysts; for example, the patent application number CN201980026409.1 discloses a method for preparing a selective bimetallic hydrogenation catalyst made of nickel and copper, using copper precursors and nickel precursors to prepare catalysts And it is applied in the selective hydrogenation reaction of olefins; but the existing copper / nickel-based metal catalysts have tended to be stable in terms of hydrogenation reaction catalytic activity, and it is difficult to have a large improvement. In order to further improve the copper / nickel-based metal catalysts in the selection Catalytic activity and catalytic stability in neutral hydrogenation reaction, the present invention provides a kind of preparation method and its application of carbon-phosphorus-boron ternary co-doped copper / nickel-based catalyst

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