CN109201074B - Method for regenerating Fischer-Tropsch synthesis catalyst of microchannel reactor - Google Patents

Method for regenerating Fischer-Tropsch synthesis catalyst of microchannel reactor Download PDF

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CN109201074B
CN109201074B CN201710532763.4A CN201710532763A CN109201074B CN 109201074 B CN109201074 B CN 109201074B CN 201710532763 A CN201710532763 A CN 201710532763A CN 109201074 B CN109201074 B CN 109201074B
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reactor
gas
fischer
tropsch synthesis
temperature
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CN109201074A (en
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徐润
侯朝鹏
田鹏程
牛传峰
夏国富
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8896—Rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • B01J38/14—Treating with free oxygen-containing gas with control of oxygen content in oxidation gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • B01J38/16—Oxidation gas comprising essentially steam and oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/34—Apparatus, reactors
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects

Abstract

A regeneration method of a Fischer-Tropsch synthesis catalyst of a microchannel reactor comprises the steps of replacing synthesis gas in the reactor with inert gas, carrying out cracking reaction on macromolecular hydrocarbons adsorbed by the Fischer-Tropsch synthesis catalyst under the cracking reaction condition to obtain methane and light hydrocarbons, and then carrying out oxidation and reduction. The cobalt-based Fischer-Tropsch synthesis catalyst of the microchannel reactor is regenerated, the physical and chemical properties and the catalytic performance of the regenerated catalyst are similar to those of a fresh catalyst, and the regeneration process has low energy consumption and low material consumption.

Description

Method for regenerating Fischer-Tropsch synthesis catalyst of microchannel reactor
Technical Field
The invention relates to a regeneration method of a Fischer-Tropsch synthesis catalyst, in particular to a regeneration method of a cobalt-based Fischer-Tropsch synthesis catalyst based on a microchannel reactor.
Background
Microchannel reaction technology is one of the new technologies in the chemical engineering discipline of the twenty-first century, and has incomparable advantages compared with the conventional reactor, such as: the reaction channel is micron level, the surface area is large, the reactor has high mass transfer and heat transfer rate, the reaction load of the reactor in unit volume is high, and the engineering amplification is simple. For some strong exothermic catalytic reactions, such as Fischer-Tropsch synthesis reaction and hydrocracking reaction, the heat transfer of the catalyst layer is enhanced, and the stable control of the reaction temperature is the premise and guarantee of obtaining a good reaction effect. By utilizing the microchannel reaction technology, the high-activity catalyst can react under the isothermal condition, and the defects of large mass transfer and diffusion influence and poor heat transfer effect of the traditional reactor are overcome.
After the fischer-tropsch synthesis reaction is carried out for a period of time, the performance of the catalyst is reduced due to factors such as carbon deposition formed on the surface of the catalyst, oxidation of active metals, coverage of active centers by macromolecules and the like, and the catalyst needs to be regenerated to recover the performance of the catalyst. Particularly for a microchannel reactor, the filling and coating of the catalyst are complicated, and compared with the traditional fixed bed and slurry bed, the catalyst needs longer operation period and longer catalyst life, and the catalyst regeneration not only reduces the catalyst cost and the operation cost, but also can reduce the consumption and the environmental pollution caused by the catalyst recovery treatment.
Researchers have developed a variety of regeneration methods for different fischer-tropsch synthesis processes. For slurry bed fischer-tropsch catalyst regeneration, due to reaction conditions, off-line regeneration is a commonly used method, and generally includes the steps of dewaxing, oxidative decarbonization, and reduction, for example: chinese patents CN101844093B and CN101688125B propose a method for regenerating a granular catalyst for slurry bed reaction, which includes dewaxing, oxidation and reduction processes, wherein the dewaxing process employs xylene to wash with a solvent and then dry. Chinese patent CN101703937B proposes a method for regenerating a slurry bed fischer-tropsch catalyst, which needs to undergo extraction, stripping, oxidation and reduction processes. Catalyst dewaxing with C7～C12The alkane is extracted and then stripped to dryness. Chinese patent CN102791377B discloses a regeneration method of a Fischer-Tropsch synthesis catalyst, wherein the catalyst is washed by paraffin to remove oil, and then is treated by steam with the pressure of 5MPa, so that a better regeneration effect can be obtained. US4399234 discloses a method for regenerating a catalyst, which comprises contacting the catalyst with an oxygen-containing gas or steam at a high temperature, and reducing and activating the regenerated catalyst with a hydrogen-containing gas at a high temperature. US2369956 discloses a process for the regeneration of fischer-tropsch synthesis catalysts by dissolving the active metals of the catalyst with an acid and then recovering the catalyst by re-precipitation of the catalyst metals. The method has effect on catalyst deactivation of various reasons, but can destroy catalyst structure, influence active metal and carrier and active metal and promoterThe interaction between the agents and the operation are complex, and the catalyst regeneration needs to be carried out in other special equipment. Chinese patent CN102259036B discloses an on-line catalyst regeneration method, which is used for fixed bed fischer-tropsch synthesis catalyst regeneration, wherein the catalyst in the reactor is subjected to purging, solvent washing, oxidation and reduction to obtain performance recovery.
In the prior art, in the regeneration process of the Fischer-Tropsch synthesis catalyst, the dewaxing step on the Fischer-Tropsch synthesis catalyst is mainly washed by a solvent, but in the solvent washing process, on one hand, the requirement on the solvent is very high, and for example, the content of impurities such as sulfur, nitrogen, oxygen, metals and the like in the solvent is strictly required, so that the catalyst is prevented from being polluted. On the other hand, the solvent washing process and the wax-containing solvent reprocessing process after washing are both processes with high energy and material consumption.
Disclosure of Invention
The invention aims to provide a method for regenerating a Fischer-Tropsch synthesis catalyst for a microchannel reactor. The method aims to solve the technical problems of high energy consumption and high material consumption in the regeneration process in the prior art.
The regeneration method provided by the invention comprises the following steps:
(1) replacing the synthesis gas in the reactor with inert gas,
(2) introducing hydrogen into the reactor, carrying out cracking reaction on macromolecular hydrocarbons adsorbed by the Fischer-Tropsch synthesis catalyst in a hydrogen atmosphere under the condition of cracking reaction to obtain methane and light hydrocarbons,
(3) contacting the Fischer-Tropsch synthesis catalyst treated in the step (2) with oxygen-containing gas, oxidizing under the oxidation condition,
(4) the oxidized Fischer-Tropsch synthesis catalyst in the step (3) contacts with hydrogen-containing gas for reduction to obtain a regenerated Fischer-Tropsch synthesis catalyst,
the Fischer-Tropsch synthesis catalyst is a cobalt-based supported Fischer-Tropsch synthesis catalyst, and the cobalt-based supported Fischer-Tropsch synthesis catalyst is filled or coated in the microchannel reactor.
The microchannel reactor is a reactor with a multi-column channel structure, channels are arranged in a layered structure in parallel and/or staggered mode, the channels are used for filling and coating catalysts or circulating heat-conducting media, the microchannel is a pore channel with the width or depth dimension of less than 1000 micrometers, and the length of the channel exceeds 1 cm.
In one embodiment of the invention, two channels, namely a reaction channel and a heat-conducting medium channel, are arranged in the microchannel reactor. The reaction channel is filled or coated with the cobalt-based supported Fischer-Tropsch synthesis catalyst to generate Fischer-Tropsch synthesis reaction; the heat-conducting medium channel is communicated with a gas-phase or liquid-phase heat-conducting medium and used for leading out reaction heat or heating the reactor. The reaction channels and the heat-conducting medium channels are alternately arranged and isolated from each other, and the material flow direction can be parallel flow, cross flow or form a certain angle (for example, 90 degrees).
The Fischer-Tropsch synthesis reaction in the microchannel reactor has the following reaction conditions: the pressure is 1-5 MPa, the temperature is 150-300 ℃, and the gas hourly space velocity is 1000-100000 h-1In the feed gas H2The volume ratio of the recycled gas to CO is 1-3, the ratio of the recycled gas to the fresh raw material gas is 0.1-10, and the preferred ratio is as follows: the reaction pressure is 2-4 MPa, the temperature is 180-250 ℃, and the gas hourly space velocity is 2000-40000 h-1In the feed gas H2The ratio of the recycled gas to the CO is 1.8-2.5, and the ratio of the recycled gas to the fresh raw material gas is 0.5-6. In the reaction process, a heat-conducting medium channel of the microchannel reactor needs to be filled with a medium to lead out heat, and the heat-conducting medium can be a gas phase, such as air and N2、H2、CO2Water vapor, etc., or a liquid phase, such as water, heat transfer oil, etc.
The cobalt-based supported Fischer-Tropsch synthesis catalyst comprises an active component cobalt, an auxiliary agent and a carrier, wherein the auxiliary agent is selected from one or more of transition metal, rare earth metal and non-metal elements, and the carrier is selected from Al2O3、SiO2、TiO2、ZrO2And one or more of the molecular sieves, wherein the cobalt content is 10-50% by weight.
The cobalt-based supported Fischer-Tropsch synthesis catalyst is prepared by any one of coprecipitation, impregnation and spraying methods. When the cobalt-based supported Fischer-Tropsch synthesis catalyst is powder, the powder is filled in a reaction channel of a micro-channel reactor, or the wall-loading mode is adopted to coat the cobalt-based supported Fischer-Tropsch synthesis catalyst on the inner wall of the reaction channel or a support body. The support can be any reaction inert object with certain strength, such as a stainless steel net, a stainless steel plate, a ceramic plate and the like.
In one embodiment of the regeneration process provided by the present invention, in step (1), the synthesis gas in the reactor is replaced with an inert gas selected from the group consisting of N2One or more of Ar and He, preferably N2The space velocity of the introduced inert gas is 2000-20000 h-1Preferably 5000 to 10000h-1. The reactor temperature is reduced to below 180 c, preferably to 150 c, while inert gas is introduced.
In one embodiment of the regeneration method provided by the invention, in the step (2), the space velocity of the introduced hydrogen is 2000h-1～8000h-1Preferably 3000h-1～5000h-1The reactor pressure is 0.5MPa to 10MPa, preferably 1.0MPa to 8.0 MPa. The temperature control process in the reactor in the step (2) is as follows: heating to 200-300 ℃, keeping the temperature for 2-10 h, heating to 300-450 ℃, keeping the temperature until the methane content in the exhaust gas is lower than 1 volume percent, reducing the temperature in the reactor to 50 ℃. Further preferably, the temperature is raised to 340 to 400 ℃, and the temperature in the reactor is lowered when the temperature is maintained until the methane content in the exhaust gas is less than 1 volume percent. The rate of temperature rise is not more than 40 ℃/h, preferably not more than 30 ℃/h. In the process, macromolecular hydrocarbons adsorbed by the Fischer-Tropsch synthesis catalyst undergo cracking reaction to obtain methane and light hydrocarbons.
Preferably, before the Fischer-Tropsch synthesis catalyst treated in the step (2) contacts with the oxygen-containing gas, inert gas is introduced for purging, and the qualified Fischer-Tropsch synthesis catalyst contacts with the oxygen-containing gas after purging, wherein the inert gas is selected from N2One or more of Ar and He; when the exhausted gas is burnt (H)2+ total hydrocarbons) is less than 0.1%, the purge is deemed acceptable.
In one embodiment of the regeneration method provided by the invention, in the step (3), the Fischer-Tropsch synthesis catalyst is connected at the temperature of the reactor lower than 50-80 ℃ and the pressure of 0.5-2.0 MPaContacting oxygen-containing gas, wherein the volume fraction of oxygen in the oxygen-containing gas at the inlet of the reactor is 0.5-2%. After the reactor is filled with oxygen-containing gas and the temperature of the reactor is not changed, the temperature of the reactor is gradually increased to 400-450 ℃, and the heating rate is not more than 40 ℃/h, preferably not more than 30 ℃/h. CO + CO in the exhaust gas to be exhausted2After the content is unchanged, increasing the integral number of oxygen in the oxygen-containing gas, wherein the volume fraction of oxygen in the oxygen-containing gas at the inlet of the reactor is 5-15%; CO + CO in the exhaust gas to be exhausted2Volume content<The oxidation was complete after 0.05%.
The purpose of the oxidation of the Fischer-Tropsch synthesis catalyst is to convert organic matters such as metal, carbon deposited on the surface and the like of the Fischer-Tropsch synthesis catalyst into metal oxides and carbon oxides in a controllable range, so that any oxidation mode can be adopted on the premise of not damaging the Fischer-Tropsch synthesis catalyst. Preferred oxygen-containing gases of the present invention are selected from oxygen and/or air mixed with inert gases or steam. Specifically, the oxygen-containing gas may be a mixed gas of oxygen and/or air and an inert gas, or a mixed gas of oxygen and/or air and water vapor. Further, a mixed gas of oxygen and an inert gas is preferable.
The cracking process in the step (2) and the oxidation process in the step (3) are both exothermic processes, preferably, a heat-conducting medium is introduced into a heat-conducting medium channel of the microchannel reactor to lead out heat, and the heat-conducting medium is a gas phase: selected from air, N2、H2、CO2One or more of water vapor or liquid phase: water or heat conducting oil.
Preferably, before the Fischer-Tropsch synthesis catalyst oxidized in the step (3) contacts with the hydrogen-containing gas, inert gas is introduced for purging, and the qualified Fischer-Tropsch synthesis catalyst after purging contacts with the hydrogen-containing gas, wherein the inert gas is selected from N2One or more of Ar and He; purge was considered acceptable when the volume fraction of oxygen in the purge gas was less than 0.1%.
In one embodiment of the regeneration method provided by the invention, in the step (4), hydrogen-containing gas is introduced into the reactor, the volume fraction of hydrogen in the hydrogen-containing gas is not more than 10%, preferably not more than 5%, and the space velocity for introducing the hydrogen-containing gas is500～5000h-1Preferably 1500 to 3000 hours-1The temperature of the reactor is 350-500 ℃, preferably 350-450 ℃, the heating rate is not more than 60 ℃/h, preferably not more than 40 ℃/h, the pressure is 0-2.0 MPa, preferably 0-1.0 MPa, and the maximum temperature difference of each point of the reactor is not more than 5 ℃, preferably not more than 3 ℃. And measuring the water content in the discharged gas until the water content is less than 5mg/L, preferably less than 2mg/L, increasing the volume fraction of hydrogen in the hydrogen-containing gas to 30-60%, preferably 40-50%, and keeping the temperature for 2-20 h.
The catalyst regeneration process can be carried out in situ in the Fischer-Tropsch synthesis device, and can also be carried out in a special device after the microchannel reactor with the catalyst is unloaded.
Compared with the prior art, the invention has the following advantages:
(1) the method has the advantages that the in-situ regeneration is realized by utilizing the characteristics of the cobalt-based supported Fischer-Tropsch synthesis catalyst, the characteristics of the microchannel reactor and the cracking performance of the cobalt-based supported Fischer-Tropsch synthesis catalyst are combined, the cracking reaction with strong heat release can be controllably generated in the microchannel reactor under the optimized regeneration condition, the damage of the heat release of the cracking reaction to the catalyst structure is avoided, the generation of a large amount of carbon deposit of the catalyst is also avoided, the solvent washing step is omitted, and the material consumption and the energy consumption in the regeneration process are effectively reduced.
(2) The regeneration method provided by the invention has the advantages of small damage to the cobalt-based supported Fischer-Tropsch synthesis catalyst, simple and convenient operation, easy realization, no additional equipment and good performance recovery of the regenerated cobalt-based supported Fischer-Tropsch synthesis catalyst.
Drawings
FIG. 1 is a schematic structural diagram of one embodiment of a microchannel reactor according to the present invention. In the figure, the number 11 is a micro-channel reactor, 12 is a reaction channel, and 13 is a heat-conducting medium channel.
FIG. 2 is a schematic structural diagram of another embodiment of the microchannel reactor of the invention. In the figure, the number 21 is a micro-channel reactor, 22 is a reaction channel, and 23 is a heat-conducting medium channel.
Detailed Description
The following examples further illustrate the process provided by the present invention, but are not intended to limit the invention thereto.
Example 1
As shown in FIG. 1, the microchannel reactor 11 comprises 8 layers of reaction channels 12 arranged side by side and 9 layers of heat transfer medium channels 13 arranged side by side, each of which has a width of 10mm, a height of 1mm and a length of 100mm, and each of which has 4 reaction channels 12. Each heat-conducting medium channel is 10mm wide, 1mm high and 100mm long, and each layer is provided with 6 heat-conducting medium channels 13. The reaction channel 12 and the heat transfer medium channel 13 intersect at 90 °. The reaction channel 12 is filled with a cobalt-based supported fischer-tropsch synthesis catalyst.
The preparation process of the cobalt-based supported Fischer-Tropsch synthesis catalyst used in the embodiment is as follows: taking alumina powder, dropwise adding distilled water to incipient wetness, recording the volume of consumed water, preparing cobalt nitrate impregnation liquid according to 27 weight percent of Co content (calculated by oxide), and preparing perrhenic acid impregnation liquid according to 0.1 weight percent of Re content (calculated by oxide). Then the solution is used for dipping alumina to incipient wetness, standing for 8 hours, then drying for 4 hours at 120 ℃, and roasting for 4 hours at 450 ℃ in a muffle furnace to prepare the cobalt-based supported Fischer-Tropsch synthesis catalyst. The granularity range of the cobalt-based supported Fischer-Tropsch synthesis catalyst is 50-200 mu m.
The prepared cobalt-based supported Fischer-Tropsch synthesis catalyst is filled in a reaction channel, and the gas space velocity is 1000h under the conditions of 0.1MPa and nitrogen atmosphere-1Under the condition, the temperature of the reactor is raised to 120 ℃ at the temperature raising rate of 30 ℃/h, the maximum temperature difference of each point of the reactor is not more than 1 ℃ in the temperature raising process, and the temperature is kept for 8 h; after the constant temperature is finished, introducing hydrogen-nitrogen mixed gas (the volume fraction of hydrogen is 5 percent) and the gas space velocity is 3000mL/mLCatalyst and process for preparing sameAnd h, heating to 280 ℃ at a specified speed of 10 ℃/h, keeping the maximum temperature difference of each point of the reactor not more than 2 ℃ in the heating process, and keeping the temperature for 12h after the temperature is raised. After the constant temperature is finished, introducing hydrogen-nitrogen mixed gas (the volume fraction of hydrogen is 5 percent) and the gas space velocity is 2000mL/mLCatalyst and process for preparing sameHeating to 400 ℃ at a specified speed of 20 ℃/h, detecting that the water content in the exhaust gas is 2mg/L after the temperature is heated to a constant temperature for 6h, increasing the volume fraction of the hydrogen of the mixed gas of hydrogen and nitrogen to 40%, and detecting the exhaust after 6hThe water content in the gas is 2mg/L, pure hydrogen is used for feeding, the temperature is kept for 6h, then the reduction is finished, and the temperature is reduced by 30 ℃/h.
The reduced cobalt-based supported Fischer-Tropsch synthesis catalyst has the following reaction conditions: the pressure is 3.0MPa, the temperature is 220 ℃, and the composition of the synthesis gas (raw material gas) is H2Volume fraction 60%, volume fraction 30% CO, N2Volume fraction of 10 percent and space velocity of 20000mL/mLCatalyst and process for preparing samePerforming Fischer-Tropsch synthesis reaction, analyzing the product by gas chromatography, and calculating CO conversion rate, methane selectivity and C5 +Hydrocarbon selectivity.
After reacting for a period of time, the cobalt-based supported Fischer-Tropsch synthesis catalyst needs to be regenerated. First, syngas feed cut-in N2Displacement reactor, gas hourly space velocity 6000mL/mLCatalyst and process for preparing sameAfter 12 hours, the catalyst bed temperature was lowered to 160 ℃ at a rate of 20 ℃/h. Cut into hydrogen, gas hourly space velocity 3000mL/mLCatalyst and process for preparing sameSetting the hydrogen partial pressure to be 4.5MPa, heating to 280 ℃ at the heating rate of 10 ℃/h, and detecting the methane content in the exhaust gas in the heating process; after the methane content begins to decrease, heating to 400 ℃ at a heating rate of 20 ℃/h; when the methane content in the exhaust gas is lower than 1 percent, the reactor temperature is reduced to 50 ℃ at the speed of 20 ℃/h, and the hydrocracking process is finished.
Cutting hydrogen into nitrogen, and replacing with combustible gas (H) in purge gas2+ total hydrocarbons) volume fraction of less than 0.1%; adding air into nitrogen gas in a certain proportion to make the volume fraction of oxygen in the oxygen-containing gas at the inlet of the reactor be 1%, raising the temperature of the catalyst to 85 ℃ due to oxidation reaction, and gradually raising the temperature of the reactor to 400 ℃ at 25 ℃ per hour after the temperature of the reactor is not changed. Keeping the temperature of 400 ℃ for 5h, increasing the volume fraction of oxygen in the oxygen-containing gas at the inlet of the reactor to 5%, keeping the temperature for 5h, switching to air constant temperature for 10h, and when CO in the purge gas is constant2Volume fraction<When the oxidation is finished at 0.05 percent, the temperature of the reactor is reduced to 150 ℃ at the speed of 30 ℃ per hour.
Cutting oxygen-containing gas into nitrogen, replacing until the volume fraction of oxygen in the purge gas is less than 0.1%, cutting into a hydrogen-nitrogen mixed gas containing 2% hydrogen by volume fraction, wherein the gas space velocity is 3000mL/mLCatalysisAgent for treating cancerAnd/h, reducing the temperature of a catalyst bed layer to 400 ℃ at the speed of 20 ℃/h, ensuring that the maximum temperature difference of each point of the reactor is not more than 3 ℃ in the temperature rising process, detecting that the moisture content in the discharged gas is 2mg/L after the temperature rises to a constant temperature for 6h, increasing the volume fraction of hydrogen of the mixed gas of hydrogen and nitrogen to 40%, detecting that the moisture content in the discharged gas is 2mg/L after 6h, changing the discharged gas into pure hydrogen to feed, reducing after constant temperature for 6h, beginning to reduce the temperature at 30 ℃/h, and ending the regeneration process of the cobalt-based supported Fischer-Tropsch synthesis catalyst.
The performance test of the regenerated cobalt-based supported Fischer-Tropsch synthesis catalyst is carried out under the same conditions, and the results of comparing the performance of the regenerated cobalt-based supported Fischer-Tropsch synthesis catalyst with that of a fresh catalyst and a catalyst before regeneration are listed in Table 1.
Example 2
As shown in FIG. 2, the microchannel reactor 21 comprises 8 layers of reaction channels 22 arranged side by side and 9 layers of heat transfer medium channels 23 arranged side by side, each reaction channel 22 having a width of 20mm, a height of 1mm and a length of 100mm, and 3 reaction channels 22 in each layer. Each heat-conducting medium channel 23 is 10mm wide, 1mm high and 100mm long, and each layer is provided with 6 heat-conducting medium channels 23. The reaction channel 22 and the heat transfer medium channel 23 intersect at 90 °. The reaction channels 22 are filled with a catalyst support coated with a cobalt-based supported fischer-tropsch synthesis catalyst.
The cobalt-based Fischer-Tropsch synthesis catalyst used in the embodiment is a coating type monolithic catalyst, and the preparation process is as follows: the cobalt-based supported catalyst is coated on a treated wave-shaped stainless steel support body, and the support body has the width of 18mm, the height of 0.8mm and the length of 90 mm. And ultrasonically oscillating the support body in an acetone solution for 30min to remove the dirt on the surface. According to 8 percent of Al powder, 5 percent of Fe and 3 percent of NH4Cl and the balance of alumina to prepare the aluminizing agent. Mixing the aluminizing agent and the stainless steel support body together, and roasting at 850 ℃ for 120 min. And preparing the stainless steel support body with the surface rich in aluminum. And ultrasonically oscillating for 45min in an acetone solution to remove surface dirt, heating to 500 ℃ at the heating rate of 2.0 ℃/min, and roasting for 120min to prepare the stainless steel sheet with the surface rich in alumina. Nitric acid and pseudo-boehmite are mixed according to a molar ratio H+/Al3+Mixing at 0.12 deg.C, stirring at 70 deg.C for 1.0 hr, reacting and aging for 12 hr to obtain aged oxygenAluminum sol; mixing the sol and 20% of polyethylene glycol, stirring to obtain uniform slurry, and coating by dripping dipping method. After coating was complete, drying was carried out at room temperature for 3 hours, then at 120 ℃ for 3 hours at a rate of 0.5 ℃/min. And after drying, placing the coated piece into a muffle furnace for roasting, wherein the roasting temperature is 700 ℃, the heating rate is 0.8 ℃/min, the time is 3 hours, and naturally cooling to room temperature to take out the sample. And placing the coated carrier member into a mixed solution containing cobalt nitrate and ammonium metatungstate for saturated impregnation, and then drying and roasting. Wherein the drying temperature is 120 ℃, the drying time is 3 hours, the roasting temperature is 350 ℃, and the roasting time is 3 hours. The cobalt nitrate is used in an amount such that the cobalt oxide content in the final Fischer-Tropsch synthesis catalyst is 45 wt% and the tungsten promoter content is about 2 wt%.
The prepared cobalt-based Fischer-Tropsch synthesis catalyst support is inserted into a reaction channel, and the gas space velocity is 1000mL/g under 0.1MPa and in a nitrogen atmosphereCatalyst and process for preparing sameHeating to 120 ℃ at a specified speed of 30 ℃/h under the condition of/h, keeping the maximum temperature difference of each point of the reactor not more than 1 ℃ in the heating process, and keeping the temperature for 8 h; after the constant temperature is finished, introducing hydrogen-nitrogen mixed gas (the volume fraction of hydrogen is 5 percent) and the gas space velocity is 3000mL/gCatalyst and process for preparing sameAnd h, heating to 280 ℃ at a specified speed of 10 ℃/h, keeping the maximum temperature difference of each point of the reactor not more than 2 ℃ in the heating process, and keeping the temperature for 12h after the temperature is raised. After the constant temperature is finished, introducing hydrogen-nitrogen mixed gas (the volume fraction of hydrogen is 5 percent) and the gas space velocity is 2000mL/gCatalyst and process for preparing sameHeating to 400 ℃ at a specified speed of 20 ℃/h, detecting that the moisture content in the exhaust gas is 2mg/L after the temperature is heated to a constant temperature for 6h, increasing the volume fraction of hydrogen of the mixed gas of hydrogen and nitrogen to 40%, detecting that the moisture content in the exhaust gas is 2mg/L after 6h, changing the hydrogen into pure hydrogen, finishing reduction after constant temperature for 6h, and starting to cool at 30 ℃/h.
The reduced cobalt-based supported Fischer-Tropsch synthesis catalyst has the following reaction conditions: the pressure is 3.0MPa, the temperature is 220 ℃, and the composition of the synthesis gas (raw material gas) is H2Volume fraction 60%, volume fraction 30% CO, N2Volume fraction of 10 percent and space velocity of 20000mL/gCatalyst and process for preparing sameH, performing Fischer-Tropsch synthesis reaction to obtainAnalyzing the product by gas chromatography, and calculating CO conversion rate, methane selectivity and C5 +Hydrocarbon selectivity.
After reacting for a period of time, regenerating the cobalt-based supported Fischer-Tropsch synthesis catalyst. First cut syngas into N2Displacement reactor, gas hourly space velocity 6000mL/gCatalyst and process for preparing sameAfter 12 hours, the reactor temperature was lowered to 160 ℃ at a rate of 20 ℃/h. Cut into hydrogen, gas hourly space velocity 3000mL/gCatalyst and process for preparing sameSetting the hydrogen partial pressure to be 3.0MPa, heating to 265 ℃ at the heating rate of 10 ℃/h, and detecting the methane content in the exhaust gas in the heating process; after the methane content begins to decrease, heating to 360 ℃ at a heating rate of 20 ℃/h; when the methane content in the exhaust gas is lower than 1 percent, the reactor temperature is reduced to 50 ℃ at the speed of 20 ℃/h, and the hydrocracking process is finished.
Cutting hydrogen into nitrogen, and replacing with combustible gas (H) in purge gas2+ total hydrocarbons) volume fraction of less than 0.1%; adding air with a certain proportion into nitrogen to ensure that the volume fraction of oxygen in oxygen-containing gas at the inlet of the reactor is 1 percent, raising the temperature of the cobalt-based supported Fischer-Tropsch synthesis catalyst to 85 ℃ due to oxidation reaction, and gradually raising the temperature of the reactor to 350 ℃ at 25 ℃ per hour after the temperature of the reactor is not changed. Keeping the temperature of 350 ℃ for 5h, increasing the volume fraction of oxygen in the oxygen-containing gas at the inlet of the reactor to 5%, keeping the temperature for 5h, switching to constant temperature of air for 10h, and when CO in the purge gas is constant2Volume fraction<When the concentration is 0.05 percent, the oxidation is finished, and the temperature is reduced to 150 ℃ at the speed of 30 ℃ per hour.
Cutting oxygen-containing gas into nitrogen, replacing until the volume fraction of oxygen in the purge gas is less than 0.1%, cutting into hydrogen-nitrogen mixed gas containing 2% hydrogen, and gas space velocity is 3000mL/gCatalyst and process for preparing sameAnd/h, reducing the temperature of the reactor to 400 ℃ at the speed of 20 ℃/h, ensuring that the maximum temperature difference of each point of the reactor is not more than 3 ℃ in the temperature rising process, detecting that the moisture content in the exhaust gas is 2mg/L after the temperature rises to a constant temperature for 6h, increasing the volume fraction of hydrogen of the mixed hydrogen-nitrogen gas to 40%, detecting that the moisture content in the exhaust gas is 2mg/L after 6h, changing the exhaust gas into pure hydrogen, finishing reduction after the constant temperature is 6h, beginning to reduce the temperature at 30 ℃/h, and finishing the regeneration process of the cobalt-based supported Fischer-Tropsch synthesis catalyst.
The performance test of the regenerated cobalt-based supported Fischer-Tropsch synthesis catalyst is carried out under the same conditions, and the results of comparing the performance of the regenerated cobalt-based supported Fischer-Tropsch synthesis catalyst with that of a fresh catalyst and a catalyst before regeneration are listed in Table 2.
TABLE 1
Figure BDA0001339777370000081
Figure BDA0001339777370000091
TABLE 2
Fresh catalyst Before regeneration Example 2
Reactor temperature,. deg.C 220 220 220
Reaction pressure, MPa 3.0 3.0 3.0
Space velocity, mL/gCatalyst and process for preparing same/h 20000 20000 20000
CO conversion rate,% 90.6 80.7 89.8
CH4Selectively, according to 7.4 11.6 7.6
C5 +Selectively, according to 88.6 84.7 88.9

Claims (13)

1. A method for regenerating a Fischer-Tropsch synthesis catalyst of a microchannel reactor comprises the following steps:
(1) replacing the synthesis gas in the reactor with inert gas,
(2) introducing hydrogen into the reactor, and carrying out cracking reaction on macromolecular hydrocarbons adsorbed by the Fischer-Tropsch synthesis catalyst in a hydrogen atmosphere under the cracking reaction condition to obtain methane and light hydrocarbons, wherein the space velocity of the introduced hydrogen is 2000h-1～8000h-1The pressure of the reactor is 0.5MPa to 10 MPa; the temperature control process in the reactor is as follows: heating to 200-300 ℃, keeping the temperature for 2-10 h, heating to 300-450 ℃, keeping the temperature until the methane content in the exhaust gas is lower than 1 volume percent, reducing the temperature in the reactor to 50 ℃;
(3) contacting the Fischer-Tropsch synthesis catalyst treated in the step (2) with oxygen-containing gas, oxidizing under the oxidation condition,
contacting the Fischer-Tropsch synthesis catalyst with oxygen-containing gas at the temperature of 50-80 ℃ and the pressure of 0.5-2.0 MPa, wherein the volume fraction of oxygen in the oxygen-containing gas at the inlet of the reactor is 0.5-2%,
after the reactor is filled with oxygen-containing gas, the temperature of the reactor is gradually increased to 400-450 ℃,
CO + CO in the exhaust gas to be exhausted2After the content is not changed, the integral number of oxygen in the oxygen-containing gas is increased, the volume fraction of oxygen in the oxygen-containing gas at the inlet of the reactor is 5-15 percent,
CO + CO in the exhaust gas to be exhausted2Volume content<Finishing oxidation after 0.05 percent;
(4) the oxidized Fischer-Tropsch synthesis catalyst in the step (3) contacts with hydrogen-containing gas for reduction to obtain a regenerated Fischer-Tropsch synthesis catalyst,
the Fischer-Tropsch synthesis catalyst is a cobalt-based supported Fischer-Tropsch synthesis catalyst,
the microchannel reactor is internally provided with two channels, namely a reaction channel and a heat-conducting medium channel, the reaction channel is filled or coated with the cobalt-based supported Fischer-Tropsch synthesis catalyst to generate Fischer-Tropsch synthesis reaction, the heat-conducting medium channel circulates gas-phase or liquid-phase heat-conducting medium and is used for leading out reaction heat or heating the reactor, the reaction channel and the heat-conducting medium channel are alternately arranged and isolated from each other, and the material circulation direction can be parallel flow, cross flow or form a certain angle.
2. The method of claim 1, wherein the inert gas of step (1) is selected from the group consisting of N2One or more of Ar and He, and the space velocity of the introduced inert gas is 2000h-1～20000h-1。
3. The method of claim 2, wherein the inert gas of step (1) is selected from the group consisting of N2The space velocity of the inert gas is 5000h-1～10000h-1。
4. The process of claim 1, wherein in step (1) the temperature of the reactor is reduced to below 180 ℃ while introducing an inert gas.
5. The process according to claim 1, wherein in step (2), the space velocity of hydrogen gas is 3000h-1～5000h-1The pressure of the reactor is 1.0MPa to 8.0 MPa.
6. The method according to claim 1, wherein, in the step (2), during the control of the temperature in the reactor: heating to 340-400 ℃, keeping the temperature until the methane content in the exhaust gas is lower than 1 volume percent, and reducing the temperature in the reactor.
7. The process of claim 1 wherein the purging step (2) is conducted by introducing an inert gas selected from the group consisting of N and inert gases before contacting the treated Fischer-Tropsch synthesis catalyst with the oxygen-containing gas and purging the qualified Fischer-Tropsch synthesis catalyst with the oxygen-containing gas2One or more of Ar and He; combustible gas H in the exhausted gas2When the volume fraction of + total hydrocarbons is less than 0.1%, the purge is qualified.
8. The process according to claim 1, wherein the oxygen-containing gas is selected from oxygen and/or a mixed gas of air and an inert gas or water vapor.
9. The process of claim 1 wherein the purge with an inert gas selected from the group consisting of N is conducted before contacting the oxidized Fischer-Tropsch synthesis catalyst of step (3) with the hydrogen containing gas and the qualified Fischer-Tropsch synthesis catalyst is contacted with the hydrogen containing gas2One or more of Ar and He; purge was considered acceptable when the volume fraction of oxygen in the purge gas was less than 0.1%.
10. The method according to claim 1, wherein in the step (4), hydrogen-containing gas is introduced into the reactor, the volume fraction of hydrogen in the hydrogen-containing gas is not more than 10%, and the space velocity for introducing the hydrogen-containing gas is 500-5000 h-1The temperature of the reactor is 350-500 ℃, the pressure is 0-2.0 MPa, and the maximum temperature difference of each point of the reactor is not more than 5 ℃.
11. The method according to claim 10, wherein in the step (4), the space velocity of the hydrogen-containing gas is 1500-3000 h-1The temperature of the reactor is 350-450 ℃, the pressure is 0-1.0 MPa, and the maximum temperature difference of each point of the reactor is not more than 3 ℃.
12. The method according to claim 1, wherein in the step (4), the water content in the exhaust gas is measured, the volume fraction of the hydrogen in the hydrogen-containing gas is increased to 30-60% when the water content is less than 5mg/L, and the temperature is kept for 2-20 h.
13. The method according to claim 1, wherein the cobalt-based supported Fischer-Tropsch synthesis catalyst comprises an active component cobalt, an auxiliary agent and a carrier, wherein the auxiliary agent is selected from one or more of transition metal, rare earth metal and non-metal elements, and the carrier is selected from Al2O3、SiO2、TiO2、ZrO2And one or more of the molecular sieves, wherein the cobalt content is 10-50% by weight.
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