A high-efficiency catalytic reactor based on metal sintered membrane

Abstract

The present invention is a high-efficiency catalytic reactor based on a metal sintered membrane, comprising a reactor body, wherein one or more layers of metal sintered membranes are arranged in layers in the reactor body, a heat exchanger is arranged in the internal space of the reactor body between two adjacent layers of sintered membranes, a liquid phase feed pipe is arranged at the bottom of the reactor body, a discharge port is arranged at the top of the reactor body, and a gas phase feed port is arranged on the side wall of the reactor body between two adjacent layers of sintered membranes; the surface of the metal sintered membrane and the inside of the pores of the metal sintered membrane are bonded with active components required for the reaction. The catalytic reactor has a simple structure, is easy to manufacture, and can be used for gas-liquid-solid three-phase reaction.

Description

Technical Field

[0001] The invention relates to the technical field of catalytic reactors, and in particular to a high-efficiency catalytic reactor which utilizes a metal sintered membrane as a catalytic bed layer to carry out a gas-liquid-solid three-phase reaction. Background Art

[0002] Gas-liquid-solid three-phase catalytic reaction is a common reaction process in chemical production, generally referring to a reaction process in which the reactants are gas-liquid two-phase and the catalyst is a solid phase. The reactor used for gas-liquid-solid three-phase reaction mainly includes a fixed bed reactor (such as a trickle bed reactor, a bubble tower reactor) with a solid fixed type and a stirred slurry bed reactor with a solid suspension type. The slurry bed reactor strengthens the mass transfer and heat transfer process between the gas-liquid-solid three-phase by reducing the catalyst particle size and violently stirring. It is widely used in industry, but there are problems such as difficulty in catalyst separation, large loss, large investment in separation equipment, and complex operation. In a fixed bed three-phase reactor, the catalyst is fixed in the reactor in the form of a bed, and there is no problem of catalyst separation in the reaction process, but the gas-liquid mass transfer resistance is large, and the gas-liquid is unevenly distributed inside the bed, which easily produces channel flow and wall flow, resulting in poor reactor operating performance and low reaction efficiency. Therefore, a gas and liquid distribution device is usually required in a fixed bed three-phase reactor to solve the problem of uniform distribution of gas and liquid. For example, patent US4708852 introduces a trickle bed reactor, which includes an inlet pre-distributor, a gas-liquid distributor, a porcelain ball bed, and a catalyst bed; its gas-liquid distributor adopts an open-hole corrugated plate structure, and the gas and liquid are in contact below the corrugated plate, which improves the uniformity of gas-liquid distribution. CN105582857 also discloses a gas-liquid-solid three-phase reactor, which improves the gas-liquid distribution inside the reactor by installing a pre-distributor, a gas-liquid distribution plate, and an annular baffle and a multi-layer gas-liquid distribution plate on the inner wall of the reactor. Although the trickle bed reactor described in the above document improves the gas-liquid distribution problem to a certain extent, the reactor structure is relatively complex, the reaction is still greatly affected by the gas-liquid mass transfer resistance, and the reaction efficiency is difficult to further improve. Summary of the invention

[0003] In view of the deficiencies in the prior art, the technical problem to be solved by the present invention is to provide a high-efficiency catalytic reactor based on a metal sintered membrane which has a simple structure, is easy to manufacture, and can be used for gas-liquid-solid three-phase reaction.

[0004] The technical solution adopted by the present invention to solve the technical problem is:

[0005] A high-efficiency catalytic reactor based on a metal sintered membrane comprises a reactor body, characterized in that one or more layers of plate-shaped metal sintered membranes are arranged in upper and lower layers in the reactor body, a heat exchanger is arranged in the internal space of the reactor body between two adjacent layers of sintered membranes, a liquid-phase feed pipe is arranged at the bottom of the reactor body, a discharge port is arranged at the top of the reactor body, and a gas-phase feed port is arranged on the side wall of the reactor body between two adjacent layers of sintered membranes; active components required for the reaction are bonded to the surface of the metal sintered membrane and the inside of the pores of the metal sintered membrane.

[0006] The active components required for the reaction to be bonded on the surface of the metal sintered film and inside the pores of the metal sintered film need to be activated through pretreatment.

[0007] The thickness of the metal sintered membrane plate is 1 to 1000 mm, the spacing between the sintered membrane plates is 2 to 50 mm, the pore size is 5 to 200 microns, preferably 20 to 100 microns, and the porosity is 10 to 50%.

[0008] The active components required for the bonding reaction on the surface of the metal sintered film and inside the pores of the metal sintered film need to be activated through pretreatment. The pretreatment activation process requires that the active components can enter the pores of the metal sintered film and react with the surface groups of the metal sintered film to produce bonding.

[0009] The pretreatment activation process is:

[0010] In the first step, the reactor and the piping system are replaced with nitrogen, and the reactor is heated to 80-200°C by passing pressurized steam through the heat exchange tubes;

[0011] In the second step, the active component treatment liquid in the storage tank is injected into the reactor in the first step, and the liquid space velocity of the treatment liquid is 1 to 10 h -1 After the reactor is continuously treated for 1 to 2 hours, a reactor loaded with active components after activation is obtained.

[0012] In specific implementation, the high-efficiency catalytic reactor based on metal sintered membrane can be used for gas-liquid-solid three-phase reaction after activation, such as the method for hydrogenation reaction as follows:

[0013] The high-efficiency catalytic reactor based on metal sintered membrane is replaced with nitrogen and activated. Then the liquid material preheated to 40-200°C is continuously added into the reactor. Hydrogen enters the reactor through the hydrogen inlet in one section or in sections. The liquid space velocity of the liquid phase material is 10-500h -1 The total feed space velocity of hydrogen is 3000~50000h -1 , the pressure in the reactor is 0.15-3.0 MPa; after the gas-liquid mixture coming out of the reactor is condensed by the condenser, the hydrogen returns to the reactor, and the reaction product is obtained in the liquid phase.

[0014] Another technical solution of the present invention is:

[0015] A high-efficiency catalytic reactor based on a metal sintered membrane adopts a shell-and-tube structure, comprising a reactor body and a plurality of shells and tubes, characterized in that a cylindrical metal sintered membrane is embedded in the shell and tubes, a heat exchange medium is passed between the shell and tubes to provide or remove reaction heat; the gap between the cylindrical metal sintered membrane and the shell and tube is closed, the diameter of the cylindrical metal sintered membrane is consistent with the inner diameter of the shell and tube, the reaction material only passes through the space where the metal sintered membrane is located, and does not pass through the gap between the two; the active components required for the reaction are bonded to the surface of the metal sintered membrane and the inside of the pores.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] The present invention provides a metal sintered membrane in the reactor, utilizes the interaction between active components and metal materials under hydrothermal conditions, loads active components onto the surface and pores of sintered metal porous materials, forms a novel reactor with catalytic effect, and the reaction can be carried out on the large specific surface provided by the sintered metal porous materials, and the reaction activity is high; there is no need to provide a gas-liquid distribution device in the reactor, and the strong mixing between the fluids formed by the gas-liquid two-phase fluid in the pores of the porous material can effectively avoid the problem of uneven gas-liquid distribution such as channel flow and wall flow, strengthens the gas-liquid mass transfer in the reaction process, enhances the heat transfer, and significantly improves the reaction efficiency. The reactor is used for nitrobenzene hydrogenation and dinitrobenzene hydrogenation reactions, and the space-time yield per unit time and unit effective bed volume can reach more than 15kg / hL.

[0018] The reactor of the present invention realizes uniform distribution of gas and liquid in the bed layer, reduces the mass transfer resistance of gas and liquid on the catalyst surface, has a simple structure, is easy to manufacture, has low cost and high efficiency, and can be used in various gas-liquid-solid three-phase reactions.

[0019] In the pretreatment activation method of the present invention, the liquid space velocity of the treatment liquid is set to 1 to 10 h -1 , select a lower airspeed. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is a schematic structural diagram of a high-efficiency catalytic reactor based on a metal sintered plate according to the present invention.

[0021] Figure 2 It is a structural schematic diagram of another embodiment of the high-efficiency catalytic reactor of the present invention.

[0022] Figure 3 It is a schematic cross-sectional view of the shell-and-tube reactor of the present invention.

[0023] Figure 4 Schematic diagram of the cross-sectional structure of a cylindrical metal sintered membrane embedded in a tube array.

[0024] In the figure, 1 is a metal sintered membrane, 2 is a reactor body, 3 is a heat exchanger, 4 is a discharge port, 5 is a liquid phase feed pipe, 6 is a gas phase feed port, 7 is a feed port, 8 is a cylindrical metal sintered membrane, and 9 is a tube array. DETAILED DESCRIPTION

[0025] The present invention is further explained below in conjunction with the accompanying drawings of the embodiments, but this is not intended to limit the scope of protection of the present application.

[0026] The present invention discloses a high-efficiency catalytic reactor based on a metal sintered membrane, comprising a reactor body 2, in which one or more layers of metal sintered membranes 1 are arranged in upper and lower layers, the edge of the metal sintered membrane is fixed to the inner wall of the reactor body, a heat exchanger 3 is arranged in the inner space of the reactor body between two adjacent layers of sintered plates, a liquid phase feed pipe 5 is arranged at the bottom of the reactor body, a discharge port 4 is arranged at the top of the reactor body, and gas phase feed ports 6 are arranged on the side walls of the reactor body between two adjacent layers of sintered membranes; the surface of the metal sintered membrane and the inside of the pores of the metal sintered membrane are bonded with active components required for the reaction.

[0027] The use process of the reactor of the present invention is as follows: the reaction liquid is continuously fed from the feed pipe at the bottom of the reactor, and hydrogen (gas phase feed) is fed in sections between each layer of metal sintered plates, or it can be fed in one section. A heat exchange tube of a certain length is added between the two layers of metal sintered membranes to provide or remove reaction heat through a heat exchange medium to maintain the reaction temperature. The geometric dimensions of the reactor, the effective sintered membrane volume (number of layers, thickness) and the length of the heat exchange tube are determined by the production capacity and the total heat release of the reaction.

[0028] The reactor equipped with metal sintered membrane needs to load the active components required for the reaction onto the surface and inside the pores of the metal sintered membrane by pretreatment activation. The pretreatment activation process requires that the active components can enter the pores of the metal sintered membrane and react with the surface groups of the metal sintered membrane to form a bond. The active components are not easy to fall off after bonding.

[0029] The thickness of the metal sintered membrane plate is 1 to 1000 mm, the spacing between the sintered membrane plates is 2 to 50 mm, the pore size is 5 to 200 microns, preferably 20 to 100 microns, and the porosity is 10 to 50%.

[0030] Metal sintered membrane is a sintered metal porous material, which is a kind of material with uniform pore structure prepared by pressing and high-temperature diffusion sintering based on metal powder, metal mesh or metal fiber. It not only inherits the excellent characteristics of the base metal material, but also shows more advantages due to the existence of internal pores, such as uniform pore size distribution, controllable porosity and permeability coefficient, large specific surface area, etc. The present application can customize metal sintered membranes with specific pore size, specific porosity size, specific geometry and size according to the reaction needs when used.

[0031] The pretreatment activation process of the above reactor is:

[0032] In the first step, the reactor and the piping system are replaced with nitrogen, and the reactor is heated to 80-200°C by passing pressurized steam through the heat exchange tubes;

[0033] In the second step, the active component treatment liquid in the storage tank is injected into the reactor in the first step, and the liquid space velocity of the treatment liquid is 1 to 10 h -1 After the reactor is continuously treated for 1 to 5 hours, a reactor loaded with active components after activation is obtained. The pretreatment activation process can adjust the treatment liquid used for activation according to the actual reaction needs, and can be carried out in sequence with the reaction process, or the reactor can be pretreated and activated in advance and used directly when the reaction needs it.

[0034] In specific implementation, the high-efficiency catalytic reactor based on metal sintered membrane can be used for gas-liquid-solid three-phase reaction after activation, such as the method for hydrogenation reaction as follows:

[0035] The high-efficiency catalytic reactor based on metal sintered membrane is replaced with nitrogen after activation, and then the liquid material preheated to 40-200°C is continuously added into the reactor. Hydrogen enters the reactor through the hydrogen inlet in one section or in sections. The liquid space velocity of the liquid phase material is 10-500h -1 The total feed space velocity of hydrogen is 3000~50000h -1 , the pressure in the reactor is 0.15-3.0 MPa; after the gas-liquid mixture coming out of the reactor is condensed by the condenser, the hydrogen returns to the reactor, and the reaction product is obtained in the liquid phase.

[0036] The reactor body and the metal sintered membrane materials described in the present invention are metal materials such as Hastelloy, carbon steel, stainless steel, titanium or zirconium. Of course, the reactor body in the present application can also be a polymer material such as glass fiber reinforced plastic that does not react with the treatment liquid. In this case, after pretreatment and activation, the active components are only bonded inside and on the surface of the metal sintered membrane material.

[0037] The treatment liquid in the second step is a mixed liquid prepared by mixing metal salt and water, and the concentration of the metal salt calculated as the active component is 0.1-10 ppm; the metal salt of the active component is a metal salt of the active component that can bond with the metal sintering membrane material under hydrothermal conditions, such as one or more salts of platinum, palladium, rhodium, ruthenium, gold, silver, copper, cerium or nickel; the mixed liquid is relatively dilute and can enter the pores of the metal sintering plate.

[0038] Example 1

[0039] The present embodiment is a high-efficiency catalytic reactor based on a metal sintered membrane, which is used for the reaction process of producing aniline by hydrogenation of nitrobenzene. The inner diameter of the reactor is 200 mm, and the materials of the reactor and the sintered membrane are 316L stainless steel. The pore size of the sintered membrane is 100 microns, the porosity is 36%, the thickness of the sintered membrane plate is 3 mm, the number of sintered membrane plates is 10, the plate spacing is 3 mm, and the effective volume of the sintered membrane plate is 0.94 L.

[0040] The reactor activation and reaction process includes the following steps:

[0041] In the first step, the reactor and the piping system with 10 layers of sintered membrane plates installed in the upper and lower positions are replaced with nitrogen, and the reactor is heated to 80°C by passing pressurized steam through the heat exchange tubes;

[0042] In the second step, the chloroplatinic acid aqueous solution with a Pt concentration of 5 ppm in the storage tank is injected into the reactor in the first step, and the liquid space velocity of the treated liquid is 1 h -1 After the reactor is continuously treated for 2 hours, an activated reactor is obtained, and the inner wall of the activated reactor body and the surface and internal pores of the metal sintered membrane plate are loaded with Pt active components;

[0043] In the third step, the reactor after loading the active components in the second step is replaced with nitrogen, and then the raw material nitrobenzene preheated to 150°C is continuously injected into the reactor, and hydrogen is introduced in stages from the hydrogen inlet of the reactor. The liquid space velocity of nitrobenzene is 21.3h -1 (nitrobenzene feed rate 20L / h), hydrogen feed space velocity 17000h -1 , equivalent to the hydrogen input amount of each membrane plate is 1780L / h, and the pressure of the reactor is 0.2MPa; after the gas-liquid mixture coming out of the reactor is condensed by the condenser, the hydrogen returns to the reactor, and the reaction product is obtained in the liquid phase. The aniline yield is 99.8%, which is equivalent to the space-time yield per unit time and unit effective bed volume of 19.3kg / hL.

[0044] Example 2

[0045] The present embodiment is a high-efficiency catalytic reactor based on a metal sintered membrane. The inner diameter of the reactor is 200 mm. The reactor wall and the sintered membrane material are made of titanium. The pore size of the sintered membrane plate is 50 microns, the porosity is 31%, the thickness of the sintered membrane plate is 2 mm, the number of sintered membrane plate layers is 10, the plate spacing is 5 mm, and the effective volume of the sintered membrane plate is 0.94 L.

[0046] For the reaction process of hydrogenating dinitrotoluene to produce toluenediamine, the reactor activation and reaction process include the following steps:

[0047] In the first step, the reactor and the piping system are replaced with nitrogen, and the reactor is heated to 200°C by passing pressurized steam through the heat exchange tubes;

[0048] In the second step, the rhodium chloride aqueous solution with a Rh concentration of 5 ppm in the storage tank is injected into the reactor in the first step, and the liquid space velocity of the treated liquid is 10h -1 After the reactor was continuously treated for 2 hours, a reactor loaded with Rh active components was obtained.

[0049] In the third step, the reactor after loading the active components in the second step is replaced with nitrogen, and then a dinitrotoluene ethanol solution (the mass concentration of dinitrotoluene is 10%) preheated to 80°C is continuously injected into the reactor, and hydrogen is introduced in stages from the hydrogen inlet of the reactor. The liquid space velocity of the liquid phase material is 500h -1 (Liquid phase feed rate 522L / h, of which the amount of dinitrotoluene is 25.2kg / h), the feed space velocity of hydrogen is 18600h -1 , equivalent to the hydrogen input amount of each membrane plate is 1750L / h, the pressure of the reactor is 3.0MPa; the gas-liquid mixture coming out of the reactor is condensed by the condenser, the hydrogen returns to the reactor, and the reaction product is obtained in the liquid phase. The yield of toluenediamine is 99.6%, which is equivalent to the space-time yield per unit time and unit effective bed volume of 17.9kg / hL.

[0050] Example 3

[0051] The present embodiment is a high-efficiency catalytic reactor based on a metal sintered membrane. The structure of the reactor and the sintered membrane material are the same as those in Example 1. The treatment liquid in the pretreatment activation process is a mixed aqueous solution of palladium chloride and copper chloride with a Pd concentration of 0.1 ppm and a Cu concentration of 5 ppm. Other pretreatment conditions are the same as those in Example 2. After the reactor is continuously treated for 2 hours, an activated reactor is obtained. The inner wall of the activated reactor body and the surface and internal pores of the metal sintered membrane plate are loaded with Pd-Cu bimetallic active components. The reactor is used for the reaction of furfural hydrogenation to generate furfuryl alcohol.

[0052] Example 4

[0053] This embodiment is a high-efficiency catalytic reactor based on a metal sintered membrane. Except that the material of the reactor and the sintered membrane is zirconium, other structures and pretreatment methods are the same as those in Example 1. After the reactor is continuously treated for 2 hours, an activated reactor is obtained. The inner wall of the activated reactor body and the surface of the metal sintered membrane are loaded with Pt active components. The reactor is used for hydrogenating nitrobenzene to prepare p-aminophenol in an acidic medium.

[0054] Example 5

[0055] This embodiment is a high-efficiency catalytic reactor based on a metal sintered membrane. The inner diameter of the reactor is 200 mm. The reactor and the sintered membrane are made of 316L stainless steel. The thickness of the metal sintered membrane is 1000 mm. The number of sintered membrane layers is single, and the effective volume of the sintered membrane is 3.14 L. The treatment liquid in the pretreatment activation process is a mixed aqueous solution of palladium chloride and cerium nitrate with a Pd concentration of 3 ppm and a Ce concentration of 5 ppm. The treatment temperature is 200 ° C, and the liquid space velocity of the treatment liquid is 1 h -1 After the reactor is continuously treated for 2 hours, an activated reactor is obtained. The inner wall of the activated reactor body and the surface and internal pores of the metal sintered plate are loaded with Pd-Ce bimetallic active components. The reactor is used for liquid-phase selective hydrogenation of C3 fraction to remove methylacetylene and propadiene.

[0056] Example 6

[0057] This embodiment is a high-efficiency catalytic reactor based on a metal sintered membrane, which adopts a shell-and-tube structure (see Figure 2-4 ), comprising a reactor body 2 and a plurality of tube arrays 9, wherein two upper and lower tube sheets for vertically mounting the plurality of tube arrays are arranged inside the reactor body, the edges of the plurality of tube arrays are sealed and connected to the two tube sheets, a cylindrical metal sintered membrane 8 is embedded in the tube array, a heat exchange medium is introduced between the tube arrays to provide or remove reaction heat; the gap between the metal sintered membrane and the tube array is closed, the diameter of the metal sintered membrane is consistent with the inner diameter of the tube array, and the reaction material only passes through the space of the metal sintered membrane, and does not pass through the gap between the two; a feed inlet 7 is arranged at the bottom of the reactor body, and the reaction liquid and the gas are mixed and enter the reactor body through the feed inlet, and a discharge port 4 is arranged at the top of the reactor body;

[0058] The reactor needs to load and bond the active components required for the reaction to the surface of the metal sintered membrane and the inside of the pores through pretreatment activation.

[0059] Example 7

[0060] This embodiment is a high-efficiency catalytic reactor based on a metal sintered membrane. The reactor is a shell-and-tube type, and the structure is the same as that of Embodiment 6. The pretreatment activation process is as follows:

[0061] In the first step, the reactor and the piping system are replaced with nitrogen, and the reactor temperature is raised to 200°C by passing pressurized steam between the pipes;

[0062] In the second step, a mixed aqueous solution of ruthenium chloride and nickel nitrate with a Ru concentration of 3 ppm and a Ni concentration of 10 ppm in a storage tank is injected into the tube array of the first step reactor equipped with a cylindrical sintered membrane. The liquid space velocity of the treated liquid is 10 h -1 After the reactor is continuously treated for 2 hours, an activated reactor is obtained. The surface and internal pores of the metal sintered film of the activated reactor are loaded with Ru-Ni bimetallic active components. The reactor is used in the reaction process of phenol hydrogenation to cyclohexanol.

[0063] Any matters not described in the present invention are applicable to the prior art.

Claims

1. A high-efficiency catalytic reactor based on a metal sintered membrane, comprising a reactor body, characterized in that: One or more layers of metal sintered membranes are arranged in layers in the reactor body, a heat exchanger is arranged in the internal space of the reactor body between two adjacent layers of sintered membranes, a liquid phase feed pipe is arranged at the bottom of the reactor body, a discharge port is arranged at the top of the reactor body, and a gas phase feed port is arranged on the side wall of the reactor body between two adjacent layers of sintered membranes; the surface of the metal sintered membrane and the inside of the pores of the metal sintered membrane are bonded with active components required for the reaction; The active components required for the bonding reaction on the surface of the metal sintered film and inside the pores of the metal sintered film need to be activated by pretreatment. The pretreatment activation process requires that the active components can enter the pores of the metal sintered film and react with the surface groups of the metal sintered film to form a bonding reaction. The pretreatment activation process is: In the first step, the reactor and the piping system are replaced with nitrogen, and the reactor is heated to 80-200°C by passing pressurized steam through the heat exchange tubes; In the second step, the active component treatment liquid in the storage tank is injected into the reactor in the first step, and the liquid space velocity of the treatment liquid is 1 to 10 h -1 After the reactor is continuously treated for 1 to 2 hours, a reactor loaded with active components after activation is obtained; The thickness of the metal sintered membrane plate is 1 to 1000 mm, the spacing between the metal sintered membrane plates is 2 to 50 mm, the pore size is 5 to 200 microns, and the porosity is 10 to 50%.

2. The catalytic reactor according to claim 1, characterized in that: The pore size of the metal sintered membrane plate is 20 to 100 microns.

3. A high-efficiency catalytic reactor based on metal sintered membrane, adopting a tube-in-tube structure, comprising a reactor body and a plurality of tubes, characterized in that: A cylindrical metal sintered membrane is embedded in the tube array, and a heat exchange medium is passed between the tube arrays to provide or remove reaction heat; the gap between the metal sintered membrane and the tube array is closed, the diameter of the metal sintered membrane is consistent with the inner diameter of the tube array, and the reaction material only passes through the space where the metal sintered membrane is located, and does not pass through the gap between the two; the surface of the metal sintered membrane and the inside of the pores are bonded with active components required for the reaction; The active components required for the bonding reaction on the surface of the metal sintered film and inside the pores of the metal sintered film need to be activated by pretreatment. The pretreatment activation process requires that the active components can enter the pores of the metal sintered film and react with the surface groups of the metal sintered film to form a bonding reaction. The pretreatment activation process is: In the first step, the reactor and the piping system are replaced with nitrogen, and the reactor is heated to 80-200°C by passing pressurized steam through the heat exchange tubes; In the second step, the active component treatment liquid in the storage tank is injected into the reactor in the first step, and the liquid space velocity of the treatment liquid is 1 to 10 h -1 After the reactor is continuously treated for 1 to 2 hours, a reactor loaded with active components after activation is obtained; The pore size of the metal sintered membrane is 5 to 200 microns, and the porosity is 10 to 50%.

4. The catalytic reactor according to claim 1 or 3, characterized in that: The treatment liquid in the second step is a mixed liquid prepared by mixing metal salt and water, and the concentration of the metal salt calculated as active component is 0.1-10 ppm; the metal salt is a metal salt of active components that can bond with the metal sintering membrane material under hydrothermal conditions.

5. The catalytic reactor according to claim 4, characterized in that: The metal salt of the active component is one or more salts of platinum, palladium, rhodium, ruthenium, gold, silver, copper, cerium or nickel.

6. The catalytic reactor according to claim 5, characterized in that: The catalytic reactor is used for gas-liquid-solid three-phase reaction after activation.

7. A method for using the catalytic reactor according to any one of claims 1 to 6 for a gas-liquid-solid three-phase hydrogenation reaction, characterized in that: The catalytic reactor is used in a gas-liquid-solid three-phase hydrogenation reaction after activation, and the specific method is as follows: The high-efficiency catalytic reactor based on metal sintered membrane is replaced with nitrogen and then the liquid material preheated to 40-200°C is continuously added into the reactor. Hydrogen enters the reactor through the hydrogen inlet in one section or in sections. The liquid space velocity of the liquid phase material is 10-500h -1 The total feed space velocity of hydrogen is 3000~50000h -1 The pressure in the reactor is 0.15 to 3.0 MPa; the gas-liquid mixture coming out of the reactor is condensed by a condenser, the hydrogen returns to the reactor, and the reaction product is obtained in the liquid phase.

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