CN212215463U - Catalytic reactor based on metal sintering membrane - Google Patents
Catalytic reactor based on metal sintering membrane Download PDFInfo
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- CN212215463U CN212215463U CN201922122386.4U CN201922122386U CN212215463U CN 212215463 U CN212215463 U CN 212215463U CN 201922122386 U CN201922122386 U CN 201922122386U CN 212215463 U CN212215463 U CN 212215463U
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 95
- 239000002184 metal Substances 0.000 title claims abstract description 95
- 238000005245 sintering Methods 0.000 title claims abstract description 80
- 239000012528 membrane Substances 0.000 title claims abstract description 51
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000011148 porous material Substances 0.000 claims abstract description 31
- 239000012071 phase Substances 0.000 claims abstract description 18
- 239000007791 liquid phase Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000007792 gaseous phase Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000001994 activation Methods 0.000 description 18
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 12
- 238000009826 distribution Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 230000004913 activation Effects 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000012530 fluid Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000011344 liquid material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002668 Pd-Cu Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910002787 Ru-Ni Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910002793 Ru–Ni Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- -1 dinitrotoluene ethanol Chemical compound 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The utility model relates to a catalytic reactor based on metal sintering membrane, including the reactor body, one deck or multilayer metal sintering membrane has been arranged according to upper and lower layering in the reactor body, and the reactor body inner space between two adjacent layers of sintering membrane sets up the heat exchanger, and reactor body bottom sets up the liquid phase inlet pipe, and reactor body top sets up the discharge gate, all is provided with the gaseous phase feed inlet on the reactor body lateral wall between two adjacent layers of sintering membrane; active components required by reaction are bonded on the surface of the metal sintering film and in the pore channel of the metal sintering film. The catalytic reactor has simple structure, is easy to manufacture and can be used for gas-liquid-solid three-phase reaction.
Description
Technical Field
The utility model relates to a catalytic reactor technical field, concretely relates to utilize metal sintering membrane to carry out gas-liquid-solid three-phase reaction's catalytic reactor as catalytic bed.
Background
The gas-liquid-solid three-phase catalytic reaction is a common reaction process in chemical production, and generally refers to a reaction process in which reactants are in a gas-liquid two-phase state, and a catalyst is in a solid phase. The reactor for gas-liquid-solid three-phase reaction mainly comprises a solid fixed-bed type reactor (such as a trickle-bed reactor and a bubble column reactor) and a solid suspension type stirred slurry bed reactor. The slurry bed reactor strengthens the mass transfer and heat transfer process between the gas phase and the liquid phase by reducing the granularity of the catalyst and stirring vigorously, and has wide industrial application, but has the problems of difficult catalyst separation, large loss, large investment on separation equipment and complex operation. The fixed bed type three-phase reactor has the advantages that the catalyst is fixed in the reactor in a bed layer mode, the separation problem of the catalyst does not exist in the reaction process, but the gas-liquid mass transfer resistance is large, the gas-liquid is unevenly distributed in the bed layer, and channeling and wall flow are easily generated, so that the operation performance of the reactor is poor, and the reaction efficiency is low. Therefore, a gas and liquid distribution device is usually required in the three-phase reactor of the fixed bed type to solve the problem of uniform distribution of gas and liquid. For example, US4708852 describes a trickle bed reactor comprising an inlet predistributor, a gas-liquid distributor, a bed of ceramic balls, a bed of catalyst; its gas-liquid distributor adopts the trompil ripple plate structure, and gas and liquid contact in the buckled plate below, have improved the homogeneity of gas-liquid distribution. CN105582857 also discloses a gas-liquid-solid three-phase reactor, which improves the gas-liquid distribution inside the reactor through a pre-distributor, a gas-liquid distribution disk, an annular baffle plate and a multilayer gas-liquid distribution disk which are arranged in the reactor, and the like. Although the trickle bed reactor described in the above-mentioned document improves the gas-liquid distribution problem to some 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.
SUMMERY OF THE UTILITY MODEL
The technical problem to be solved by the utility model is to provide a simple structure, easily make, can be used for the solid three-phase reaction of gas-liquid based on metal sintering membrane's catalytic reactor.
The utility model provides a technical scheme that technical problem adopted is:
a high-efficiency catalytic reactor based on metal sintering films comprises a reactor body and is characterized in that one or more layers of plate-shaped metal sintering films are arranged in the reactor body in a layered mode from top to bottom, a heat exchanger is arranged in the inner space of the reactor body between two adjacent layers of sintering films, a liquid-phase feeding pipe is arranged at the bottom of the reactor body, a discharging hole is formed in the top of the reactor body, and gas-phase feeding holes are formed in the side walls of the reactor body between two adjacent layers of sintering films; active components required by reaction are bonded on the surface of the metal sintering film and in the pore channel of the metal sintering plate.
The active components required by the reaction are bonded on the surface of the metal sintering film and the inside of the pore channels of the metal sintering film by means of pretreatment and activation.
The thickness of the metal sintered membrane plate is 1-1000 mm, the distance between the sintered membrane plates is 2-50 mm, the pore diameter is 5-200 microns, the preferred pore diameter is 20-100 microns, and the porosity is 10-50%.
The active components required by the reaction on the surface of the metal sintering film and the inside of the pore channel of the metal sintering film are bonded in a pretreatment activation mode, and the pretreatment activation process requires that the active components can enter the pore channel of the metal sintering film and react with the surface groups of the metal sintering film to generate bonding action. This pre-treatment activation process can be directly achieved using existing techniques. The following activation process may also be employed:
the pretreatment activation process comprises the following steps:
replacing a reactor and a pipeline system with nitrogen, and heating the reactor to 80-200 ℃ by introducing pressurized steam into a heat exchange tube;
secondly, pumping the active component treating fluid configured in the storage tank into the reactor in the first step, wherein the liquid airspeed of the treating fluid is 1-10 h-1And continuously treating for 1-2 h by using the reactor to obtain the activated reactor loaded with the active components.
In specific implementation, the high-efficiency catalytic reactor based on the metal sintered membrane can be used for gas-liquid-solid three-phase reaction after being activated, and for example, the method for hydrogenation reaction comprises the following steps:
replacing the activated high-efficiency catalytic reactor based on the metal sintered membrane with nitrogen, continuously adding a liquid material preheated to 40-200 ℃ into the reactor, introducing hydrogen into the reactor from a hydrogen inlet of the reactor in a one-section or sectional manner, and allowing the liquid air speed of the liquid material to be 10-500 h-1The total feeding airspeed of hydrogen is 3000-50000 h-1The pressure in the reactor is 0.15-3.0 MPa; and condensing the gas-liquid mixture from the reactor through a condenser, returning the hydrogen to the reactor, and obtaining a reaction product in a liquid phase.
The other technical scheme of the utility model is:
a high-efficiency catalytic reactor based on a metal sintering film adopts a tubular structure and comprises a reactor body and a plurality of tubes, and is characterized in that cylindrical metal sintering films are embedded in the tubes, and heat exchange media are introduced among the tubes to provide or remove reaction heat; the gap between the cylindrical metal sintering film and the tube array is closed, the diameter of the cylindrical metal sintering film is consistent with the inner diameter of the tube array, and the reaction materials only pass through the space where the metal sintering film is located, but the gap between the metal sintering film and the tube array is not left; active components required by reaction are bonded on the surface of the metal sintering film and in the pore channel.
Compared with the prior art, the beneficial effects of the utility model are that:
the utility model discloses set up the metal sintering membrane in the reactor, utilize active ingredient and metal material under hydrothermal condition's interact, load active ingredient to sintering metal porous material surface and pore in, form the novel reactor with catalytic action, the reaction can be gone on the big specific surface that sintering metal porous material provided, the reactivity is high; the gas-liquid distribution device is not needed to be arranged in the reactor, and the strong mixing of the gas-liquid two-phase fluid in the fluid formed in the pores of the porous material is utilized, so that the problem of uneven gas-liquid distribution such as channel wall flow and the like can be effectively avoided, the gas-liquid mass transfer in the reaction process is enhanced, the heat transfer is enhanced, and the reaction efficiency is obviously improved. Nitrobenzene hydrogenation and dinitrobenzene hydrogenation are carried out on the reactor, and the space-time yield per unit time and unit effective bed layer volume can reach more than 15 kg/h.L.
The utility model discloses the reactor has realized the evenly distributed of gas-liquid in the bed, has reduced the mass transfer resistance of gas-liquid on the catalyst surface, and simple structure easily makes, and is with low costs, and is efficient, can be arranged in various gas-liquid solid three-phase reactions.
Drawings
Fig. 1 is a schematic structural diagram of a high-efficiency catalytic reactor based on a metal sintering plate.
Fig. 2 is a schematic structural diagram of another embodiment of the high-efficiency catalytic reactor of the present invention.
FIG. 3 is a schematic cross-sectional view of the shell and tube reactor of the present invention.
Fig. 4 is a schematic cross-sectional structure of a cylindrical metal sintered film embedded in a tube array.
In the figure, 1 is a metal sintered film, 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 film, and 9 is a tube.
Detailed Description
The invention is further explained with reference to the drawings, which are examples, but not to be construed as limiting the scope of the invention.
The utility model discloses high-efficient catalytic reactor based on metal sintering membrane, including reactor body 2, one deck or multilayer metal sintering membrane 1 has been arranged according to upper and lower layering in reactor body, and the edge of metal sintering membrane is fixed with the inner wall of reactor body, sets up heat exchanger 3 in the reactor body inner space between adjacent two-layer sintering board, and reactor body bottom sets up liquid phase inlet pipe 5, and reactor body top sets up discharge gate 4, all is provided with gaseous phase feed inlet 6 on the reactor body lateral wall between adjacent two-layer sintering membrane; active components required by reaction are bonded on the surface of the metal sintering film and in the pore channel of the metal sintering film.
The utility model discloses the use of reactor is: the reaction liquid is continuously fed from a feeding pipe at the bottom of the reactor, and hydrogen (gas phase feeding) enters from each layer of metal sintering plate in a subsection mode or enters from one section. A heat exchange tube with a certain length is added between the two metal sintering films to provide or remove reaction heat through a heat exchange medium and maintain the reaction temperature. The geometry of the reactor, the effective sintered plate volume (number of layers, thickness) and the length of the heat exchange tubes are determined by the production capacity and the total exotherm of the reaction.
The reactor provided with the sintered metal membrane needs to load active components required by the reaction on the surface of the metal sintered membrane and in the pore canal by means of pretreatment and activation. The pretreatment activation process requires that active components can enter the pore channels of the metal sintering film and can react with surface groups of the metal sintering film to generate bonding effect, and the active components are not easy to fall off after bonding.
The thickness of the metal sintering film is 1-1000 mm, the distance between sintering film plates is 2-50 mm, the aperture is 5-200 microns, preferably 20-100 microns, and the porosity is 10-50%.
The sintered metal membrane is a sintered metal porous material, which is a kind of material containing uniform pore structure prepared by pressing and high-temperature diffusion sintering processes based on metal powder, metal wire mesh or metal fiber, not only inherits the excellent characteristics of the base metal material, but also exhibits 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 metal sintered membrane with specific pore size, specific porosity size and specific geometric shape and size can be customized according to reaction requirements when the metal sintered membrane is used.
The pretreatment activation process of the reactor comprises the following steps:
replacing a reactor and a pipeline system with nitrogen, and heating the reactor to 80-200 ℃ by introducing pressurized steam into a heat exchange tube;
secondly, pumping the active component treating fluid configured in the storage tank into the reactor in the first step, wherein the liquid airspeed of the treating fluid is 1-10 h-1And continuously treating the reactor for 1-5 hours to obtain the activated reactor loaded with the active components. The pretreatment and activation process can adjust the treatment liquid used for activation according to the actual reaction requirement, can be selected to be carried out in sequence with the reaction process, and can also be carried out on the reactor in advanceAnd (4) pretreating and activating, and directly taking the mixture for use when the reaction is needed.
In specific implementation, the high-efficiency catalytic reactor based on the metal sintered membrane can be used for gas-liquid-solid three-phase reaction after being activated, and for example, the method for hydrogenation reaction comprises the following steps:
replacing the activated high-efficiency catalytic reactor based on the metal sintered membrane with nitrogen, continuously adding a liquid material preheated to 40-200 ℃ into the reactor, introducing hydrogen into the reactor from a hydrogen inlet of the reactor in a one-section or sectional manner, wherein the liquid airspeed of the liquid material is 10-500 h-1The total feeding airspeed of hydrogen is 3000-50000 h-1The pressure in the reactor is 0.15-3.0 MPa; and condensing the gas-liquid mixture from the reactor through a condenser, returning the hydrogen to the reactor, and obtaining a reaction product in a liquid phase.
The reactor body and the metal sintering membrane material of the utility model are made of metal materials such as Hastelloy, carbon steel, stainless steel, titanium or zirconium. In this case, after the pretreatment activation, active components are bonded only inside and on the surface of the metal sintered membrane material.
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 by active components is 0.1-10 ppm; the metal salt of the active component is one or more of the metal salts of the active component which can be bonded with the metal sintering film material under hydrothermal conditions, such as platinum, palladium, rhodium, ruthenium, gold, silver, copper, cerium or nickel salt; the mixed liquid is diluted and can enter the pore channel of the metal sintering plate.
Example 1
The embodiment is a high-efficient catalytic reactor based on metal sintering membrane for with nitrobenzene hydrogenation production aniline reaction process, reactor internal diameter 200mm, reactor and sintering membrane material are 316L stainless steel, sintering lamina membranacea aperture 100 microns, porosity 36%, lamina membranacea thickness 3mm, sintering lamina membranacea number of piles 10 layers, the inter-plate spacing 3mm, sintering lamina membranacea effective volume 0.94L.
The activation and reaction process of the reactor comprises the following steps:
firstly, replacing a reactor and a pipeline system which are provided with 10 layers of sintered membrane plates according to the upper and lower positions with nitrogen, and heating the reactor to 80 ℃ by introducing pressurized steam into a heat exchange tube;
secondly, the chloroplatinic acid aqueous solution with the Pt concentration of 5ppm which is configured in the storage tank is pumped into the reactor in the first step, and the liquid space velocity of the treatment liquid is 1h-1After the reactor is continuously treated for 2 hours, an activated reactor is obtained, and Pt active components are loaded on the inner wall of the activated reactor body and the surface and inner pore channels of the metal sintered membrane plate;
thirdly, replacing the reactor loaded with the active components in the second step with nitrogen, continuously feeding the nitrobenzene preheated to 150 ℃ into the reactor, introducing hydrogen into the reactor from a hydrogen inlet of the reactor in a segmented manner, wherein the liquid space velocity of the nitrobenzene is 21.3h-1(nitrobenzene feed rate 20L/h), and hydrogen feed space velocity of 17000h-1The hydrogen inlet amount of each layer of membrane plate is 1780L/h, and the pressure of the reactor is 0.2 MPa; after the gas-liquid mixture from the reactor is condensed by a condenser, hydrogen returns to the reactor, and the reaction product is obtained in a liquid phase, wherein the yield of aniline is 99.8 percent, and the space-time yield in unit time unit effective bed volume can be 19.3 kg/h.L.
Example 2
This embodiment is a high-efficient catalytic reactor based on metal sintering membrane, reactor internal diameter 200mm, reactor wall and sintering membrane material are the titanium material, and sintering diaphragm plate aperture is 50 microns, and the porosity 31%, sintering diaphragm plate thickness 2mm, and the number of layers of sintering diaphragm plate is 10 layers, and the board interval is 5mm, and sintering diaphragm plate effective volume is 0.94L.
The method is used for the reaction process of producing toluenediamine by hydrogenating dinitrotoluene, and the activation and reaction process of the reactor comprises the following steps:
replacing a reactor and a pipeline system with nitrogen, and heating the reactor to 200 ℃ by introducing pressurized steam into a heat exchange tube;
secondly, the rhodium chloride aqueous solution with Rh concentration of 5ppm which is arranged in the storage tank is pumped into the reactor in the first step, and the liquid space velocity of the treatment liquid is 10h-1The reactor is continuousAfter 2h of treatment, a reactor loaded with Rh active component was obtained.
Thirdly, replacing the reactor loaded with the active components in the second step with nitrogen, then continuously pumping the dinitrotoluene ethanol solution (the mass concentration of the dinitrotoluene is 10%) preheated to 80 ℃ into the reactor, introducing hydrogen into the reactor by stages from a hydrogen inlet of the reactor, and keeping the liquid air speed of liquid-phase materials at 500h-1(522L/h of liquid phase feed, 25.2kg/h of dinitrotoluene) and 18600h of hydrogen feed space velocity-1The hydrogen feeding amount of each layer of the membrane plate is 1750L/h, and the pressure of the reactor is 3.0 MPa; after the gas-liquid mixture from the reactor is condensed by a condenser, hydrogen returns to the reactor, and the liquid phase obtains a reaction product, wherein the yield of the toluenediamine is 99.6 percent, and the space-time yield which is reduced to the unit time unit effective bed volume can be 17.9 kg/h.L.
Example 3
The structure of the reactor and the sintered membrane material of the high-efficiency catalytic reactor based on the metal sintered membrane is the same as that of the reactor 1, the pretreatment and activation process treatment solution is a mixed aqueous solution of palladium chloride and copper chloride with the concentration of Pd of 0.1ppm and the concentration of Cu of 5ppm, other pretreatment conditions are the same as those of the embodiment 2, the activated reactor is obtained after the reactor is continuously treated for 2 hours, Pd-Cu bimetallic active components are loaded on the inner wall of the activated reactor body and on the surface and inner pore channels of the metal sintered membrane plate, and the reactor is used for the reaction of furfural hydrogenation to generate furfuryl alcohol.
Example 4
The reactor and the sintered membrane are made of zirconium materials, other structures and pretreatment methods are the same as those in the embodiment 1 except that the reactor and the sintered membrane are continuously treated for 2 hours to obtain an activated reactor, the activated reactor is loaded with Pt active components on the inner wall of a reactor body and the surface of the metal sintered membrane, and the activated reactor is used for preparing p-aminophenol by hydrogenating nitrobenzene in an acidic medium.
Example 5
This example is a high-efficiency catalytic reactor based on metal sintered membrane, the reactor inner diameter is 200mm, the reactor and sintered membrane are 316L stainless steel, the metal is sinteredThe thickness of a film is 1000mm, the number of layers of the sintering film is single, and the effective volume of the sintering film is 3.14L. The treatment temperature of the treatment liquid in the pretreatment activation process is 200 ℃ and the liquid space velocity of the treatment liquid is 1h, wherein the treatment liquid is a mixed aqueous solution of palladium chloride and cerium nitrate with the Pd concentration of 3ppm and the Ce concentration of 5ppm-1And continuously treating for 2 hours by using the reactor to obtain an activated reactor, wherein Pd-Ce bimetallic active components are loaded on the inner wall of the activated reactor body and on the surface and inner pore channels of the metal sintering plate, and the activated reactor is used for removing methylacetylene and propadiene by using carbon three-fraction liquid phase selective hydrogenation.
Example 6
The high-efficiency catalytic reactor based on the metal sintered membrane adopts a tube array structure (see fig. 2-4), and comprises a reactor body 2 and a plurality of tubes 9, wherein an upper tube plate and a lower tube plate for vertically installing the tubes are arranged in the reactor body, the edges of the tubes are hermetically connected with the two tube plates, cylindrical metal sintered membranes 8 are embedded in the tubes, and heat exchange media are introduced between the tubes to provide or remove reaction heat; the gap between the metal sintering film and the tube array is closed, the diameter of the metal sintering film is consistent with the inner diameter of the tube array, and the reaction materials only pass through the space of the metal sintering film without leaving the gap between the metal sintering film and the tube array; a feed inlet 7 is formed in the bottom of the reactor body, reaction liquid and gas are mixed and then enter the reactor body through the feed inlet, and a discharge outlet 4 is formed in the top of the reactor body;
the reactor needs to bond active components needed by the reaction on the surface of the metal sintered membrane and in the pore canal in a loading way through pretreatment activation.
Example 7
The high-efficiency catalytic reactor based on the metal sintering film is of a tube type and has the same structure as that of the embodiment 6, and the pretreatment and activation process comprises the following steps:
replacing a reactor and a pipeline system with nitrogen, and heating the reactor to 200 ℃ by introducing pressurized steam between pipes;
secondly, the mixed water solution of ruthenium chloride and nickel nitrate with Ru concentration of 3ppm and Ni concentration of 10ppm which is arranged in the storage tank is pumped into the tube nest of the first step reactor which is provided with the cylindrical sintering film,the liquid space velocity of the treatment liquid is 10h-1And continuously treating the reactor for 2 hours to obtain the activated reactor, wherein Ru-Ni bimetallic active components are loaded on the surface and the inner pore channels of the metal sintered membrane of the activated reactor, and the reactor is used for the reaction process of preparing cyclohexanol by phenol hydrogenation.
The utility model discloses the nothing is mentioned the part and is applicable to prior art.
Claims (4)
1. A catalytic reactor based on metal sintering films comprises a reactor body and is characterized in that one or more layers of metal sintering films are arranged in the reactor body in a layered mode from top to bottom, a heat exchanger is arranged in the inner space of the reactor body between two adjacent layers of sintering films, a liquid-phase feeding pipe is arranged at the bottom of the reactor body, a discharging hole is formed in the top of the reactor body, and gas-phase feeding holes are formed in the side wall of the reactor body between two adjacent layers of sintering films; active components required by reaction are bonded on the surface of the metal sintering film and in the pore channel of the metal sintering film.
2. The catalytic reactor of claim 1, wherein the thickness of the metal sintered membrane plates is 1-1000 mm, the distance between the sintered membrane plates is 2-50 mm, the pore diameter is 5-200 μm, and the porosity is 10-50%.
3. The catalytic reactor of claim 2, wherein the pore size of the metal sintered membrane is 20-100 μm.
4. A catalytic reactor based on metal sintered membrane, adopt the tubular structure, including reactor body and several calandrias, characterized by that, imbed the cylindrical metal sintered membrane in the said calandria, inject the heat transfer medium among the calandria in order to provide or remove the reaction heat; the gap between the metal sintering film and the tube array is closed, the diameter of the metal sintering film is consistent with the inner diameter of the tube array, and the reaction material only passes through the space where the metal sintering film is located, but does not leave the gap between the metal sintering film and the tube array; active components required by reaction are bonded on the surface of the metal sintered film and in the pore channel.
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