CN112958104B - Preparation method of hydrodesulfurization catalyst - Google Patents
Preparation method of hydrodesulfurization catalyst Download PDFInfo
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- CN112958104B CN112958104B CN202110241314.0A CN202110241314A CN112958104B CN 112958104 B CN112958104 B CN 112958104B CN 202110241314 A CN202110241314 A CN 202110241314A CN 112958104 B CN112958104 B CN 112958104B
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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
- B01J23/76—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
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
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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
- B01J23/76—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
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention belongs to the technical field of catalyst preparation, and discloses a preparation method of a hydrodesulfurization catalyst. The novel hydrogenation catalyst prepared by the invention has larger specific surface area, dense active components and rich active sites, and is beneficial to sulfur-containing macromolecules to pass through the inner pore canal of the catalyst, thereby greatly reducing the mass transfer resistance of the catalyst and improving the hydrodesulfurization efficiency of the catalyst.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a preparation method of a hydrodesulfurization catalyst.
Background
Fossil fuels are the most important resource in various countries, but substances such as sulfur, nitrogen and the like in petroleum have serious influence on the ecological environment, wherein sulfides contained in the petroleum mainly comprise hydrogen sulfide, elemental sulfur, mercaptan, thiophene, benzothiophene and the like. With the increase of petroleum consumption, the world has more and more concern about environmental problems, and environmental protection regulations are successively developed in various countries, wherein the implementation of the national six-emission standard of motor vehicle pollutants in China puts higher requirements on the emission standards of carbon monoxide, nitrogen oxides and sulfur-containing compounds, so that people try to reduce the sulfur content in oil products by using a new process, and most of the researches mainly focus on hydrodesulfurization, especially deep hydrodesulfurization.
Since there is an interaction between the supported catalyst carrier and the active component and the loading of the active substance on the carrier is limited, the catalytic activity is difficult to be greatly improved, and thus, finding a catalyst with higher activity becomes a hot spot. The organic foam is widely applied to a plurality of fields as a novel material, has a three-dimensional grid structure with high opening rate, excellent sound absorption, flame retardance, heat insulation, heat-resistant stability and the like, has unique chemical and physical stability due to a unique chemical structure and a three-dimensional net-shaped cross-linking system, cannot be aged and decomposed in weak acid and weak alkali environments, has no residual free formaldehyde, and has a large number of active groups such as hydroxyl, amino and the like on the surface, so other functional groups are easy to graft.
Therefore, how to provide a catalyst with higher activity is a technical problem to be solved urgently by those skilled in the art.
Disclosure of Invention
The invention aims to solve the problems of small loading capacity and low utilization rate of active components of the existing supported catalyst, and provides a preparation method of a hydrodesulfurization catalyst, in particular to a novel three-dimensional macroporous cobalt, nickel and molybdenum bulk hydrodesulfurization catalyst which is used for the desulfurization process of oil products and has the advantages of high specific surface area, small mass transfer resistance, high catalytic activity and high utilization rate of the active components.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a hydrodesulfurization catalyst comprises the following steps:
(1) Organic foam pretreatment: ultrasonically cleaning organic foam by using acetone, deionized water and absolute ethyl alcohol respectively, and then drying;
(2) Preparing a precursor mixed solution: dissolving a molybdenum salt, a cobalt salt and/or a nickel salt in a solvent to obtain a solution containing the molybdenum salt, the cobalt salt and/or the nickel salt, and dissolving a surfactant in the solution containing the molybdenum salt, the cobalt salt and/or the nickel salt to obtain a precursor solution;
(3) Preparation of hydrodesulfurization catalyst: and (3) dipping the pretreated organic foam in the precursor solution, and drying and roasting to obtain the hydrodesulfurization catalyst.
In the preparation method provided by the invention, firstly, the organic foam is ultrasonically washed by acetone, deionized water and absolute ethyl alcohol respectively to remove stains, and then is dried; then respectively preparing mixed precursor solutions of molybdenum salt, cobalt salt and/or nickel salt and a surfactant in different proportions; and finally, soaking the cleaned organic foam in a precursor solution, taking out the organic foam after full soaking, drying the organic foam, repeating the drying for a plurality of times, and roasting the organic foam in a tubular furnace to obtain the three-dimensional macroporous hydrodesulfurization catalyst.
Preferably, the solvent in the step (2) is any one or a mixture of several of water, ethanol and methanol.
The beneficial effects of the above technical scheme are as follows: the molybdenum salt, the cobalt salt and the nickel salt used for preparing the precursor mixed solution are easy to dissolve in the water, ethanol and methanol solvent, and meanwhile, the precursor solution prepared by adopting the solvent can fully infiltrate the pore channels of the organic foam, so that the mass transfer resistance of the catalyst is reduced, and the hydrodesulfurization efficiency of the catalyst is improved.
Preferably, the cobalt salt in the step (2) is any one of cobalt nitrate, cobalt chloride and cobalt acetate.
Preferably, the nickel salt in step (2) is any one of nickel nitrate, nickel chloride and nickel acetate.
Preferably, in the step (2), the molybdenum salt is any one of ammonium molybdate and sodium molybdate.
The beneficial effects of the above technical scheme are that: the selected salts are easily dissolved in water, ethanol and methanol, are main catalyst auxiliaries and are beneficial to improving the hydrodesulfurization efficiency of the catalyst.
Preferably, in the step (2), molybdenum salt and cobalt salt are dissolved in the solvent, and the molar ratio of the cobalt salt to the molybdenum salt is 0.5-4.0, preferably 1.0-3.0, and more preferably 2.0;
or dissolving nickel salt and molybdenum salt in a solvent, wherein the molar ratio of the nickel salt to the molybdenum salt is 0.5-4.0, preferably 0.5-2.0, and more preferably 1.0;
or dissolving cobalt salt, nickel salt and molybdenum salt in a solvent, wherein the molar ratio of the cobalt salt to the sum of the nickel salt and the molybdenum salt is 0.5-4.0, preferably 1.0-2.5, more preferably 2.0, and the molar ratio of the nickel salt to the molybdenum salt is 0.5-2.0, preferably 1.0-2.0, more preferably 1.5.
The beneficial effects of the above technical scheme are that: the catalyst prepared by the precursor solution prepared by selecting the salts with proper proportion has the advantages of high catalytic activity and high utilization rate of active components.
Preferably, in the step (2), the surfactant is any one or a mixture of PVP-4000, P123, F127 and CTAB, and the addition amount of the surfactant is 0.1-3.0 wt% of the weight of the solution containing the molybdenum salt, the cobalt salt and/or the nickel salt.
The beneficial effects of the above technical scheme are that: the addition of the surfactant can stabilize salts in the precursor solution, and simultaneously, the active phase in the catalyst is more dispersed, and the utilization rate of the active components is higher.
Preferably, the organic foam is any one of melamine foam and polyurethane foam.
The beneficial effects of the above technical scheme are that: the organic foam has a three-dimensional grid structure with high aperture ratio, excellent sound absorption, flame retardance, heat insulation, heat-resisting stability and the like, in addition, the chemical structure and the three-dimensional net-shaped cross-linking system of the organic foam enable the organic foam to have unique chemical and physical stability, the organic foam cannot be aged and decomposed in weak acid and weak base environments, no residual free formaldehyde exists, and a large number of active groups such as hydroxyl groups, amino groups and the like exist on the surface of the organic foam, so other functional groups are easy to graft.
Preferably, the dipping times are 1 to 4 times, and the dipping time is 1 to 6 hours.
The beneficial effects of the above technical scheme are that: the precursor solution fully infiltrates the organic foam, so that the prepared catalyst has more active sites, the utilization rate of active components is higher, and the hydrodesulfurization activity is obviously improved.
Preferably, the drying in step (3) includes any one of oven drying and vacuum drying, and the drying temperature is: drying at 30-60 deg.C for 4-10 hr.
The beneficial effects of the above technical scheme are that: the drying condition can promote the in-situ solidification of the precursor in the organic foam pore canal and maintain the stability of the catalytic action.
Preferably, the roasting in the step (3) is carried out in a tubular furnace, the temperature is firstly increased from room temperature to 300 ℃ at the heating rate of 1 ℃/min in the nitrogen atmosphere, the roasting is kept for 3 hours, then the temperature is reduced to room temperature at the cooling rate of 2 ℃/min, the temperature is increased to 400-600 ℃ at the heating rate of 1 ℃/min in the air atmosphere, the roasting is kept for 5 hours, and finally the temperature is reduced to room temperature at the cooling rate of 2 ℃/min.
The beneficial effects of the above technical scheme are as follows: and a proper roasting procedure is set to facilitate the removal of organic foam, and the active phase precursor is decomposed in a high-temperature environment to form the hydrodesulfurization catalyst with a three-dimensional pore structure.
According to the technical scheme, compared with the prior art, the preparation method of the hydrodesulfurization catalyst disclosed by the invention has the following beneficial effects:
the hydrodesulfurization catalyst prepared by the method has the advantages of simple preparation process, easy operation, safety and environmental protection, no adverse effect on human bodies and environment caused by used reagents, high catalytic activity, high utilization rate of active components, higher specific surface area, developed pore structure, contribution to the diffusion of sulfur-containing compounds in pore channels, and capability of effectively solving the problems of small loading capacity and low utilization rate of the active components of the existing supported catalyst.
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 obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1:
(1) The melamine foam is divided into square blocks of 2cm multiplied by 0.5cm, ultrasonic washing is respectively carried out by acetone, deionized water and absolute ethyl alcohol, the washing is carried out for 3 times, 15min each time, the melamine foam is cleaned and dried overnight for standby.
(2) And (2) taking 10ml of deionized water as a solvent, adding 3.8804g of cobalt nitrate, 1.1770g of ammonium molybdate and 0.1g of CTAB to prepare a precursor mixed solution, adding the melamine foam prepared in the step (1), soaking for 2 times for 4 hours respectively, and drying in an oven at 30 ℃ for 10 hours respectively.
(3) And (3) roasting the sample prepared in the step (2) in a tubular furnace, firstly heating from room temperature to 300 ℃ at the heating rate of 1 ℃/min in the nitrogen atmosphere, staying for 3 hours, then cooling to room temperature at the cooling rate of 2 ℃/min, then heating to 400 ℃ at the heating rate of 1 ℃/min in the air atmosphere, staying for 5 hours, and finally cooling to room temperature at the cooling rate of 2 ℃/min.
Example 2:
(1) Cutting polyurethane foam into blocks of 2cm × 2cm × 0.5cm, ultrasonically washing with acetone, deionized water and anhydrous ethanol for 3 times, 15min each time, cleaning, and drying overnight.
(2) And (2) taking 10ml of deionized water as a solvent, adding 3.8804g of cobalt nitrate, 1.1770g of ammonium molybdate and 0.1g of CTAB to prepare a precursor mixed solution, adding the polyurethane foam prepared in the step (1), soaking for 2 times, wherein the soaking time is 4 hours respectively, and drying in an oven at 30 ℃ for 10 hours respectively.
(3) And (3) roasting the sample prepared in the step (2) in a tubular furnace, firstly heating from room temperature to 300 ℃ at the heating rate of 1 ℃/min in the nitrogen atmosphere, staying for 3 hours, then cooling to room temperature at the cooling rate of 2 ℃/min, then heating to 400 ℃ at the heating rate of 1 ℃/min in the air atmosphere, staying for 5 hours, and finally cooling to room temperature at the cooling rate of 2 ℃/min.
Example 3:
(1) The melamine foam is divided into blocks of 2cm multiplied by 0.5cm, ultrasonic washing is carried out by acetone, deionized water and absolute ethyl alcohol, each washing is carried out for 3 times, each time is 15min, and the melamine foam is dried overnight for standby.
(2) And (2) taking 10ml of deionized water as a solvent, adding 3.8772g of nickel nitrate, 1.1770g of ammonium molybdate and 0.1g of CTAB to prepare a precursor mixed solution, adding the melamine foam prepared in the step (1), soaking for 2 times for 4 hours respectively, and drying in an oven at 40 ℃ for 10 hours respectively.
(3) And (3) roasting the sample prepared in the step (2) in a tubular furnace, firstly heating from room temperature to 300 ℃ at the heating rate of 1 ℃/min in the nitrogen atmosphere, staying for 3 hours, then cooling to room temperature at the cooling rate of 2 ℃/min, then heating to 400 ℃ at the heating rate of 1 ℃/min in the air atmosphere, staying for 5 hours, and finally cooling to room temperature at the cooling rate of 2 ℃/min.
Example 4:
(1) The melamine foam is divided into blocks of 2cm multiplied by 0.5cm, ultrasonic washing is carried out by acetone, deionized water and absolute ethyl alcohol, each washing is carried out for 3 times, each time is 15min, and the melamine foam is dried overnight for standby.
(2) Taking 10ml of deionized water as a solvent, adding 2.9103g of cobalt nitrate, 1.4540g of nickel nitrate, 0.8828g of ammonium molybdate and 0.1g of CTAB to prepare a precursor, mixing, adding the melamine foam prepared in the step (1), dipping for 2 times for 4 hours respectively, and drying in an oven at 40 ℃ for 10 hours respectively.
(3) And (3) roasting the sample prepared in the step (2) in a tubular furnace, firstly heating to 300 ℃ from room temperature at the heating rate of 1 ℃/min in a nitrogen atmosphere, staying for 3 hours, then cooling to room temperature at the cooling rate of 2 ℃/min, heating to 400 ℃ at the heating rate of 1 ℃/min in an air atmosphere, staying for 5 hours, and finally cooling to room temperature at the cooling rate of 2 ℃/min.
Example 5:
(1) The melamine foam is divided into blocks of 2cm multiplied by 0.5cm, ultrasonic washing is carried out by acetone, deionized water and absolute ethyl alcohol, each washing is carried out for 3 times, each time is 15min, and the melamine foam is dried overnight for standby.
(2) Taking a mixture system of 4.4ml of deionized water and 5.6ml of absolute ethyl alcohol as a solvent, adding 3.8804g of cobalt nitrate, 1.1770g of ammonium molybdate and 0.1g of CTAB to prepare a precursor mixed solution, adding the melamine foam prepared in the step (1), dipping for 2 times for 4 hours respectively, and drying in an oven at 40 ℃ for 10 hours respectively.
(3) And (3) roasting the sample prepared in the step (2) in a tubular furnace, firstly heating to 300 ℃ from room temperature at the heating rate of 1 ℃/min in a nitrogen atmosphere, staying for 3 hours, then cooling to room temperature at the cooling rate of 2 ℃/min, heating to 400 ℃ at the heating rate of 1 ℃/min in an air atmosphere, staying for 5 hours, and finally cooling to room temperature at the cooling rate of 2 ℃/min.
Example 6:
(1) The melamine foam is divided into blocks of 2cm multiplied by 0.5cm, ultrasonic washing is carried out by acetone, deionized water and absolute ethyl alcohol, each washing is carried out for 3 times, each time is 15min, and the melamine foam is dried overnight for standby.
(2) Taking 4.4ml of deionized water and 5.6ml of absolute ethyl alcohol mixed system as a solvent, adding 3.8772g of nickel nitrate, 1.1770g of ammonium molybdate and 0.1g of CTAB to prepare a precursor mixed solution, adding the melamine foam prepared in the step (1), soaking for 2 times for 4 hours respectively, and drying in a 40 ℃ oven for 10 hours respectively.
(3) And (3) roasting the sample prepared in the step (2) in a tubular furnace, firstly heating to 300 ℃ from room temperature at the heating rate of 1 ℃/min in a nitrogen atmosphere, staying for 3 hours, then cooling to room temperature at the cooling rate of 2 ℃/min, heating to 400 ℃ at the heating rate of 1 ℃/min in an air atmosphere, staying for 5 hours, and finally cooling to room temperature at the cooling rate of 2 ℃/min.
Example 7:
(1) The melamine foam is divided into blocks of 2cm multiplied by 0.5cm, ultrasonic washing is carried out by acetone, deionized water and absolute ethyl alcohol, washing is carried out for 3 times and 15min each time, and the blocks are cleaned and dried overnight for standby.
(2) And (2) taking 10ml of deionized water as a solvent, adding 3.8804g of cobalt nitrate, 1.1770g of ammonium molybdate and 0.05g of P123 to prepare a precursor mixed solution, adding the melamine foam prepared in the step (1), soaking for 2 times for 4 hours respectively, and drying in an oven at 40 ℃ for 10 hours respectively.
(3) And (3) roasting the sample prepared in the step (2) in a tubular furnace, firstly heating from room temperature to 300 ℃ at the heating rate of 1 ℃/min in a nitrogen atmosphere, staying for 3 hours, then cooling to room temperature at the cooling rate of 2 ℃/min, then heating to 400 ℃ at the heating rate of 1 ℃/min in an air atmosphere, staying for 5 hours, and finally cooling to room temperature at the cooling rate of 2 ℃/min.
Example 8:
(1) Cutting polyurethane foam into blocks of 2cm × 2cm × 0.5cm, ultrasonically washing with acetone, deionized water and anhydrous ethanol for 3 times, 15min each time, cleaning, and drying overnight.
(2) And (2) taking 10ml of deionized water as a solvent, adding 3.8804g of cobalt nitrate, 1.1770g of ammonium molybdate and 0.05g of P123 to prepare a precursor mixed solution, adding the polyurethane foam prepared in the step (1), soaking for 2 times, wherein the soaking time is 4 hours respectively, and drying in an oven at 40 ℃ for 10 hours respectively.
(3) And (3) roasting the sample prepared in the step (2) in a tubular furnace, firstly heating from room temperature to 300 ℃ at the heating rate of 1 ℃/min in a nitrogen atmosphere, staying for 3 hours, then cooling to room temperature at the cooling rate of 2 ℃/min, then heating to 400 ℃ at the heating rate of 1 ℃/min in an air atmosphere, staying for 5 hours, and finally cooling to room temperature at the cooling rate of 2 ℃/min.
Example 9:
(1) Cutting polyurethane foam into blocks of 2cm × 2cm × 0.5cm, ultrasonically washing with acetone, deionized water and anhydrous ethanol for 3 times, 15min each time, cleaning, and drying overnight.
(2) And (2) taking 10ml of deionized water as a solvent, adding 3.8772g of nickel nitrate, 1.1770g of ammonium molybdate and 0.05g of P123 to prepare a precursor mixed solution, adding the polyurethane foam prepared in the step (1), soaking for 2 times, wherein the soaking time is 4 hours respectively, and drying in an oven at 40 ℃ for 10 hours respectively.
(3) And (3) roasting the sample prepared in the step (2) in a tubular furnace, firstly heating to 300 ℃ from room temperature at the heating rate of 1 ℃/min in a nitrogen atmosphere, staying for 3 hours, then cooling to room temperature at the cooling rate of 2 ℃/min, then heating to 400 ℃ in an air atmosphere at the heating rate of 1 ℃/min, staying for 5 hours, and finally cooling to room temperature at the cooling rate of 2 ℃/min.
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 (8)
1. A preparation method of a hydrodesulfurization catalyst is characterized by comprising the following steps:
(1) Organic foam pretreatment: ultrasonically cleaning organic foam with acetone, deionized water and absolute ethyl alcohol respectively, and drying;
(2) Preparing a precursor mixed solution: dissolving a molybdenum salt, a cobalt salt and/or a nickel salt in a solvent to obtain a solution containing the molybdenum salt, the cobalt salt and/or the nickel salt, and dissolving a surfactant in the solution containing the molybdenum salt, the cobalt salt and/or the nickel salt to obtain a precursor solution;
(3) Preparation of hydrodesulfurization catalyst: dipping the pretreated organic foam in the precursor solution, and drying and roasting to obtain a hydrodesulfurization catalyst;
the organic foam in the step (1) is any one of melamine foam and polyurethane foam;
the surfactant in the step (2) is any one or a mixture of PVP-4000, P123, F127 and CTAB;
the roasting in the step (3) is carried out in a tubular furnace, firstly the temperature is increased from room temperature to 300 ℃ at the heating rate of 1 ℃/min in the nitrogen atmosphere, the roasting is kept for 3 hours, then the temperature is reduced to room temperature at the cooling rate of 2 ℃/min, the temperature is increased to 400-600 ℃ at the heating rate of 1 ℃/min in the air atmosphere, the roasting is kept for 5 hours, and finally the temperature is reduced to room temperature at the cooling rate of 2 ℃/min.
2. The method for preparing a hydrodesulfurization catalyst according to claim 1, wherein the solvent in step (2) is any one or a mixture of water, ethanol and methanol.
3. The method of claim 1, wherein the cobalt salt in step (2) is any one of cobalt nitrate, cobalt chloride and cobalt acetate.
4. The method for preparing a hydrodesulfurization catalyst according to claim 1, wherein the nickel salt in step (2) is any one of nickel nitrate, nickel chloride and nickel acetate.
5. The method of claim 1, wherein the molybdenum salt in step (2) is any one of ammonium molybdate and sodium molybdate.
6. The method of claim 1, wherein in the step (2), molybdenum salt and cobalt salt are dissolved in the solvent, and the molar ratio of the cobalt salt to the molybdenum salt is 0.5-4.0;
or dissolving nickel salt and molybdenum salt in a solvent, wherein the molar ratio of the nickel salt to the molybdenum salt is 0.5-4.0;
or dissolving cobalt salt, nickel salt and molybdenum salt in a solvent, wherein the molar ratio of the cobalt salt to the sum of the nickel salt and the molybdenum salt is 0.5-4.0, and the molar ratio of the nickel salt to the molybdenum salt is 0.5-2.0.
7. The method of claim 1, wherein the surfactant is added in an amount of 0.1wt% to 3.0wt% based on the weight of the solution containing the molybdenum salt, cobalt salt and/or nickel salt.
8. The method for preparing a hydrodesulfurization catalyst according to claim 1, wherein the drying in the step (3) comprises any one of oven drying and vacuum drying.
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| US20210024436A1 (en) * | 2019-07-24 | 2021-01-28 | King Fahd University Of Petroleum And Minerals | Hydrodesulfurization catalyst with a zeolite-graphene material composite support and methods thereof |
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