CN113634290A - Regeneration method of coal liquefaction catalyst - Google Patents
Regeneration method of coal liquefaction catalyst Download PDFInfo
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- CN113634290A CN113634290A CN202110919342.3A CN202110919342A CN113634290A CN 113634290 A CN113634290 A CN 113634290A CN 202110919342 A CN202110919342 A CN 202110919342A CN 113634290 A CN113634290 A CN 113634290A
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- 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
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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
- 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
- B01J23/74—Iron group metals
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- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
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- 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
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Abstract
The invention discloses a regeneration method of a coal liquefaction catalyst, which specifically comprises the following steps: soaking and filtering a coal liquefaction catalyst to be regenerated by using solvent oil to obtain filter residues; taking the filter residue, and sequentially carrying out primary purging and secondary purging by adopting inert gas to obtain a purging product; contacting the blowing product with oxygen-containing gas, and carrying out oxidation treatment to obtain an oxidation product; contacting the oxidation product with hydrogen-containing gas, and carrying out reduction treatment to obtain a reduction product; and loading the reduction product with an active component, and aging, drying and roasting to finally obtain the regenerated coal liquefaction catalyst. Moreover, the method disclosed by the invention is simple to operate, low in cost, easy to industrially popularize and has practical application value; the temperature can be reasonably controlled in the operation process, the resource utilization rate is improved, and the activity of the coal liquefaction catalyst is prevented from being reduced due to ultrahigh temperature.
Description
Technical Field
The invention relates to the technical field of catalyst regeneration, in particular to a regeneration method of a coal liquefaction catalyst.
Background
Fischer-Tropsch synthesis (FT reaction), which is one of the coal indirect liquefaction technologies, is a process for synthesizing liquid fuel mainly containing paraffin hydrocarbons from synthesis gas under a catalyst and appropriate reaction conditions. The catalyst is one of the key technologies of Fischer-Tropsch synthesis, and the catalyst mainly used in the industry at present comprises iron base and cobalt base.
In the Fischer-Tropsch synthesis process, the activity and the selectivity of the Fischer-Tropsch synthesis catalyst are reduced along with the prolonging of the running time of the Fischer-Tropsch synthesis catalyst, so that the conversion rate of raw material gas is reduced, the yield of synthetic oil is reduced, the selectivity of byproducts is increased, and the like. The deterioration of the catalyst performance is mainly caused by the contamination of the catalyst by poisons, the carbon deposition of the catalyst, the sintering of the catalyst, the phase change of the active metal, the structural change of the catalyst itself, and the like, wherein the reversible deactivation process can recover the performance of the catalyst by regeneration, such as the carbon deposition of the catalyst, the phase change of the active metal and the adsorption of some removable poisons. Therefore, after the activity of the Fischer-Tropsch synthesis catalyst is reduced to a certain degree, the Fischer-Tropsch synthesis catalyst is regenerated or activated to improve the performance of the catalyst, so that the service life of the catalyst is prolonged, and the method has important industrial significance.
However, in the activation process of the fischer-tropsch synthesis catalyst, when the reaction atmosphere and the operation temperature are not properly adjusted, a severe overtemperature phenomenon occurs, and the overtemperature can damage the activity of the fischer-tropsch synthesis catalyst, and finally the performance of the fischer-tropsch synthesis catalyst is reduced.
Accordingly, it is an urgent problem for those skilled in the art to provide a method for regenerating a coal liquefaction catalyst to overcome the above-mentioned phenomenon.
Disclosure of Invention
In view of the above, the invention provides a regeneration method of a coal liquefaction catalyst, which can reasonably control the temperature and provide a new way for recycling the deactivated cobalt-based Fischer-Tropsch synthesis catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
a regeneration method of a coal liquefaction catalyst specifically comprises the following steps:
(1) soaking and filtering a coal liquefaction catalyst to be regenerated by using solvent oil to obtain filter residues;
(2) taking the filter residue, and sequentially carrying out primary purging and secondary purging by adopting inert gas to obtain a purging product;
(3) contacting the blowing product with oxygen-containing gas, and carrying out oxidation treatment to obtain an oxidation product;
(4) contacting the oxidation product with hydrogen-containing gas, and carrying out reduction treatment to obtain a reduction product;
(5) and loading the reduction product with an active component, and aging, drying and roasting to finally obtain the regenerated coal liquefaction catalyst.
The beneficial effects of the preferred technical scheme are as follows: the carbon deposit on the surface of the coal liquefaction catalyst to be regenerated can be preliminarily removed through the solvent oil; the residual carbon deposit and the like in the filter residue can be effectively removed by combining the primary blowing and the secondary blowing so as to effectively improve the activity of the catalyst; the content of the carbonaceous material in the catalyst can be further reduced by the oxidation treatment; the reduction treatment can convert all or part of the active metal in the catalyst from an oxidation state to a reduction state, which is beneficial to improving the activity of the catalyst; by loading the active component, the carrier, the auxiliary agent and the active component cobalt of the deactivated catalyst are reused, and the dosage of the re-loaded active component cobalt is less.
Preferably, the coal liquefaction catalyst comprises an iron-based catalyst or a cobalt-based catalyst, wherein the iron-based catalyst takes silicon dioxide as a carrier, copper as an auxiliary agent and iron as an active component; the cobalt-based catalyst takes silicon dioxide as a carrier, zirconium as an auxiliary agent and cobalt as an active component.
Preferably, the solvent oil in the step (1) comprises one or more of petroleum ether, benzene, toluene, n-octane and ethanol;
the soaking temperature is 40-50 ℃.
Preferably, the inert gas in step (2) comprises one or more of nitrogen, argon and helium;
the temperature of the primary purging is 150-230 ℃, and the space velocity of the inert gas is 300-2000 h-1The pressure is 0.5-1.0 MPa, and the time is 0.5-1.5 h;
the temperature of the secondary purging is 240-300 ℃, and the space velocity of the inert gas is 300-2000 h-1The pressure is 1.2-2.8 MPa, and the time is 2.5-5 h.
The beneficial effects of the preferred technical scheme are as follows: the temperature, the airspeed, the pressure, the time and the like of the inert gas set in the primary blowing and the secondary blowing processes are reasonably matched, so that the energy can be effectively saved, and the activity of the catalyst is damaged due to the serious overtemperature phenomenon.
Preferably, the volume fraction of oxygen in the oxygen-containing gas in the step (3) is 2-4%;
the temperature of the oxidation treatment is 360-420 ℃, the pressure of the oxidation treatment is 1.0-2.0 MPa, and the reaction end point of the oxidation treatment is that the weight of the carbon-containing substances in the oxidation products is less than 0.4%.
Preferably, the oxygen-containing gas in step (3) is oxygen or a mixed gas of air and an inert gas; the inert gas comprises one or more of nitrogen, argon and helium.
Preferably, the volume fraction of hydrogen in the hydrogen-containing gas in the step (4) is 75-98%;
the temperature of the reduction treatment is 385-395 ℃, the pressure is 0.1-1.0 MPa, and the time is 4-8 h.
Preferably, the hydrogen-containing gas in the step (4) is a mixed gas of hydrogen and an inert gas; the inert gas comprises one or more of nitrogen, argon and helium.
Preferably, the step (5) of loading the active component is to take the reduction product and add the reduction product into an aqueous solution of ferric nitrate or cobalt nitrate for impregnation; the mass ratio of the reduction product to the aqueous solution of ferric nitrate or cobalt nitrate is (15-25): 20-35), and the mass percentage concentration of the aqueous solution of ferric nitrate or cobalt nitrate is 2-8%.
Preferably, the aging time in the step (5) is 50-100 hours, and the aging temperature is 25-35 ℃;
the drying temperature is 80-120 ℃, and the drying time is 10-15 h;
the roasting temperature is 300-450 ℃, and the roasting time is 2-10 h.
The beneficial effects of the preferred technical scheme are as follows: the invention can effectively make up the defect of reduced catalyst activity caused by the hydrothermal action of the active component cobalt and the carrier to generate cobalt silicate, cobalt titanate and cobalt aluminate compounds by loading the active cobalt; and the generated cobalt silicate, cobalt titanate and cobalt aluminate compounds can inhibit the hydrothermal reaction of the regenerated cobalt-based coal liquefaction catalyst, thereby prolonging the service life of the catalyst.
According to the technical scheme, compared with the prior art, the invention discloses a method for regenerating the coal liquefaction catalyst, which has the following beneficial effects:
(1) the method disclosed by the invention is simple to operate, low in cost, easy to industrially popularize and has practical application value;
(2) the invention can effectively solve the problem of deactivation of the coal liquefaction catalyst caused by poison pollution, carbon deposition of the catalyst, catalyst sintering, phase change of active metal, structural change of the catalyst and the like, and can effectively improve the activity of the coal liquefaction catalyst;
(3) in addition, the method disclosed by the invention can reasonably control the temperature, improve the resource utilization rate and avoid reducing the activity of the coal liquefaction catalyst due to ultrahigh temperature.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a regeneration method of a coal liquefaction catalyst, wherein the coal liquefaction catalyst comprises an iron-based catalyst or a cobalt-based catalyst, the iron-based catalyst takes silicon dioxide as a carrier, copper as an auxiliary agent and iron as an active component; the cobalt-based catalyst takes silicon dioxide as a carrier, zirconium as an auxiliary agent and cobalt as an active component, and specifically comprises the following steps:
(1) soaking the coal liquefaction catalyst to be regenerated by using solvent oil at 40-50 ℃, and filtering to obtain filter residues; wherein the solvent oil comprises one or more of petroleum ether, benzene, toluene, n-octane and ethanol;
(2) taking filter residues, and sequentially performing primary purging and secondary purging by adopting inert gas to obtain a purging product;
wherein, the inert gas comprises one or more of nitrogen, argon and helium;
the temperature of the primary purging is 150-230 ℃, and the space velocity of the inert gas is 300-2000 h-1The pressure is 0.5-1.0 MPa, and the time is 0.5-1.5 h;
the temperature of the secondary purging is 240-300 ℃, and the space velocity of the inert gas is 300-2000 h-1The pressure is 1.2-2.8 MPa, and the time is 2.5-5 h;
(3) taking the sweeping product to contact with oxygen-containing gas, and carrying out oxidation treatment to obtain an oxidation product;
the oxygen-containing gas is oxygen and/or a mixed gas of air and inert gas, and the volume fraction of the oxygen in the oxygen-containing gas is 2-4%;
the temperature of the oxidation treatment is 360-420 ℃, the pressure of the oxidation treatment is 1.0-2.0 MPa, and the reaction end point of the oxidation treatment is that the weight of the carbon-containing substances in the oxidation products is less than 0.4%.
(4) Taking the oxidation product to contact with hydrogen-containing gas, and carrying out reduction treatment to obtain a reduction product;
the hydrogen-containing gas is a mixed gas of hydrogen and inert gas, and the volume fraction of the hydrogen in the hydrogen-containing gas is 75-98%;
the temperature of the reduction treatment is 385-395 ℃, the pressure is 0.1-1.0 MPa, and the time is 4-8 h;
(5) adding the reduction product into an aqueous solution of ferric nitrate or cobalt nitrate for impregnation, and then aging, drying and roasting to finally obtain a regenerated coal liquefaction catalyst;
the mass ratio of the reduction product to the ferric nitrate or cobalt nitrate aqueous solution is (15-25): 20-35, and the mass percentage concentration of the ferric nitrate or cobalt nitrate aqueous solution is 2-8%;
the aging time is 50-100 h, and the aging temperature is 25-35 ℃;
the drying temperature is 80-120 ℃, and the drying time is 10-15 h;
the roasting temperature is 300-450 ℃, and the roasting time is 2-10 h.
Example 1
Embodiment 1 of the present invention provides a method for regenerating a coal liquefaction catalyst, wherein the coal liquefaction catalyst uses silicon dioxide as a carrier, copper as an auxiliary agent, and iron as an active component, and specifically includes the following steps:
(1) soaking the coal liquefaction catalyst to be regenerated by using solvent oil at 40-50 ℃, and filtering to obtain filter residues; wherein the solvent oil is the mixture of toluene, n-octane and ethanol in equal volume ratio;
(2) taking filter residues, and sequentially performing primary purging and secondary purging by adopting inert gas to obtain a purging product;
wherein the inert gas is argon;
the temperature of the primary purging is 170 ℃, and the space velocity of the inert gas is 1000h-1The pressure is 0.6MPa, and the time is 0.8 h;
the temperature of the secondary purging is 260 ℃, and the inert gas is usedThe space velocity of the sex gas is 1200h-1The pressure is 1.8MPa, and the time is 4 h;
(3) taking the sweeping product to contact with oxygen-containing gas, and carrying out oxidation treatment to obtain an oxidation product;
the oxygen-containing gas is a mixed gas of oxygen and argon, and the volume fraction of the oxygen in the oxygen-containing gas is 3%;
the temperature of the oxidation treatment is 380 ℃, the pressure of the oxidation treatment is 1.4MPa, and the reaction end point of the oxidation treatment is that the weight of the carbon-containing substances in the oxidation products is less than 0.4 percent.
(4) Taking the oxidation product to contact with hydrogen-containing gas, and carrying out reduction treatment to obtain a reduction product;
the hydrogen-containing gas is a mixed gas of hydrogen and argon, and the volume fraction of the hydrogen in the hydrogen-containing gas is 75-98%;
the temperature of the reduction treatment is 390 ℃, the pressure is 0.6MPa, and the time is 6 h;
(5) adding the reduction product into an iron nitrate aqueous solution for impregnation, and then aging, drying and roasting to finally obtain a regenerated coal liquefaction catalyst;
the mass ratio of the reduction product to the ferric nitrate aqueous solution is 18:23, and the mass percentage concentration of the ferric nitrate aqueous solution is 6%;
the aging time is 85h, and the aging temperature is 28 ℃;
the drying temperature is 90 ℃, and the drying time is 13 h;
the roasting temperature is 350 ℃, and the roasting time is 8 h.
Example 2
Embodiment 2 of the present invention relates to a method for regenerating a coal liquefaction catalyst, wherein the coal liquefaction catalyst uses silicon dioxide as a carrier, copper as an auxiliary agent, and iron as an active component, and specifically includes the following steps:
(1) soaking the coal liquefaction catalyst to be regenerated at 47 ℃ by using solvent oil, and filtering to obtain filter residues; wherein the solvent oil is petroleum ether and toluene mixed in equal volume ratio;
(2) taking filter residues, and sequentially performing primary purging and secondary purging by adopting inert gas to obtain a purging product;
wherein the inert gas is nitrogen;
the temperature of the primary purging is 210 ℃, and the space velocity of the inert gas is 1800h-1The pressure is 0.9MPa, and the time is 0.9 h;
the temperature of the secondary purging is 290 ℃, and the space velocity of the inert gas is 1900h-1The pressure is 2.5MPa, and the time is 3.5 h;
(3) taking the sweeping product to contact with oxygen-containing gas, and carrying out oxidation treatment to obtain an oxidation product;
the oxygen-containing gas is a mixed gas of air and nitrogen, and the volume fraction of oxygen in the oxygen-containing gas is 2.5%;
the temperature of the oxidation treatment is 360-420 ℃, the pressure of the oxidation treatment is 1.0-2.0 MPa, and the reaction end point of the oxidation treatment is that the weight of the carbon-containing substances in the oxidation products is less than 0.4%.
(4) Taking the oxidation product to contact with hydrogen-containing gas, and carrying out reduction treatment to obtain a reduction product;
the hydrogen-containing gas is a mixed gas of hydrogen and nitrogen, and the volume fraction of the hydrogen in the hydrogen-containing gas is 88%;
the temperature of the reduction treatment is 389 ℃, the pressure is 0.7MPa, and the time is 6 h;
(5) adding the reduction product into an iron nitrate aqueous solution for impregnation, and then aging, drying and roasting to finally obtain a regenerated coal liquefaction catalyst;
the mass ratio of the reduction product to the ferric nitrate aqueous solution is 22:31, and the mass percentage concentration of the ferric nitrate aqueous solution is 7%;
the aging time is 80h, and the aging temperature is 28 ℃;
the drying temperature is 82 ℃, and the drying time is 14 h;
the roasting temperature is 450 ℃, and the roasting time is 10 hours.
Example 3
Embodiment 3 of the present invention provides a method for regenerating a coal liquefaction catalyst, wherein the coal liquefaction catalyst uses silicon dioxide as a carrier, copper as an auxiliary agent, and iron as an active component, and specifically includes the following steps:
(1) soaking the coal liquefaction catalyst to be regenerated at 50 ℃ by using solvent oil, and filtering to obtain filter residues; wherein the solvent oil is benzene;
(2) taking filter residues, and sequentially performing primary purging and secondary purging by adopting inert gas to obtain a purging product;
wherein the inert gas is helium;
the temperature of the primary purging is 230 ℃, and the space velocity of the inert gas is 2000h-1The pressure is 1.0MPa, and the time is 1.5 h;
the temperature of the secondary purging is 300 ℃, and the space velocity of the inert gas is 2000h-1The pressure is 2.8MPa, and the time is 5 h;
(3) taking the sweeping product to contact with oxygen-containing gas, and carrying out oxidation treatment to obtain an oxidation product;
the oxygen-containing gas is a mixed gas of air and helium, and the volume fraction of oxygen in the oxygen-containing gas is 4%;
the temperature of the oxidation treatment was 420 ℃, the pressure of the oxidation treatment was 2.0MPa, and the reaction end point of the oxidation treatment was less than 0.4% by weight of carbonaceous matter in the oxidation product.
(4) Taking the oxidation product to contact with hydrogen-containing gas, and carrying out reduction treatment to obtain a reduction product;
the hydrogen-containing gas is a mixed gas of hydrogen and helium, and the volume fraction of the hydrogen in the hydrogen-containing gas is 98%;
the temperature of the reduction treatment is 395 ℃, the pressure is 1.0MPa, and the time is 8 h;
(5) adding the reduction product into an iron nitrate aqueous solution for impregnation, and then aging, drying and roasting to finally obtain a regenerated coal liquefaction catalyst;
the mass ratio of the reduction product to the ferric nitrate aqueous solution is 25:20, and the ferric nitrate aqueous solution is 8% by mass of a loaded active component;
the aging time is 100h, and the aging temperature is 35 ℃;
the drying temperature is 120 ℃, and the drying time is 15 h;
the roasting temperature is 450 ℃, and the roasting time is 10 hours.
Example 4
Embodiment 4 of the present invention provides a method for regenerating a coal liquefaction catalyst, wherein the coal liquefaction catalyst specifically includes the following steps with silica as a carrier, zirconium as an auxiliary agent, and cobalt as an active component:
(1) soaking the coal liquefaction catalyst to be regenerated at 45 ℃ by using solvent oil, and filtering to obtain filter residues; wherein the solvent oil is obtained by mixing benzene, n-octane and ethanol according to the volume ratio of 1:2: 1;
(2) taking filter residues, and sequentially performing primary purging and secondary purging by adopting inert gas to obtain a purging product;
wherein the inert gas is nitrogen;
the temperature of the primary purging is 200 ℃, and the space velocity of the inert gas is 1000h-1The pressure is 0.8MPa, and the time is 1.0 h;
the temperature of the secondary purging is 280 ℃, and the space velocity of the inert gas is 1500h-1The pressure is 2.0MPa, and the time is 4 h;
(3) taking the sweeping product to contact with oxygen-containing gas, and carrying out oxidation treatment to obtain an oxidation product;
the oxygen-containing gas is a mixed gas of oxygen and nitrogen, and the volume fraction of the oxygen in the oxygen-containing gas is 3%;
the temperature of the oxidation treatment is 400 ℃, the pressure of the oxidation treatment is 1.5MPa, and the reaction end point of the oxidation treatment is that the weight of the carbon-containing substances in the oxidation products is less than 0.4 percent.
(4) Taking the oxidation product to contact with hydrogen-containing gas, and carrying out reduction treatment to obtain a reduction product;
the hydrogen-containing gas is a mixed gas of hydrogen and nitrogen, and the volume fraction of the hydrogen in the hydrogen-containing gas is 85%;
the temperature of the reduction treatment is 390 ℃, the pressure is 0.5MPa, and the time is 6 h;
(5) adding the reduction product into a cobalt nitrate aqueous solution for impregnation, and then aging, drying and roasting to finally obtain a regenerated coal liquefaction catalyst;
the mass ratio of the reduction product to the cobalt nitrate aqueous solution is 20:25, and the mass percentage concentration of the cobalt nitrate aqueous solution is 4 percent to load active components;
the aging time is 80h, and the aging temperature is 30 ℃;
the drying temperature is 90 ℃, and the drying time is 13 h;
the roasting temperature is 340 ℃, and the roasting time is 8 h.
Example 5
Embodiment 1 of the present invention provides a method for regenerating a coal liquefaction catalyst, wherein the coal liquefaction catalyst specifically includes the following steps with silica as a carrier, zirconium as an auxiliary agent, and cobalt as an active component:
(1) soaking the coal liquefaction catalyst to be regenerated at 40 ℃ by using solvent naphtha, and filtering to obtain filter residues; wherein the solvent oil is obtained by mixing n-octane and ethanol according to the volume ratio of 1: 1;
(2) taking filter residues, and sequentially performing primary purging and secondary purging by adopting inert gas to obtain a purging product;
wherein, the inert gas comprises argon and helium which are mixed according to the ratio of 1: 2;
the temperature of the primary purging is 150 ℃, and the space velocity of the inert gas is 300h-1The pressure is 0.5MPa, and the time is 0.5 h;
the temperature of the secondary purging is 240 ℃, and the space velocity of the inert gas is 300h-1The pressure is 1.2MPa, and the time is 2.5 h;
(3) taking the sweeping product to contact with oxygen-containing gas, and carrying out oxidation treatment to obtain an oxidation product;
the oxygen-containing gas is a mixed gas of oxygen and helium, and the volume fraction of the oxygen in the oxygen-containing gas is 2%;
the temperature of the oxidation treatment is 360 ℃, the pressure of the oxidation treatment is 1.0MPa, and the reaction end point of the oxidation treatment is that the weight of the carbon-containing substances in the oxidation products is less than 0.4 percent.
(4) Taking the oxidation product to contact with hydrogen-containing gas, and carrying out reduction treatment to obtain a reduction product;
the hydrogen-containing gas is a mixed gas of hydrogen and helium, and the volume fraction of the hydrogen in the hydrogen-containing gas is 75%;
the temperature of the reduction treatment is 385 ℃, the pressure is 0.1MPa, and the time is 4 h;
(5) adding the reduction product into a cobalt nitrate aqueous solution for impregnation, and then aging, drying and roasting to finally obtain a regenerated coal liquefaction catalyst;
the mass ratio of the reduction product to the cobalt nitrate aqueous solution is 15:35, and the mass percentage concentration of the cobalt nitrate aqueous solution is 2%;
the aging time is 50h, and the aging temperature is 25 ℃;
the drying temperature is 80 ℃, and the drying time is 10 hours;
the roasting temperature is 300 ℃, and the roasting time is 2 h.
Comparative example 1
The operation steps and technical parameters of comparative example 1 of the present invention are substantially the same as those of example 3, and only step (1) is omitted.
Comparative example 2
The operation steps and technical parameters of comparative example 2 of the present invention are substantially the same as those of example 3, and only step (2) is omitted.
Comparative example 3
The operation steps and technical parameters of comparative example 3 of the present invention are substantially the same as those of example 3, and only step (3) is omitted.
Comparative example 4
The operation steps and technical parameters of comparative example 4 of the present invention are substantially the same as those of example 3, and only step (4) is omitted.
Comparative example 5
Comparative example 5 of the present invention was substantially the same in the operational procedure and technical parameters as example 3, and only step (5) was omitted.
And respectively taking the final products prepared in the examples 1-5 and the comparative examples 1-5, and carrying out catalyst performance detection.
The experimental method comprises the following steps: reducing for 12 hours in a high-pressure continuous stirred tank reactor by taking paraffin as a solvent and pure hydrogen at 350 ℃ under the pressure of 1.0 MPa; the synthesis gas is switched to react after the temperature is reduced, the reaction effluent is respectively collected by a hot trap and a cold trap, and the reaction conditions are 180 ℃ and 250 ℃ for 1000h-1、2.0MPa、H2The operation was carried out for 100 hours with a molar ratio of 2/CO. The results of the evaluation of the obtained catalyst activity are shown in Table 1 below.
TABLE 1
From the results in table 1, it can be seen that the comprehensive performance of the regenerated coal liquefaction catalysts prepared in the embodiments 1 to 5 of the present invention is obviously the same as that of the comparative examples 1 to 5, so that the technical effect of the regeneration method disclosed by the present invention is more excellent.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The regeneration method of the coal liquefaction catalyst is characterized by comprising the following steps:
(1) soaking and filtering a coal liquefaction catalyst to be regenerated by using solvent oil to obtain filter residues;
(2) taking the filter residue, and sequentially carrying out primary purging and secondary purging by adopting inert gas to obtain a purging product;
(3) contacting the blowing product with oxygen-containing gas, and carrying out oxidation treatment to obtain an oxidation product;
(4) contacting the oxidation product with hydrogen-containing gas, and carrying out reduction treatment to obtain a reduction product;
(5) and loading the reduction product with an active component, and aging, drying and roasting to finally obtain the regenerated coal liquefaction catalyst.
2. The method for regenerating a coal liquefaction catalyst according to claim 1, wherein the coal liquefaction catalyst comprises an iron-based catalyst or a cobalt-based catalyst, the iron-based catalyst having silica as a carrier, copper as an auxiliary agent, and iron as an active component; the cobalt-based catalyst takes silicon dioxide as a carrier, zirconium as an auxiliary agent and cobalt as an active component.
3. The method for regenerating the coal liquefaction catalyst according to claim 1 or 2, wherein the solvent oil in the step (1) comprises one or more of petroleum ether, benzene, toluene, n-octane, and ethanol;
the soaking temperature is 40-50 ℃.
4. The method for regenerating the coal liquefaction catalyst according to claim 1 or 2, wherein the inert gas in the step (2) comprises one or more of nitrogen, argon and helium;
the temperature of the primary purging is 150-230 ℃, and the space velocity of the inert gas is 300-2000 h-1The pressure is 0.5-1.0 MPa, and the time is 0.5-1.5 h;
the temperature of the secondary purging is 240-300 ℃, and the space velocity of the inert gas is 300-2000 h-1The pressure is 1.2-2.8 MPa, and the time is 2.5-5 h.
5. The method for regenerating the coal liquefaction catalyst according to claim 1 or 2, wherein the volume fraction of oxygen in the oxygen-containing gas in the step (3) is 2 to 4%;
the temperature of the oxidation treatment is 360-420 ℃, the pressure of the oxidation treatment is 1.0-2.0 MPa, and the reaction end point of the oxidation treatment is that the weight of the carbon-containing substances in the oxidation products is less than 0.4%.
6. The method for regenerating a coal liquefaction catalyst according to claim 5, wherein the oxygen-containing gas in the step (3) is oxygen or a mixed gas of air and an inert gas.
7. The method for regenerating the coal liquefaction catalyst according to claim 1 or 2, wherein the volume fraction of hydrogen in the hydrogen-containing gas in the step (4) is 75 to 98%;
the temperature of the reduction treatment is 385-395 ℃, the pressure is 0.1-1.0 MPa, and the time is 4-8 h.
8. The method for regenerating a coal liquefaction catalyst according to claim 7, wherein the hydrogen-containing gas in the step (4) is a mixed gas of hydrogen and an inert gas.
9. The method for regenerating the coal liquefaction catalyst according to claim 1 or 2, wherein the step (5) of loading the active component is to take the reduction product and add the reduction product into an aqueous solution of ferric nitrate or cobalt nitrate for impregnation; the mass ratio of the reduction product to the aqueous solution of ferric nitrate or cobalt nitrate is (15-25): 20-35), and the mass percentage concentration of the aqueous solution of ferric nitrate or cobalt nitrate is 2-8%.
10. The method for regenerating the coal liquefaction catalyst according to claim 9, wherein the aging time in the step (5) is 50-100 hours, and the aging temperature is 25-35 ℃;
the drying temperature is 80-120 ℃, and the drying time is 10-15 h;
the roasting temperature is 300-450 ℃, and the roasting time is 2-10 h.
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| CA2081718A1 (en) * | 1991-11-05 | 1993-05-06 | Yuji Noguchi | Process for regenerating hydrocarbon oil hydrogenation catalysts |
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| CA2081718A1 (en) * | 1991-11-05 | 1993-05-06 | Yuji Noguchi | Process for regenerating hydrocarbon oil hydrogenation catalysts |
| CN1750876A (en) * | 2002-01-29 | 2006-03-22 | 埃克森美孚研究工程公司 | Catalyst regeneration |
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