CN109746005B

CN109746005B - Acetylene hydrochlorination catalyst based on porous pipe wall hollow foam material and preparation method and application thereof

Info

Publication number: CN109746005B
Application number: CN201711088716.1A
Authority: CN
Inventors: 张劲松; 杨晓丹; 王鹏; 高勇; 杨振明
Original assignee: Institute of Metal Research of CAS
Current assignee: Institute of Metal Research of CAS
Priority date: 2017-11-08
Filing date: 2017-11-08
Publication date: 2022-01-14
Anticipated expiration: 2037-11-08
Also published as: CN109746005A

Abstract

本发明涉及催化剂领域，具体地说是一种基于多孔管壁中空泡沫材料的乙炔氢氯化反应催化剂及制备方法和应用。该催化剂的第一载体含有多孔管壁中空泡沫材料，该材料在宏观上由三维连通的支撑骨架网络构建而成，支撑骨架自身为三维连通的具有中空结构的微通道，微通道管壁含有埃级和/或纳米级和/或微米级孔径孔隙的多孔结构。采用本发明所述的催化剂的制备方法，制得基于多孔管壁中空泡沫材料的催化剂具有如下优点：乙炔氢氯化反应所用的催化活性组分、助催化组分、第二载体均可在多孔管壁中空泡沫材料的各尺度孔隙内实现高分散度的可控负载，强化反应过程中的热量传递、质量传递，延长催化剂使用寿命。The invention relates to the field of catalysts, in particular to an acetylene hydrochlorination reaction catalyst based on a porous tube wall hollow foam material, a preparation method and application thereof. The first carrier of the catalyst contains a hollow foam material with a porous tube wall. The material is macroscopically constructed from a three-dimensionally connected support framework network. The support framework itself is a three-dimensionally connected microchannel with a hollow structure. The wall of the microchannel contains angstroms. Porous structure of pore size and/or nanoscale and/or microscale pore size. Using the preparation method of the catalyst of the present invention, the preparation of the catalyst based on the porous tube-wall hollow foam material has the following advantages: the catalytically active component, the promoter component and the second carrier used in the acetylene hydrochlorination reaction can all be in porous The high-dispersion controllable load is realized in the pores of each dimension of the hollow foam material of the tube wall, which strengthens the heat transfer and mass transfer in the reaction process and prolongs the service life of the catalyst.

Description

Acetylene hydrochlorination catalyst based on porous pipe wall hollow foam material and preparation method and application thereof

Technical Field

The invention relates to the field of catalysts, in particular to an acetylene hydrochlorination catalyst based on a porous pipe wall hollow foam material, and a preparation method and application thereof.

Background

The reaction for preparing vinyl chloride by hydrochlorinating acetylene is still one of important links in the chlor-alkali industry in China, and the production process of vinyl chloride monomer mainly adopts a calcium carbide method because China is limited by resources such as rich coal, poor oil and little gas. Currently, the catalyst used for the hydrochlorination of acetylene is a HgCl/C granular catalyst. Because acetylene hydrochlorination is exothermic reaction, and the temperature rise of a catalyst bed is highly related to the reaction space velocity and the bed heat transfer condition, the problems of heat-induced inactivation and volatilization loss of a mercury catalyst are inevitably faced, and the problem of non-negligible environmental pollution is caused. With the increasing shortage of mercury resources and the serious pollution caused by mercury catalysts in China, particularly, the water guarantee treaty has been added in China, so that the sustainable development of the process route of the acetylene method is severely restricted. Therefore, the pollution problem caused by mercury loss is solved, and the development of a clean process route for preparing vinyl chloride by using a mercury-free catalyst to catalyze the hydrochlorination reaction of acetylene is urgent.

Heretofore, a mercury-free catalyst for catalyzing acetylene hydrochlorination mainly takes rare and precious metals such as gold, ruthenium, platinum and the like as active components, and can obtain a better catalytic effect, but because the rare and precious metal catalyst has higher temperature sensitivity and poorer thermal shock resistance, the rare and precious metal catalyst is easier to inactivate, in the production of vinyl chloride by acetylene hydrochlorination, the mercury catalyst needs to be replaced, the rare and precious metal catalyst is urgently required to greatly improve the technical problems of the stability and the service life of the catalyst, on one hand, the active component with high stability needs to be developed urgently, and on the other hand, the precise mass transfer and heat transfer process regulation and control of the catalytic reaction process in a catalytic bed layer needs to be performed urgently.

Disclosure of Invention

The invention aims to provide an acetylene hydrochlorination catalyst based on a porous pipe wall hollow foam material and a preparation method thereof, and solves the problems that mass transfer and heat transfer processes cannot be finely regulated and controlled in the prior art.

The technical scheme of the invention is as follows:

an acetylene hydrochlorination catalyst based on a porous pipe wall hollow foam material, wherein the hollow foam material is a porous pipe wall hollow foam material with macroscopic three-dimensional communication open pores, and the structure of the material is macroscopically communicated by a support skeleton (a) in a three-dimensional way to form an open pore (b) network structure; the supporting framework (a) is provided with a hollow microchannel (c) with controllable size, the cross section of the inner cavity of the microchannel (c) is triangular, rectangular, approximately circular or elliptical, the framework between the wall surface corresponding to the outer diameter of the microchannel (c) and the inner wall of the inner cavity of the microchannel (c) is a microchannel pipe wall with a porous structure, and the microchannel pipe wall contains a porous structure with angstrom-scale and/or nanometer-scale and/or micron-scale pore diameters.

The catalyst for hydrochlorination of acetylene based on the porous pipe wall hollow foam material comprises the hollow foam material, wherein the size (d1) of the meshes of the hollow foam material is 0.2-20 mm, and the hollow foam material is three-dimensionally communicated by a supporting framework to form an open-pore network structure; the outer diameter (d2) of the hollow micro-channel is 0.1 mm-10 mm, and the inner diameter (d3) is 0.02 mm-9 mm; the pore size of pores contained in the porous pipe wall or the porous micro-channel pipe wall ranges from 0.1nm to 100 mu m, and the porosity p is more than 0 and less than or equal to 70 percent.

The acetylene hydrochlorination catalyst based on the porous pipe wall hollow foam material comprises one or two specific bearing parts which are directly used as catalytic carriers and used for loading catalytic active components and cocatalyst components, wherein the specific bearing parts are one or two parts of the porous pipe wall hollow foam material contained in the catalyst: the inner wall of the hollow foam material, the outer wall of the hollow foam material, the porous pipe wall body of the hollow foam material and the porous pipe wall body of the hollow foam material contain pores with angstrom-scale and/or nanometer-scale and/or micron-scale pore diameters.

The catalyst for the hydrochlorination of acetylene based on the porous pipe wall hollow foam material contains a second carrier, and the existence form of the second carrier is one or more than two of the following modes:

(1) the second carrier is filled in the three-dimensional communicated open pore;

(2) the second carrier is filled in the hollow inner cavity;

(3) the second carrier is filled in the pores with the nanometer and/or micron-sized pore diameters contained in the porous pipe wall body;

(4) the second carrier is loaded on the inner wall surface of the porous pipe wall;

(5) the second carrier is loaded on the outer wall surface of the porous pipe wall;

(6) the second carrier is loaded on the pore wall surface with the nanometer and/or micron-sized pore diameter contained in the porous pipe wall body;

the catalytic active component and the cocatalyst component are dispersed only in a local area of 1 nm-500 μm on the surface of the second carrier, or uniformly dispersed on the surface and inside of the second carrier.

The catalyst for hydrochlorination of acetylene based on the porous pipe wall hollow foam material comprises second carriers in the presence forms (1) to (3), wherein the filling rate of the second carriers is 5 to 100 percent of the pore volume of filled pores; the catalyst comprises a second carrier in the form of (4) to (6), the second carrier having a supporting thickness of 1nm to 1000. mu.m.

The second carrier of the acetylene hydrochlorination catalyst based on the porous pipe wall hollow foam material is one or more than two of the following substances: gamma-Al₂O₃、η-Al₂O₃、θ-Al₂O₃、δ-Al₂O₃、α-Al₂O₃Magnesium oxide, titanium oxide, molecular sieves, mesoporous silica, amorphous silica, graphite, amorphous carbon, graphene, diamond, activated carbon, ordered mesoporous carbon, unordered mesoporous carbon, carbon fibers, carbon nanotubes, carbon aerogel, silicon carbide, silica gel, silicon aerogel;

the catalyst has the cocatalyst component of one or more than two of the following substances: rare earth element ion, rare earth oxide, transition metal oxide, alkali metal ion, alkali metal oxide, alkaline earth metal ion, alkaline earth metal oxide, NH₃Carbonate, nitrate, acetate, oxalate, citrate, tartrate, chloride.

The catalyst for acetylene hydrochlorination based on the porous pipe wall hollow foam material comprises the following catalytic active components and one or more than two of compounds or complexes thereof: w, Ta, Mo, Ti, Zr, Fe, Ni, Co, Cr, Pt, Rh, Pd, Cu, Al, Au, Mn, Ru, Ag, Zn, Cd, In, Pb, As, Bi, Sb, Se, Te, Ba, Hg.

The compound is one or more than two of the following substance classes: chloride, oxide, sulfide, carbide, bromide, iodide, fluoride, phosphate, nitrate, nitrite, sulfate, sulfite, acetate, oxalate, citrate, tartrate, thiosulfate;

the ligand of the complex is one or more than two of the following: h₂O、NH₃、Cl^-、CN^-En ethylenediamine, EDTA^-Ethylenediaminetetraacetic acid radical, alkenes, alkynes, alkyls, aromatic rings, RNH₂Amine, pH₃Phosphine, hydride, CO carbonyl, OH^-Hydroxy group, F^-、Br^-、I^-、NO₂ ^-、N₂Double nitrogen Oxide Nitride Oxide (ONO)^-Nitrite, SCN^-Thiocyanate, NCS^-Isothiocyanate, ox oxalate, o-phen phenanthroline and bipy bipyridine.

The catalytic active component is preferably one or the combination of more than two of the following substances: chloroauric acid, chloroplatinic acid, palladium chloride, ruthenium chloride, rhodium chloride, MoS₂。

The acetylene hydrochlorination catalyst based on the porous pipe wall hollow foam material comprises the porous pipe wall hollow foam material, and the main component substances of the porous pipe wall hollow foam material are one or more than two of the following categories: nickel200, Nickel201, Monel400, Inconel600, Inconel625, Incoloy800, Incoloy825, Hastelloy C-4, Avesta254, Hastelloy B-2, carbon steel, 304 stainless steel, 316L stainless steel, titanium, zirconium, tantalum, quartz SiO₂Borosilicate glass, silicon carbide, zirconium carbide, tungsten carbide, titanium carbide, boron carbide, tantalum carbide, vanadium carbide, chromium carbide, niobium carbide, molybdenum carbide, iron carbide, manganese carbide, alpha-Si₃N₄、β-Si₃N₄、AlN、Si_6-xAl_xO_xN_8-xBN, Si, graphite, amorphous carbon, graphene, diamond, activated carbon, ordered mesoporous carbon, unordered mesoporous carbon, carbon fiber, carbon nanotube.

The preparation method of the catalyst for the hydrochlorination of acetylene based on the porous pipe wall hollow foam material comprises one or the combination of two of the following methods:

(1) the direct impregnation method of the porous pipe wall hollow foam material without the second carrier comprises the following steps: directly immersing a porous pipe wall hollow foam material serving as a first carrier into a feed liquid containing a catalytic active component and a cocatalyst component, taking out and drying to obtain a structural catalyst for acetylene hydrochlorination; wherein, the content of the catalytic active component is 0.001wt percent to 70wt percent, and the content of the cocatalyst component is 0.001wt percent to 50wt percent;

(2) the preparation method comprising the second carrier comprises the following steps:

load of the second washcoat preform: completely immersing the porous pipe wall hollow foam material serving as a first carrier into a feed liquid containing a second carrier or a precursor of the second carrier, taking out the feed liquid to a required position, removing redundant feed liquid, drying and curing the load, and circularly immersing, removing redundant feed liquid, drying and curing the load to reach the load quantity required by the content of the second carrier; wherein the content of the second carrier or the precursor of the second carrier is 1wt% -80 wt%;

preparing a second carrier coating: pyrolyzing the sample loaded with the second carrier coating prefabricated body obtained in the step one, wherein the pyrolysis temperature is 300-1000 ℃, the time is 0.5-12 hours, and the atmosphere is Ar and N₂、CO、CO₂、NH₃、H₂、CH₄、HCl、C₂H₂、C₂H₆、C₃H₈To prepare a porous pipe wall hollow foam material loaded with a second carrier coating;

③ loading of catalytic active component and cocatalyst component: immersing the porous pipe wall hollow foam material loaded with the second carrier coating obtained in the step two into a feed liquid containing a catalytic active component and a cocatalyst component, taking out and drying to obtain a structural catalyst for acetylene hydrochlorination; wherein, the content of the catalytic active component is 0.001wt percent to 70wt percent, and the content of the cocatalyst component is 0.001wt percent to 50wt percent;

(3) and a second preparation method containing a second carrier comprises the following steps:

load of the catalytic coating preform: completely immersing a porous pipe wall hollow foam material serving as a first carrier into a feed liquid containing a second carrier or a precursor of the second carrier, a catalytic active component and a cocatalyst component, taking out the feed liquid to a required position, removing redundant feed liquid, drying and curing the load, and circularly immersing, removing redundant feed liquid, drying and curing to a load capacity required by the content of the second carrier; wherein, the content of the second carrier or the precursor of the second carrier is 1wt percent to 80wt percent, the content of the catalytic active component is 0.001wt percent to 70wt percent, and the content of the cocatalyst component is 0.001wt percent to 50wt percent;

preparing a catalytic coating: carrying out heat treatment on the sample loaded with the second carrier coating prefabricated body obtained in the step one, wherein the pyrolysis temperature is 100-1000 ℃, the time is 0.5-12 hours, and the atmosphere is Ar and N₂、CO、CO₂、NH₃、H₂、CH₄、HCl、C₂H₂、C₂H₆、C₃H₈One or more than two of the first carrier, the second carrier, the catalytic active component and the cocatalyst component are loaded to prepare the hollow foam material with the porous pipe wall of the catalytic coating.

The preparation method of the catalyst for acetylene hydrochlorination based on the porous pipe wall hollow foam material comprises the following steps of: the drying method in the preparation method of the catalyst is one or more than two of the following methods: heating for drying, freeze drying, and supercritical drying.

The catalyst is applied to acetylene hydrochlorination, and the application mode of the catalyst is one or more than two of the following modes:

(1) all the species in the reaction system enter from a three-dimensional communication open pore (b) mesh inlet of the porous pipe wall hollow foam material and a porous pipe wall hollow micro-channel inner cavity (c) inlet of the porous pipe wall hollow foam material at the same time, and carry out catalytic reaction through catalytic active sites at one or more than two of the three positions near the outer wall of the porous pipe wall hollow micro-channel (c), near the inner wall of the porous pipe wall hollow micro-channel (c) and in the pore of the porous pipe wall body, and all the products and all the unconsumed reactants leave through the three-dimensional communication open pore (b) mesh outlet or/and leave through the hollow micro-channel (c) inner cavity outlet; or one or more species in the product and/or one or more species in the unconsumed reactant leave through the mesh outlet of the three-dimensional communicating opening (b), and the rest one or more species in the product and/or the rest one or more species in the unconsumed reactant leave from the cavity outlet of the hollow microchannel (c) after mass transfer across the membrane of the porous tube wall to the cavity of the hollow microchannel (c);

(2) all the species in the reaction system enter from a mesh inlet of a three-dimensional communication open pore (b) of the hollow foam material of the porous pipe wall, perform catalytic reaction through catalytic active sites loaded on a secondary carrier filled in the mesh of the three-dimensional communication open pore (b), and/or perform mass transfer to an inner cavity of a hollow micro-channel (c) through the porous pipe wall across a membrane, perform catalytic reaction with the catalytic active sites loaded on the secondary carrier filled in the inner cavity of the hollow micro-channel (c) of the porous pipe wall, leave through an inner cavity outlet of the hollow micro-channel (c) or perform mass transfer to the mesh of the three-dimensional communication open pore (b) through the porous pipe wall across the membrane, and leave from a mesh outlet of the three-dimensional communication open pore (b); or one or more species in the product and/or one or more species in the unconsumed reactants exit through the inner cavity outlet of the hollow micro-channel (c), and the rest one or more species in the product and/or the rest one or more species in the unconsumed reactants exit from the mesh outlet of the three-dimensional communicating open pore (b) after mass transfer across the membrane through the porous tube wall to the meshes of the three-dimensional communicating open pore (b);

(3) all the species in the reaction system enter from the inlet of a hollow micro-channel (c) of the hollow foam material with the porous pipe wall, carry out catalytic reaction through catalytic active sites loaded on a secondary carrier filled in the inner cavity of the hollow micro-channel (c), and/or carry out mass transfer to meshes of a three-dimensional communication open pore (b) through the porous pipe wall in a transmembrane manner, then carry out catalytic reaction with the catalytic active sites loaded on the secondary carrier filled in the meshes of the three-dimensional communication open pore (b), and leave all the products and all unconsumed reactants through the mesh outlet of the three-dimensional communication open pore (b) or leave from the inner cavity outlet of the hollow micro-channel (c) through the porous pipe wall in a transmembrane manner after carrying out mass transfer to the inner cavity outlet of the hollow micro-channel (c); or one or more species in the product and/or one or more species in the unconsumed reactant leave through the mesh outlet of the three-dimensional communicating opening (b), and the rest one or more species in the product and/or the rest one or more species in the unconsumed reactant leave from the cavity outlet of the hollow microchannel (c) after mass transfer across the membrane of the porous tube wall to the cavity of the hollow microchannel (c);

(4) all the species in the reaction system enter from the three-dimensional communicating open pore (b) mesh inlet of the porous pipe wall hollow foam material, and carry out catalytic reaction through the catalytic active sites near the outer wall of the porous pipe wall hollow microchannel (c), and all the products and all the unconsumed reactants leave through the three-dimensional communicating open pore (b) mesh outlet or pass through the porous pipe wall to transfer mass to the inner cavity of the hollow microchannel (c) and then leave from the inner cavity outlet of the hollow microchannel (c); or one or more species in the product and/or one or more species in the unconsumed reactant leave through the mesh outlet of the three-dimensional communicating opening (b), and the rest one or more species in the product and/or the rest one or more species in the unconsumed reactant leave from the cavity outlet of the hollow microchannel (c) after mass transfer across the membrane of the porous tube wall to the cavity of the hollow microchannel (c);

(5) all the species in the reaction system enter from an inlet of an inner cavity (c) of a hollow microchannel of the porous tube wall of the hollow foam material of the porous tube wall, and carry out catalytic reaction through catalytic active sites near the inner wall of the hollow microchannel of the porous tube wall, and all the products and all the unconsumed reactants leave through an outlet of the inner cavity (c) of the hollow microchannel of the porous tube wall or leave from a mesh outlet of the three-dimensional communicating open pore (b) after transmembrane mass transfer to the mesh of the three-dimensional communicating open pore (b) through the porous tube wall; or one or more species in the product and/or one or more species in the unconsumed reactants exit through the outlet of the hollow micro-channel inner cavity (c) of the porous pipe wall, and the rest one or more species in the product and/or the rest one or more species in the unconsumed reactants exit from the outlet of the mesh of the three-dimensional communicating open pore (b) after mass transfer across the porous pipe wall to the mesh of the three-dimensional communicating open pore (b);

(6) all species in the reaction system enter from a mesh inlet of a three-dimensional communication open pore (b) of the hollow foam material of the porous pipe wall, are subjected to transmembrane mass transfer through the porous pipe wall to a catalytic active site near the inner wall of the inner cavity of the hollow microchannel (c) for catalytic reaction, and leave from an outlet of the inner cavity (c) of the hollow microchannel of the porous pipe wall or leave from a mesh outlet of the three-dimensional communication open pore (b) after being subjected to transmembrane mass transfer through the porous pipe wall to the mesh of the three-dimensional communication open pore (b) together with all unconsumed reactants; or one or more species in the product and/or one or more species in the unconsumed reactants exit through the outlet of the hollow micro-channel inner cavity (c) of the porous pipe wall, and the rest one or more species in the product and/or the rest one or more species in the unconsumed reactants exit from the outlet of the mesh of the three-dimensional communicating open pore (b) after mass transfer across the porous pipe wall to the mesh of the three-dimensional communicating open pore (b);

(7) all the species in the reaction system enter from an inlet of an inner cavity (c) of the hollow microchannel with the porous tube wall, are subjected to transmembrane mass transfer through the porous tube wall to a catalytic active site near the outer wall of the hollow microchannel with the porous tube wall for catalytic reaction, and leave from an outlet of a mesh of the three-dimensional communicating opening (b) or leave from an outlet of the inner cavity of the hollow microchannel (c) after being subjected to transmembrane mass transfer through the porous tube wall to the inner cavity of the hollow microchannel (c) together with all the unconsumed reactants; or one or more species in the product and/or one or more species in the unconsumed reactant leave through the mesh outlet of the three-dimensional communicating opening (b), and the rest one or more species in the product and/or the rest one or more species in the unconsumed reactant leave from the cavity outlet of the hollow microchannel (c) after mass transfer across the membrane of the porous tube wall to the cavity of the hollow microchannel (c);

(8) all species in the reaction system enter from a three-dimensional communication open pore (b) mesh inlet of the porous pipe wall hollow foam material, are subjected to mass transfer through a porous pipe wall to catalytic active sites distributed in pores in a porous pipe wall body to perform catalytic reaction, and all products and all unconsumed reactants are subjected to mass transfer through the porous pipe wall to the outer wall of the porous pipe wall hollow micro-channel and then leave from the three-dimensional communication open pore (b) mesh outlet or leave from the inner cavity outlet of the hollow micro-channel (c) through mass transfer through the porous pipe wall to the inner cavity of the hollow micro-channel (c); or one or more species in the product and/or one or more species in the unconsumed reactant are subjected to mass transfer across the porous pipe wall to the outer wall of the hollow micro-channel of the porous pipe wall and then are discharged through the mesh outlet of the three-dimensional communicating opening (b), and the rest one or more species in the product and/or the rest one or more species in the unconsumed reactant are subjected to mass transfer across the porous pipe wall to the inner cavity of the hollow micro-channel (c) and then are discharged from the inner cavity outlet of the hollow micro-channel (c);

(9) all the species in the reaction system enter from an inner cavity inlet of a hollow microchannel (c) of the porous tube wall hollow foam material, are subjected to mass transfer through a porous tube wall to catalytic active sites distributed in pores in a porous tube wall body for catalytic reaction, and all the products and all unconsumed reactants are subjected to mass transfer through the porous tube wall to the inner wall of the porous tube wall hollow microchannel and then leave through an inner cavity outlet of the hollow microchannel (c) or are subjected to mass transfer through the porous tube wall to the outer wall of the porous tube wall hollow microchannel and then leave from a mesh outlet of a three-dimensional communicating opening (b); or one or more species in the product and/or one or more species in the unconsumed reactant are subjected to mass transfer across the porous pipe wall to the inner wall of the hollow micro-channel of the porous pipe wall and then are discharged from the inner cavity outlet of the hollow micro-channel (c), and the rest one or more species in the product and/or the rest one or more species in the unconsumed reactant are subjected to mass transfer across the porous pipe wall to the outer wall of the hollow micro-channel of the porous pipe wall and then are discharged from the mesh outlet of the three-dimensional communicating open hole (b);

(10) one or more species in the reaction system enter from the three-dimensional communication open pore (b) mesh inlet of the porous pipe wall hollow foam material, the other one or more species in the reaction system enter from the hollow micro-channel (c) inner cavity inlet of the porous pipe wall hollow foam material and transfer mass to the outer wall of the porous pipe wall hollow micro-channel through the porous pipe wall transmembrane mass, the catalytic active site near the outer wall of the porous pipe wall hollow micro-channel (c) and the reactant species entering from the three-dimensional communication open pore (b) mesh inlet participate in the catalytic reaction together, and all the products and all the unconsumed reactants leave through the three-dimensional communication open pore (b) mesh outlet or transfer mass to the inner cavity of the hollow micro-channel (c) through the porous pipe wall transmembrane mass, and then leave from the hollow micro-channel (c) inner cavity outlet; or one or more species in the product and/or one or more species in the unconsumed reactant leave through the mesh outlet of the three-dimensional communicating opening (b), and the rest one or more species in the product and/or the rest one or more species in the unconsumed reactant leave from the cavity outlet of the hollow microchannel (c) after mass transfer across the membrane of the porous tube wall to the cavity of the hollow microchannel (c);

(11) one or more species in the reaction system enter from the inner cavity inlet of the hollow microchannel (c) of the porous tube wall hollow foam material, the rest one or more species in the reaction system enter from the three-dimensional communication open pore (b) mesh inlet of the porous tube wall hollow foam material and transfer mass to the inner wall of the porous tube wall hollow microchannel through the porous tube wall transmembrane mass transfer from the outer wall of the porous tube wall hollow microchannel (c), the catalytic active sites near the inner wall of the hollow microchannel (c) on the porous tube wall participate in catalytic reaction together with reactant species entering from the inner cavity inlet of the hollow microchannel (c) on the porous tube wall, and all products and all unconsumed reactants leave through the inner cavity outlet of the hollow microchannel (c) on the porous tube wall or leave from the mesh outlet of the three-dimensional communicating open pore (b) after mass transfer to the outer wall of the hollow microchannel (c) through the transmembrane of the porous tube wall; or one or more species in the product and/or one or more species in the unconsumed reactant leave through the inner cavity outlet of the hollow microchannel (c) on the porous pipe wall, and the rest one or more species in the product and/or the rest one or more species in the unconsumed reactant leave from the mesh outlet of the three-dimensional communicating open pore (b) after mass transfer across the porous pipe wall to the outer wall of the hollow microchannel (c);

(12) one or more species in the reaction system enter from a three-dimensional communication open pore (b) mesh inlet of the porous pipe wall hollow foam material and transfer mass to the inner pores of the porous pipe wall body through the porous pipe wall, the rest one or more species in the reaction system enter from a hollow microchannel (c) inner cavity inlet of the porous pipe wall hollow foam material and transfer mass to the inner pores of the porous pipe wall body through the porous pipe wall, and then participate in catalytic reaction with reactant species which enter from the three-dimensional communication open pore (b) mesh inlet and transfer mass to the inner pores of the porous pipe wall body through the porous pipe wall at catalytic active sites distributed in the inner pores of the porous pipe wall body, all products and all unconsumed reactants transfer mass to the outer wall of the hollow microchannel (c) through the porous pipe wall, leave from a three-dimensional communication open pore (b) mesh outlet or transfer mass to the inner cavity of the hollow microchannel (c) through the porous pipe wall, exiting from the lumen outlet of the hollow microchannel (c); or one or more species in the product and/or one or more species in the unconsumed reactant are subjected to transmembrane mass transfer to the outer wall of the hollow microchannel (c) through the porous tube wall and then are discharged from the mesh outlet of the three-dimensional communicating opening (b), and the rest one or more species in the product and/or the rest one or more species in the unconsumed reactant are subjected to transmembrane mass transfer to the inner cavity of the hollow microchannel (c) through the porous tube wall and then are discharged from the inner cavity outlet of the hollow microchannel (c).

The catalyst utilizes multi-scale pores possessed by the porous pipe wall hollow foam material to regulate and control the dipping, loading or drying process of catalytic active components, so that the active components are promoted to reach controllable high dispersion degree, and the catalytic activity, selectivity and service life of the acetylene hydrochlorination catalyst are further improved;

or in the application process of the catalyst, the following process is finely regulated and controlled by utilizing multi-scale pores possessed by the hollow foam material on the porous pipe wall: the material transfer process of reactants and/or products, and the introduction or removal process of heat generated by reaction or required heat, so as to improve the catalytic activity, selectivity and service life of the catalyst for acetylene hydrochlorination.

The design idea of the invention is as follows:

the invention creatively introduces the porous pipe wall hollow foam material as a carrier material into the structural design and preparation process of the acetylene hydrochlorination catalyst, and develops the acetylene hydrochlorination catalyst based on the porous pipe wall hollow foam material. The porous pipe wall hollow foam material has rich and multi-scale pore structures, is beneficial to the precise regulation and control process of mass transfer and heat transfer in the process of embedding catalytic reaction in the structural design, preparation and application processes of the catalyst, and is mainly and intensively reflected in the following aspects: (1) in the preparation process of the catalyst, the loading capacity of the catalytic active component can be regulated and controlled by utilizing the pore structure of the carrier material; (2) in the preparation process of the catalyst, the loading quality, namely the dispersion degree, of the catalytic active component can be regulated and controlled by utilizing the pore structure of the carrier material; (3) in the application process of the catalyst, the pore structure of the carrier material can be used for regulating and controlling mass transfer and heat transfer processes related to the catalytic reaction process.

The porous pipe wall hollow foam material is a special porous pipe wall hollow foam material. The structure of the micro-channel is macroscopically constructed by a three-dimensionally communicated support framework network, the support framework is a three-dimensionally communicated micro-channel with a hollow structure, and the wall of the micro-channel is a pore with a nano-scale and/or micro-scale pore diameter. The material with the structure has the advantages of light weight, adjustable porosity, high permeability and the like. The mass transfer, momentum transfer and heat transfer efficiency of the fluid in the three-dimensional communicated openings can be effectively improved. Meanwhile, the mass transfer process and the heat transfer process of the hydrochlorination reaction of acetylene can be finely regulated and controlled by utilizing a micro-channel: when the hollow micro-channel with the porous structure tube wall is used as a carrier membrane to load a catalytic coating, the reactant C can be treated₂H₂And HCl is finely distributed in situ or the product chloroethylene is finely separated in situ, and the reaction heat is finely moved in or out in situ. Therefore, the acetylene hydrochlorination catalyst based on the porous pipe wall hollow foam material is successfully developed in view of the technical requirements of finely regulating and controlling the mass transfer and heat transfer processes in the acetylene hydrochlorination process so as to improve the stability and service life of the catalyst, and is one of the main innovation points of the invention.

The invention has the following advantages and beneficial effects:

1. the acetylene hydrochlorination catalyst based on the porous pipe wall hollow foam material can carry out in-situ fine distribution on acetylene and/or hydrogen chloride and can also carry out in-situ fine separation on a product vinyl chloride monomer when the hollow micro-channel with the porous pipe wall is used as a carrier membrane to load a catalytic coating.

2. According to the acetylene hydrochlorination catalyst based on the porous pipe wall hollow foam material, when the porous pipe wall hollow micro-channel is used as a carrier to load a catalytic coating, the required heat or the heat generated by the reaction can be finely moved in or out in situ, so that the inactivation of catalytic active components caused by temperature runaway is reduced, the occurrence of side reactions is reduced, and the service life of the catalyst is prolonged.

3. According to the acetylene hydrochlorination catalyst based on the porous pipe wall hollow foam material, the multi-scale pores of the porous pipe wall hollow foam material are beneficial to regulating and controlling the dipping, loading or drying process of the catalytic active component, so that the active component is promoted to reach controllable high dispersity, and the catalytic activity, selectivity and service life of the acetylene hydrochlorination catalyst are further improved.

4. The catalyst based on the porous pipe wall hollow foam material prepared by the preparation method of the catalyst has the following advantages: the catalytic active component, the cocatalyst component and the second carrier used in the hydrochlorination reaction of acetylene can realize controllable loading in pores of various scales of the hollow foam material of the porous pipe wall, so that the heat transfer and mass transfer in the reaction process are enhanced, and the service life of the catalyst is prolonged.

5. The invention has simple technical process and does not need complex equipment.

Drawings

FIG. 1 is a macroscopic view of a hollow foam material as a support material for an acetylene hydrochlorination catalyst based on a porous tube wall hollow foam material according to the present invention. Wherein a is a three-dimensionally communicated support skeleton, b is a macroscopic open pore, c is a hollow microchannel, d1 is a macroscopic open pore size, d2 is a hollow microchannel outer diameter, and d3 is a hollow microchannel inner diameter.

FIG. 2 is a schematic cross-sectional view of a hollow microchannel of the porous tube wall hollow foam of the present invention, i.e., a cross-sectional view of a circular or near-circular hollow cavity. Wherein a is a hollow inner cavity of the hollow microchannel, b is the inner wall of the hollow microchannel, c is the wall body of the hollow microchannel with a porous structure, and d is the outer wall of the hollow microchannel.

FIG. 3 is a schematic cross-sectional view of a hollow microchannel of a porous tube wall hollow foam material of the present invention, the cross-sectional view of a rectangular hollow cavity. Wherein a is a hollow inner cavity of the hollow microchannel, b is the inner wall of the hollow microchannel, c is the wall body of the hollow microchannel with a porous structure, and d is the outer wall of the hollow microchannel.

FIG. 4 is a schematic cross-sectional view of a hollow microchannel of a porous tube wall hollow foam material of the present invention, the cross-sectional view of a triangular hollow cavity. Wherein a is a hollow inner cavity of the hollow microchannel, b is the inner wall of the hollow microchannel, c is the wall body of the hollow microchannel with a porous structure, and d is the outer wall of the hollow microchannel.

FIG. 5 is a schematic cross-sectional view of the hollow micro-channel of the porous tube wall hollow foam material of the present invention, the cross-sectional view of the oval hollow cavity. Wherein a is a hollow inner cavity of the hollow microchannel, b is the inner wall of the hollow microchannel, c is the wall body of the hollow microchannel with a porous structure, and d is the outer wall of the hollow microchannel.

FIG. 6 is a scanning electron micrograph of the distribution of any one or more of the catalytically active component, the cocatalyst component and the second support in and out of the walls of the hollow microchannel having a porous wall.

Detailed Description

In the specific implementation mode of the acetylene hydrochlorination catalyst based on the porous pipe wall hollow foam material and the preparation method thereof, the acetylene hydrochlorination catalyst based on the porous pipe wall hollow foam material is constructed by taking the hollow foam materials with different structural parameters as carrier materials and loading catalytic activity coatings with different catalytic activities, and the specific implementation mode is as follows:

example 1

The hollow foam activated carbon material with the porous structure microchannel wall is used as a carrier, the average size of macroscopically three-dimensionally communicated open pores is 3mm, the average size of the outer diameter of the hollow microchannel is 1mm, the average size of the inner diameter is 500 mu m, the average pore diameter of pores contained in the microchannel wall body is 1 mu m, and the porosity is 10%. The hollow foam activated carbon material is soaked in a chloroauric acid solution and dried to prepare the acetylene hydrochlorination reaction catalyst which is based on the porous pipe wall hollow foam material and uniformly loads a gold trichloride catalytic active component on a hollow micro-channel pipe wall body with a porous structure, wherein the gold content is 0.001-1 wt%. The catalyst is applied to acetylene hydrochlorination, and mixed gas of acetylene and hydrogen chloride is simultaneously introduced into an inner cavity of a hollow micro-channel and a macroscopic three-dimensional communicated open pore network, wherein the mixed gas comprises the following components in parts by weight: and (3) carrying out catalytic reaction on acetylene 1.1 under the conditions of 0.01MPa of reaction pressure and 110-200 ℃ of reaction temperature. The catalytic performance results were: the acetylene conversion rate is 98 percent, and the vinyl chloride selectivity is 100 percent.

Example 2

The hollow foam material which is composed of 50wt% of activated carbon and 50wt% of molecular sieve and has a porous structure microchannel tube wall is used as a carrier, the average size of macroscopic three-dimensional communication open pores is 3mm, the average size of the outer diameter of the hollow microchannel is 1mm, the average size of the inner diameter is 500 mu m, the average pore diameter of pores contained in the tube wall body is 1 mu m, and the porosity is 10%. The hollow foam (active carbon-molecular sieve) material is soaked in chloroauric acid solution and dried to prepare the acetylene hydrochlorination reaction catalyst which is based on the porous pipe wall hollow foam material and uniformly loads gold trichloride catalytic active components on the hollow microchannel pipe wall body with the porous structure, wherein the gold content is 0.001-1 wt%. The catalyst is applied to acetylene hydrochlorination, and mixed gas of acetylene and hydrogen chloride is simultaneously introduced into an inner cavity of a hollow micro-channel and a macroscopic three-dimensional communicated open pore network, wherein the mixed gas comprises the following components in parts by weight: and (3) carrying out catalytic reaction on acetylene 1.1 under the conditions of 0.01MPa of reaction pressure and 110-200 ℃ of reaction temperature. The catalytic performance results were: the acetylene conversion rate is 99 percent, and the chloroethylene selectivity is 99 percent.

Example 3

The hollow foam silicon nitride material with the porous structure microchannel wall is used as a carrier, the average size of macroscopic three-dimensional communication open pores is 4mm, the average size of the outer diameter of the hollow microchannel is 1.5mm, the cross section of a cavity in the hollow microchannel is a rectangle with the diameter of 200 microns multiplied by 300 microns, the average aperture of pores contained in the microchannel wall body is 1 micron, and the porosity is 20%. And (3) loading a second carrier coating on the outer side of the pipe wall of the hollow micro-channel by circularly carrying out operations of 'slurry dipping-excess slurry removal-half drying', wherein the components of the second carrier coating are 90 wt% of activated carbon and 10 wt% of graphene, and the thickness of the coating is 80 microns. And then dipping the sample in a chloroauric acid solution, and drying to prepare the acetylene hydrochlorination reaction catalyst which is based on the porous pipe wall hollow foam material and loads a gold trichloride catalytic active coating on the outer side of the pipe wall of the hollow micro-channel with the porous structure. Wherein the gold content in the catalytic coating is 0.001wt% -1 wt%. The catalyst is applied to acetylene hydrochlorination, HCl with the temperature of 100 ℃ is introduced into the cavity of a hollow micro-channel, and a mixed gas of acetylene and hydrogen chloride is introduced into a macroscopic three-dimensional communicated open pore network, wherein the mixed gas comprises the following components in parts by weight: and (3) carrying out catalytic reaction on acetylene 1.1 under the conditions of 0.01MPa of reaction pressure and 110-200 ℃ of reaction temperature. The catalytic performance results were: the acetylene conversion rate is 99.9 percent, and the vinyl chloride selectivity is 100 percent.

Example 4

The method is characterized in that a hollow foam silicon nitride material with a porous structure micro-channel pipe wall is used as a carrier, the average size of macro three-dimensional communication open pores is 4mm, the average size of the outer diameter of a hollow micro-channel is 1.5mm, the average size of the inner diameter is 800 mu m, a second carrier coating is loaded on the outer side of the hollow micro-channel pipe wall by circularly carrying out operations of slurry dipping, excessive slurry removing and semi-drying, the composition is 90 wt% of activated carbon and 10 wt% of carbon aerogel, and the coating thickness is 80 mu m. And then dipping the sample in a chloroauric acid solution, and drying to prepare the acetylene hydrochlorination reaction catalyst which is based on the porous pipe wall hollow foam material and loads a gold trichloride catalytic active coating on the outer side of the pipe wall of the hollow micro-channel with the porous structure. Wherein the gold content in the catalytic coating is 0.001wt% -1 wt%. The catalyst is applied to acetylene hydrochlorination, HCl with the temperature of 100 ℃ is introduced into the cavity of a hollow micro-channel, and a mixed gas of acetylene and hydrogen chloride is introduced into a macroscopic three-dimensional communicated open pore network, wherein the mixed gas comprises the following components in parts by weight: and (3) carrying out catalytic reaction on acetylene 1.1 under the conditions of 0.01MPa of reaction pressure and 110-200 ℃ of reaction temperature. The catalytic performance results were: the acetylene conversion rate is 99.9 percent, and the vinyl chloride selectivity is 100 percent.

Example 5

The method is characterized in that a hollow foam silicon nitride material with a porous structure microchannel tube wall is used as a carrier, the average size of macro three-dimensional communication open pores is 4mm, the average size of the outer diameter of a hollow microchannel is 1.5mm, the average size of the inner diameter is 800 mu m, a second carrier coating is loaded on the outer side of the hollow microchannel tube wall by circularly carrying out operations of 'slurry dipping, excess slurry removing and half drying', the composition is 90 wt% of activated carbon and 10 wt% of carbon nano tubes, and the coating thickness is 80 mu m. And then dipping the sample in a chloroauric acid solution, and drying to prepare the acetylene hydrochlorination reaction catalyst which is based on the porous pipe wall hollow foam material and loads a gold trichloride catalytic active coating on the outer side of the pipe wall of the hollow micro-channel with the porous structure. Wherein the gold content in the catalytic coating is 0.001wt% -1 wt%. The catalyst is applied to acetylene hydrochlorination, HCl with the temperature of 100 ℃ is introduced into the cavity of a hollow micro-channel, and a mixed gas of acetylene and hydrogen chloride is introduced into a macroscopic three-dimensional communicated open pore network, wherein the mixed gas comprises the following components in parts by weight: and (3) carrying out catalytic reaction on acetylene 1.1 under the conditions of 0.01MPa of reaction pressure and 110-200 ℃ of reaction temperature. The catalytic performance results were: the acetylene conversion rate is 99.9 percent, and the chloroethylene selectivity is 99.9 percent.

Example 6

The hollow foam material which is composed of 95 wt% of activated carbon and 5 wt% of graphene and is provided with a porous structure microchannel tube wall is used as a carrier, the average size of macroscopic three-dimensional communication open pores is 3mm, the average size of the outer diameter of the hollow microchannel is 1mm, the average size of the inner diameter is 500 mu m, the average pore diameter of pores contained in the tube wall body is 1 mu m, and the porosity is 10%. The hollow foam (active carbon-graphene) material is soaked in a chloroauric acid solution and dried to prepare the acetylene hydrochlorination reaction catalyst which is based on the porous pipe wall hollow foam material and uniformly loads gold trichloride catalytic active components on the hollow microchannel pipe wall body with the porous structure, wherein the gold content is 0.001-1 wt%. The catalyst is applied to acetylene hydrochlorination, and mixed gas of acetylene and hydrogen chloride is simultaneously introduced into an inner cavity of a hollow micro-channel and a macroscopic three-dimensional communicated open pore network, wherein the mixed gas comprises the following components in parts by weight: and (3) carrying out catalytic reaction on acetylene 1.1 under the conditions of 0.01MPa of reaction pressure and 110-200 ℃ of reaction temperature. The catalytic performance results were: the acetylene conversion rate is 99 percent, and the chloroethylene selectivity is 100 percent.

Example 7

The composition material is 50wt% Si_6-xAl_xO_xN_8-xThe hollow foam material with the porous structure microchannel tube wall of 40 wt% of activated carbon and 10 wt% of disordered mesoporous carbon is used as a carrier, the average size of macroscopic three-dimensional communication open pores is 3mm, the average size of the outer diameter of the hollow microchannel is 1mm, the average size of the inner diameter is 500 mu m, the average pore diameter of pores contained in the tube wall body is 1 mu m, and the porosity is 10%. The hollow foam material is soaked in a chloroauric acid solution, and the acetylene hydrochlorination reaction catalyst which is based on the porous pipe wall hollow foam material and is uniformly loaded with gold trichloride catalytic active components on the pipe wall body of the hollow micro-channel with the porous structure is prepared after drying, wherein the gold content is 0.001-1 wt%. The catalyst is applied to acetylene hydrochlorination, and mixed gas of acetylene and hydrogen chloride is simultaneously introduced into an inner cavity of a hollow micro-channel and a macroscopic three-dimensional communicated open pore network, wherein the mixed gas comprises the following components in parts by weight: and (3) carrying out catalytic reaction on acetylene 1.1 under the conditions of 0.01MPa of reaction pressure and 110-200 ℃ of reaction temperature. The catalytic performance results were: the acetylene conversion rate is 80%, and the vinyl chloride selectivity is 100%.

Example 8

Hollow foam Si with porous structure micro-channel tube wall_6-xAl_xO_xN_8-xThe material is a carrier, the average size of macro three-dimensional communicated open pores is 4mm, the average size of the outer diameter of the hollow micro-channel is 1.5mm, the cross section of a cavity in the hollow micro-channel is an equilateral triangle with the side length of 300 mu m, the average pore diameter of pores contained in the tube wall body is 1 mu m, and the porosity is 10%. And circularly carrying out operations of 'slurry dipping-excess slurry removal-half drying' to load a second carrier coating on the outer side of the pipe wall of the hollow micro-channel, wherein the second carrier coating comprises 70wt% of activated carbon, 10 wt% of magnesium oxide, 10 wt% of graphite and 10 wt% of carbon aerogel, and the thickness of the coating is 100 micrometers. Then dipping the sample in chloroauric acid solution, drying and preparing the catalytic active coating layer which loads gold trichloride on the outer side of the tube wall of the hollow micro-channel with the porous structureBased on porous pipe wall hollow foam material. Wherein the gold content in the catalytic coating is 0.001wt% -1 wt%. The catalyst is applied to acetylene hydrochlorination, HCl with the temperature of 100 ℃ is introduced into the cavity of a hollow micro-channel, and a mixed gas of acetylene and hydrogen chloride is introduced into a macroscopic three-dimensional communicated open pore network, wherein the mixed gas comprises the following components in parts by weight: and (3) carrying out catalytic reaction on acetylene 1.1 under the conditions of 0.01MPa of reaction pressure and 110-200 ℃ of reaction temperature. The catalytic performance results were: the acetylene conversion rate is 99.9 percent, and the vinyl chloride selectivity is 100 percent.

Example 9

The method is characterized in that a hollow foam HastelloyB-2 material with a porous structure microchannel wall is used as a carrier, the average size of macro three-dimensional communication open pores is 4mm, the average size of the outer diameter of a hollow microchannel is 1.5mm, the average size of the inner diameter is 800 mu m, a second carrier coating is loaded on the outer side of the hollow microchannel wall by circularly carrying out 'slurry dipping, excess slurry removing and half drying' operation, and the composition is 90 wt% of activated carbon and 10 wt% of carbon aerogel, and the coating thickness is 200 mu m. And then dipping the sample in a chloroauric acid solution, and drying to prepare the acetylene hydrochlorination reaction catalyst which is based on the porous pipe wall hollow foam material and loads a gold trichloride catalytic active coating on the outer side of the pipe wall of the hollow micro-channel with the porous structure. Wherein the gold content in the catalytic coating is 0.001wt% -1 wt%. The catalyst is applied to acetylene hydrochlorination, HCl with the temperature of 100 ℃ is introduced into the cavity of a hollow micro-channel, and a mixed gas of acetylene and hydrogen chloride is introduced into a macroscopic three-dimensional communicated open pore network, wherein the mixed gas comprises the following components in parts by weight: and (3) carrying out catalytic reaction on acetylene 1.1 under the conditions of 0.01MPa of reaction pressure and 110-200 ℃ of reaction temperature. The catalytic performance results were: the acetylene conversion rate is 99.6 percent, and the vinyl chloride selectivity is 100 percent.

Example 10

The hollow foam material which is composed of 40 wt% of silicon carbide, 50wt% of activated carbon and 10 wt% of disordered mesoporous carbon and is provided with a porous structure microchannel pipe wall is used as a carrier, the average size of macroscopic three-dimensional communicated open pores is 3mm, the average size of the outer diameter of the hollow microchannel is 1mm, the average size of the inner diameter is 500 mu m, the average pore diameter of pores contained in the pipe wall body is 1 mu m, and the porosity is 10%. The hollow foam material is soaked in mercuric chloride solution, and the acetylene hydrochlorination reaction catalyst which is based on the porous tube wall hollow foam material and is uniformly loaded with mercuric chloride catalytic active components on the tube wall body of the hollow micro-channel with the porous structure is prepared after drying, wherein the mercury content is 0.001-1 wt%. The catalyst is applied to acetylene hydrochlorination, and mixed gas of acetylene and hydrogen chloride is simultaneously introduced into an inner cavity of a hollow micro-channel and a macroscopic three-dimensional communicated open pore network, wherein the mixed gas comprises the following components in parts by weight: and (3) carrying out catalytic reaction on acetylene 1.1 under the conditions of 0.01MPa of reaction pressure and 110-200 ℃ of reaction temperature. The catalytic performance results were: the acetylene conversion rate is 90%, and the vinyl chloride selectivity is 100%.

Example 11

The method is characterized in that a hollow foam silicon nitride material with a porous structure microchannel tube wall is used as a carrier, the average size of macro three-dimensional communication open pores is 4mm, the average size of the outer diameter of a hollow microchannel is 1.5mm, the average size of the inner diameter is 800 mu m, a second carrier coating is loaded on the outer side of the hollow microchannel tube wall by circularly carrying out operations of 'slurry dipping, excess slurry removing and half drying', the composition is 90 wt% of activated carbon and 10 wt% of carbon nano tubes, and the coating thickness is 80 mu m. And then dipping the sample in a palladium chloride solution, and drying to prepare the acetylene hydrochlorination reaction catalyst which is based on the porous pipe wall hollow foam material and is provided with a palladium chloride catalytic active coating on the outer side of the pipe wall of the hollow micro-channel with the porous structure. Wherein the palladium content in the catalytic coating is 0.001wt% -1 wt%. The catalyst is applied to acetylene hydrochlorination, HCl with the temperature of 100 ℃ is introduced into the cavity of a hollow micro-channel, and a mixed gas of acetylene and hydrogen chloride is introduced into a macroscopic three-dimensional communicated open pore network, wherein the mixed gas comprises the following components in parts by weight: and (3) carrying out catalytic reaction on acetylene 1.1 under the conditions of 0.01MPa of reaction pressure and 110-200 ℃ of reaction temperature. The catalytic performance results were: the acetylene conversion rate is 80 percent, and the chloroethylene selectivity is 90 percent.

Example 12

The method is characterized in that a hollow foam silicon nitride material with a porous structure and a microchannel tube wall is used as a carrier, the average size of macro three-dimensional communicated open pores is 4mm, the average size of the outer diameter of a hollow microchannel is 1.5mm, the average size of the inner diameter is 800 mu m, a second carrier coating is loaded on the outer side of the hollow microchannel tube wall by circularly carrying out operations of 'slurry dipping, excess slurry removing and half drying', the composition is 90 wt% of activated carbon and 10 wt% of ordered mesoporous carbon, and the coating thickness is 80 mu m. And then dipping the sample in a ruthenium chloride solution, and drying to prepare the acetylene hydrochlorination reaction catalyst which is based on the porous pipe wall hollow foam material and is loaded with a ruthenium chloride catalytic active coating on the outer side of the pipe wall of the hollow micro-channel with the porous structure. Wherein the ruthenium content in the catalytic coating is 0.001wt% -1 wt%. The catalyst is applied to acetylene hydrochlorination, HCl with the temperature of 100 ℃ is introduced into the cavity of a hollow micro-channel, and a mixed gas of acetylene and hydrogen chloride is introduced into a macroscopic three-dimensional communicated open pore network, wherein the mixed gas comprises the following components in parts by weight: and (3) carrying out catalytic reaction on acetylene 1.1 under the conditions of 0.01MPa of reaction pressure and 110-200 ℃ of reaction temperature. The catalytic performance results were: the acetylene conversion rate is 90%, and the vinyl chloride selectivity is 90%.

From fig. 1 it can be seen the macroscopic morphology of the hollow foam material as the support material for the acetylene hydrochlorination catalyst based porous tube wall hollow foam material according to the invention. Wherein a is a three-dimensionally communicated support skeleton, b is a macroscopic open pore, c is a hollow microchannel, d1 is a macroscopic open pore size, d2 is a hollow microchannel outer diameter, and d3 is a hollow microchannel inner diameter.

As can be seen from FIG. 2, the cross section of the hollow micro-channel of the porous pipe wall hollow foam material of the present invention is schematically shown-the cross section of the circular or nearly circular hollow cavity. Wherein a is a hollow inner cavity of the hollow microchannel, b is the inner wall of the hollow microchannel, c is the wall body of the hollow microchannel with a porous structure, and d is the outer wall of the hollow microchannel.

As can be seen from FIG. 3, the cross section of the hollow micro-channel of the porous pipe wall hollow foam material of the present invention is a schematic view-the cross section of a rectangular hollow cavity. Wherein a is a hollow inner cavity of the hollow microchannel, b is the inner wall of the hollow microchannel, c is the wall body of the hollow microchannel with a porous structure, and d is the outer wall of the hollow microchannel.

As can be seen from FIG. 4, the cross section of the hollow micro-channel of the porous pipe wall hollow foam material of the present invention is a schematic view-the cross section of the triangular hollow cavity. Wherein a is a hollow inner cavity of the hollow microchannel, b is the inner wall of the hollow microchannel, c is the wall body of the hollow microchannel with a porous structure, and d is the outer wall of the hollow microchannel.

As can be seen from FIG. 5, the cross section of the hollow micro-channel of the porous pipe wall hollow foam material of the present invention is a schematic view, namely the cross section of an elliptical hollow inner cavity. Wherein a is a hollow inner cavity of the hollow microchannel, b is the inner wall of the hollow microchannel, c is the wall body of the hollow microchannel with a porous structure, and d is the outer wall of the hollow microchannel.

As shown in FIG. 6, the scanning electron micrographs of any one or more of the catalytically active component, the co-catalyst component and the second carrier of the present invention are distributed inside and outside the walls of the hollow micro-channel with porous walls. As can be seen from FIG. 6, the hollow microchannel tube wall body is a porous structure, and the reactant or product is transferred on two sides of the hollow microchannel tube wall of the porous structure. Meanwhile, the inner wall and the outer wall of the hollow micro-channel with the porous structure can be uniformly loaded with the catalytic active coating.

The results of the examples show that the main constituent materials of the acetylene hydrochlorination catalyst based on the porous pipe wall hollow foam material comprise the porous pipe wall hollow foam material, and the whole catalyst is a three-dimensional communicated open-cell foam material macroscopically; the open-cell foam material skeleton contains a hollow inner cavity, and the cross section of the inner cavity is triangular, rectangular, circular, nearly circular or elliptical. The porous pipe wall can be used as a catalytic carrier material to directly load a catalytic active component and a cocatalyst component, or used as a first catalytic carrier to load a second carrier, the cocatalyst component and the catalytic active component on the basis of the first catalytic carrier. Wherein, any one or more than two of the catalytic active component, the cocatalyst component and the second carrier can be loaded on the outer side or the inner side of the porous structure pipe wall, and can also be uniformly distributed in pores contained in the porous pipe wall body. The acetylene hydrochlorination catalyst based on the porous pipe wall hollow foam material is innovative in that: after the porous pipe wall hollow foam material is introduced, the catalyst can carry out in-situ fine distribution on acetylene and/or hydrogen chloride, and can also carry out in-situ fine separation on a product vinyl chloride monomer, so that the catalyst is favorable for carrying out optimized distribution on a catalytic active component and a cocatalyst component on space, and carrying out in-situ fine transfer or transfer on reaction heat, thereby reducing the inactivation of the catalytic active component caused by temperature runaway, reducing the occurrence of side reactions, and prolonging the service life of the catalyst.

Claims

1. The acetylene hydrochlorination catalyst is characterized in that the hollow foam material is a porous pipe wall hollow foam material with macroscopic three-dimensional communicated open pores, and the structure of the material is macroscopically communicated by a support skeleton (a) in a three-dimensional way to form an open pore (b) network structure; the supporting framework (a) is provided with a hollow microchannel (c) with controllable size, the cross section of the inner cavity of the microchannel (c) is triangular, rectangular, approximately circular or elliptical, the framework between the wall surface corresponding to the outer diameter of the microchannel (c) and the inner wall of the inner cavity of the microchannel (c) is a microchannel pipe wall with a porous structure, and the microchannel pipe wall contains a porous structure with angstrom-scale and/or nanometer-scale and/or micron-scale pore diameter pores;

the hollow foam material contained in the catalyst is three-dimensionally communicated by a supporting framework to form an open-cell network structure, and the mesh size (d1) is 0.2-20 mm; the outer diameter (d2) of the hollow micro-channel is 0.1 mm-10 mm, and the inner diameter (d3) is 0.02 mm-9 mm; the pore size range of pores contained in the porous pipe wall or the porous micro-channel pipe wall is 0.1 nm-100 mu m, and the porosity p is more than 0 and less than or equal to 70 percent;

the catalyst contains a porous pipe wall hollow foam material, and one or two upper parts of the porous pipe wall hollow foam material are directly used as a specific bearing part of a catalytic carrier for loading a catalytic active component and a cocatalyst component: the inner wall of the hollow foam material, the outer wall of the hollow foam material, the porous pipe wall body of the hollow foam material and the porous pipe wall body of the hollow foam material contain pores with angstrom-scale and/or nanometer-scale and/or micron-scale pore diameters;

the preparation method of the acetylene hydrochlorination catalyst based on the porous pipe wall hollow foam material comprises the steps of directly immersing the porous pipe wall hollow foam material serving as a first carrier into a feed liquid containing a catalytic active component and a cocatalyst component, taking out and drying to obtain the acetylene hydrochlorination structural catalyst; wherein, the content of the catalytic active component is 0.001wt percent to 70wt percent, and the content of the cocatalyst component is 0.001wt percent to 50wt percent.

2. The catalyst for hydrochlorination of acetylene based on a porous pipe wall hollow foam material according to claim 1, characterized in that the catalyst contains a second carrier, and the second carrier is present in one or more of the following ways:

(2) the second carrier is filled in the hollow inner cavity;

the catalytic active component and the cocatalyst component are only dispersed on the local area of 1 nm-500 mu m on the surface of the second carrier, or are uniformly dispersed on the surface and in the second carrier.

3. The acetylene hydrochlorination catalyst based on the porous pipe wall hollow foam material is characterized in that the catalyst comprises second carriers in the presence forms (1) to (3), and the filling rate of the second carriers is 5-100% of the pore volume of filled pores; the catalyst comprises a second carrier in the form of (4) to (6), wherein the second carrier has a loading thickness of 1nm to 1000 μm.

4. The acetylene hydrochlorination catalyst based on the porous pipe wall hollow foam material is characterized in that the second carrier of the catalyst is one or two of the following substancesThe method comprises the following steps: gamma-Al₂O₃、η-Al₂O₃、θ-Al₂O₃、δ-Al₂O₃、α-Al₂O₃Magnesium oxide, titanium oxide, molecular sieves, mesoporous silica, amorphous silica, graphite, amorphous carbon, graphene, diamond, activated carbon, ordered mesoporous carbon, unordered mesoporous carbon, carbon fibers, carbon nanotubes, carbon aerogel, silicon carbide, silica gel, silicon aerogel;

5. The catalyst for acetylene hydrochlorination based on the porous pipe wall hollow foam material according to claim 2, characterized in that the catalytically active components of the catalyst are one or more than two of the following substances and compounds or complexes thereof: w, Ta, Mo, Ti, Zr, Fe, Ni, Co, Cr, Pt, Rh, Pd, Cu, Al, Au, Mn, Ru, Ag, Zn, Cd, In, Pb, As, Bi, Sb, Se, Te, Ba, Hg.

6. The catalyst for hydrochlorination of acetylene based on a porous tube wall hollow foam material according to claim 5, characterized in that the compound is one or more than two of the following substance classes: chloride, oxide, sulfide, carbide, bromide, iodide, fluoride, phosphate, nitrate, nitrite, sulfate, sulfite, acetate, oxalate, citrate, tartrate, thiosulfate;

7. The catalyst for hydrochlorination of acetylene based on a porous tube wall hollow foam material according to claim 6, characterized in that the catalytically active component is one or a combination of two or more of the following substances: chloroauric acid, chloroplatinic acid, palladium chloride, ruthenium chloride, rhodium chloride, MoS₂。

8. The catalyst for hydrochlorination of acetylene based on a hollow foam material with porous tube walls according to claim 1, characterized in that the hollow foam material with porous tube walls contained in the catalyst mainly comprises one or more than two of the following categories: nickel200, Nickel201, Monel400, Inconel600, Inconel625, Incoloy800, Incoloy825, Hastelloy C-4, Avesta254, Hastelloy B-2, carbon steel, 304 stainless steel, 316L stainless steel, titanium, zirconium, tantalum, quartz SiO₂Borosilicate glass, silicon carbide, zirconium carbide, tungsten carbide, titanium carbide, boron carbide, tantalum carbide, vanadium carbide, chromium carbide, niobium carbide, molybdenum carbide, iron carbide, manganese carbide, alpha-Si₃N₄、β- Si₃N₄、AlN、Si_6-xAl_xO_xN_8-xBN, Si, graphite, amorphous carbon, graphene, diamond, activated carbon, ordered mesoporous carbon, unordered mesoporous carbon, carbon fiber, carbon nanotube.

9. The method for preparing a catalyst for hydrochlorination of acetylene based on a porous tube wall hollow foam material according to any one of claims 1 to 8, characterized in that the method for preparing the catalyst is one or a combination of two of the following methods:

10. The method for preparing the catalyst for hydrochlorination of acetylene based on the hollow foam material with porous pipe walls according to claim 9, characterized in that the feed liquid in the method for preparing the catalyst is one or more than two of the following materials: the drying method in the preparation method of the catalyst is one or more than two of the following methods: heating for drying, freeze drying, and supercritical drying.

11. Use of the catalyst for acetylene hydrochlorination based on porous tube wall hollow foam material according to one of claims 1 to 8, characterized in that the catalyst is used for acetylene hydrochlorination in one or more of the following modes:

12. The application of the catalyst for acetylene hydrochlorination based on the porous pipe wall hollow foam material is characterized in that the catalyst utilizes multi-scale pores of the porous pipe wall hollow foam material to regulate and control the dipping, loading or drying process of a catalytic active component, so that the active component is promoted to reach controllable high dispersity, and the catalytic activity, selectivity and service life of the catalyst for acetylene hydrochlorination are further improved;