CN114425344A - Catalyst and preparation method and application thereof - Google Patents

Catalyst and preparation method and application thereof Download PDF

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Publication number
CN114425344A
CN114425344A CN202011027021.4A CN202011027021A CN114425344A CN 114425344 A CN114425344 A CN 114425344A CN 202011027021 A CN202011027021 A CN 202011027021A CN 114425344 A CN114425344 A CN 114425344A
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catalyst
gas
oxide
methane
powder
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邵芸
赵清锐
武洁花
刘东兵
张明森
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
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
    • 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
    • B01J23/83—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 rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/864—Removing carbon monoxide or hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/108—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide

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  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a catalyst and a preparation method and application thereof. The preparation raw materials of the catalyst comprise: 100 parts by weight of catalyst powder, 0.5-8 parts by weight of extrusion aid, 5-20 parts by weight of adhesive and 24-38 parts by weight of peptizing agent, wherein the mass concentration of the peptizing agent is 2.9-8%, and the catalyst powder is prepared by adding Ce in CexZr1‑xO2Loading active components on the powder and roasting to obtain the catalyst. The catalyst prepared by the method has high mechanical strength, high conversion rate for carbon monoxide and hydrogen in the methane oxidative coupling tail gas, and low conversion rate for methane, so that the methane which is not completely reacted in the tail gas can be used as a raw material gas to continue the reaction.

Description

Catalyst and preparation method and application thereof
Technical Field
The invention relates to a catalyst, a preparation method and application thereof, in particular to application of the catalyst in removing carbon monoxide and hydrogen in tail gas of methane oxidative coupling reaction.
Background
The Oxidative Coupling of Methane (OCM) technology is a process for preparing ethylene by directly oxidative dehydrogenation of methane as a raw material under the action of a catalyst and high temperature (more than 600 ℃).
In the OCM technology, about 50 wt% of methane is converted into ethylene and ethane as main products and hydrogen, carbon monoxide and carbon dioxide as by-products after a single pass of each feedstock through the catalyst bed. The main by-products of the reactor output material after removal of carbon dioxide and separation of ethylene and ethane are carbon monoxide, hydrogen and unreacted methane.
CN108137435A discloses a process for oxidative coupling of methane, in particular, comprising a reaction step comprising treating a gas stream comprising methane and oxygen under methane oxidative coupling conditions to obtain a gas stream comprising methane, ethane and ethylene; a first adsorption step comprising contacting the gas stream comprising methane, ethane and ethylene resulting from the reaction step with an adsorbent having a lower affinity for methane than for ethane and a lower affinity for ethane than for ethylene, resulting in ethane and ethylene being adsorbed by the adsorbent, obtaining a gas stream comprising methane and ethane; a first desorption step comprising desorbing ethane and ethylene adsorbed in the first adsorption step obtaining a gas stream comprising ethane and ethylene; a second adsorption step comprising contacting the gas stream comprising methane and ethane resulting from the first adsorption step with an adsorbent having a lower affinity for methane than for ethane, resulting in ethane being adsorbed by the adsorbent and obtaining a gas stream comprising methane; a second desorption step comprising desorbing ethane adsorbed in the second adsorption step obtaining a gas stream comprising ethane; and optionally a recovery step comprising recovering the methane comprising gas stream resulting from the second adsorption step to the reaction step. Which recovers unreacted methane by means of adsorption-desorption, mainly involving the treatment of a gas stream comprising methane and oxygen under methane oxidative coupling conditions, with the aim of obtaining a gas stream comprising methane, ethane and ethylene.
The selective catalytic oxidation technology can be used for purifying OCM tail gas, so that after the OCM tail gas passes through a catalyst bed layer at a certain temperature, carbon monoxide and hydrogen are oxidized, and methane is not consumed or is rarely consumed. The purified methane and fresh methane are fed together, so that the utilization efficiency of the methane is improved.
For industrial heterogeneous catalysts it is desirable to have the necessary mechanical strength. The catalyst forming process is one of the important steps in the industrial catalyst preparation process. So far, the forming mode of the catalyst carrier suitable for the purification treatment of the OCM tail gas is not reported.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a catalyst, and a preparation method and application thereof. The catalyst provided by the invention has enough mechanical strength, can better remove carbon monoxide and hydrogen in the tail gas of the methane oxidative coupling reaction, and has low conversion rate to methane.
The first aspect of the present invention provides a catalyst, wherein the preparation raw material of the catalyst comprises:
Figure BDA0002702424150000021
the mass concentration of the peptizing agent is 2.9-8%.
According to a preferred embodiment of the catalyst of the present invention, the preparation raw materials comprise:
Figure BDA0002702424150000022
the mass concentration of the peptizing agent is 2.9-8%.
According to some embodiments of the catalyst of the present invention, the catalyst powder is prepared by adding cerium oxide to CexZr1-xO2The powder is loaded with active components and is obtained by roasting. In the present invention, the supporting method may be an immersion method or a precipitation method.
According to a preferred embodiment of the catalyst of the present invention, the active component accounts for 5 to 10 wt% of the catalyst powder.
According to some embodiments of the catalyst of the present invention, the active component is selected from at least one of group VB metal oxides, group VIB metal oxides, group VIIB metal oxides, group VIII metal oxides, and group IB metal oxides.
According to a preferred embodiment of the catalyst of the present invention, the active component is selected from at least one of iron oxide, copper oxide, manganese oxide, cobalt oxide, nickel oxide and chromium oxide.
According to a preferred embodiment of the catalyst of the present invention, the active component is selected from at least one of iron oxide, manganese oxide and copper oxide.
According to a particular embodiment of the catalyst according to the invention, the active component is copper oxide.
According to some embodiments of the catalyst of the present invention, the CexZr1-xO2The powder is prepared from water-soluble cerium salt and water-soluble zirconium salt by a coprecipitation method, a sol-gel method or a hydrothermal method.
According to a preferred embodiment of the catalyst of the present invention, the water-soluble cerium salt is at least one selected from the group consisting of cerium nitrate, cerium ammonium nitrate, cerium sulfate and cerium chloride.
According to a preferred embodiment of the catalyst of the present invention, the water-soluble zirconium salt is selected from at least one of zirconium oxychloride, zirconium chloride, zirconium sulfate and zirconium nitrate.
According to a preferred embodiment of the catalyst of the present invention, CexZr1-xO2Wherein x is 0.1 to 0.7. Such as 0.1, 0.3, 0.4, 0.5, 0.7, and any value therebetween.
According to a preferred embodiment of the catalyst of the present invention, CexZr1-xO2Wherein x is 0.1 to 0.5.
According to some embodiments of the catalyst of the present invention, the extrusion aid is selected from at least one of talc, graphite, stearic acid, stearate, starch, and sesbania powder.
According to the specific embodiment of the catalyst, the extrusion aid is sesbania powder.
According to some embodiments of the catalyst of the present invention, the binder is selected from at least one of water glass, silica sol and aluminum sol.
According to a preferred embodiment of the catalyst according to the invention, the binder is an aluminium sol.
According to a particular embodiment of the catalyst according to the invention, the binder is pseudoboehmite.
According to some embodiments of the catalyst of the present invention, the peptizing agent is selected from at least one of hydrochloric acid, nitric acid, formic acid, acetic acid, citric acid, malonic acid, and trichloroacetic acid.
According to a particular embodiment of the catalyst of the invention, the peptizing agent is nitric acid.
According to some embodiments of the catalyst of the present invention, the mass concentration of the peptizing agent is 2.9% to 8%. Such as 2.9%, 4.5%, 5.1%, 6.2%, 7.7%, 8%, and any value in between.
According to some embodiments of the catalyst of the present invention, the mechanical strength of the catalyst is > 30N/pellet. In the present invention, the method for testing the mechanical strength of the catalyst may be: the mechanical strength of 50 catalysts with a length of 3mm and a diameter of 2mm was measured using a particle strength meter, and the average mechanical strength was calculated.
In different embodiments of the present invention, catalysts of different specifications can be prepared according to different needs. For example, the diameter of the catalyst can be 2mm, the length can be 3mm, and the mechanical strength of the catalyst can reach more than 30N/particle by adopting a particle strength tester. Therefore, the catalyst has higher mechanical strength, can obviously improve the stability, and can be recycled.
In a second aspect, the present invention provides a method for preparing a catalyst, comprising the steps of:
step A, kneading catalyst powder, extrusion aid, adhesive and peptizing agent to obtain a mixture;
step B, extruding and molding the mixture to obtain a wet molding body;
and step C, drying the wet formed body, and then roasting to obtain the catalyst.
According to some embodiments of the method of manufacturing of the present invention, step a further comprises: at CexZr1-xO2And loading an active component on the powder and roasting to obtain the catalyst powder. In the present invention, the supporting method may be an immersion method or a precipitation method.
According to a preferable embodiment of the preparation method of the present invention, the active component accounts for 5 to 10 wt% of the catalyst powder.
According to some embodiments of the method of making of the present invention, the active component is selected from at least one of a group VB metal oxide, a group VIB metal oxide, a group VIIB metal oxide, a group VIII metal oxide, and a group IB metal oxide.
According to a preferred embodiment of the production method of the present invention, the active component is selected from at least one of iron oxide, copper oxide, manganese oxide, cobalt oxide, nickel oxide, and chromium oxide.
According to a preferred embodiment of the production method of the present invention, the active component is selected from at least one of iron oxide, manganese oxide, and copper oxide.
According to a particular embodiment of the preparation process according to the invention, the active component is copper oxide.
According to a preferred embodiment of the production method of the present invention, CexZr1-xO2Wherein x is 0.1 to 0.7. Such as 0.1, 0.3, 0.4, 0.5, 0.7, and any value therebetween.
According to a preferred embodiment of the production method of the present invention, CexZr1-xO2Wherein x is 0.1 to 0.5.
According to some embodiments of the preparation method of the present invention, the weight ratio of the catalyst powder, the extrusion aid, the binder and the peptizing agent is 100: 0.5-8: 5-20: 24 to 38.
According to a preferred embodiment of the preparation method, the weight ratio of the catalyst powder, the extrusion aid, the adhesive and the peptizing agent is 100: 2-6: 8-16: 26 to 34.
According to some embodiments of the method of manufacturing of the present invention, the extrusion aid is selected from at least one of talc, graphite, stearic acid, stearate, starch, and sesbania powder.
According to the specific implementation mode of the preparation method, the extrusion aid is sesbania powder.
According to some embodiments of the method of manufacturing of the present invention, the binder is selected from at least one of water glass, silica sol, and aluminum sol.
According to a preferred embodiment of the production method of the present invention, the binder is an aluminum sol.
According to a particular embodiment of the preparation process according to the invention, the binder is pseudoboehmite.
According to some embodiments of the method of manufacturing of the present invention, the peptizing agent is selected from at least one of hydrochloric acid, nitric acid, formic acid, acetic acid, citric acid, malonic acid, and trichloroacetic acid.
According to a specific embodiment of the preparation method of the present invention, the peptizing agent is nitric acid.
According to a preferred embodiment of the preparation method of the present invention, the mass concentration of the peptizing agent is 2.9% to 8%. Such as 2.9%, 4.5%, 5.1%, 6.2%, 7.7%, 8%, and any value in between.
According to some embodiments of the method of preparing of the present invention, the calcination conditions during the preparation of the catalyst powder in step a include: the temperature is 200-1000 ℃, and the time is 2-10 h.
According to a preferred embodiment of the preparation method of the present invention, the firing conditions in step a include: the temperature is 400-700 ℃, and the time is 4-8 h.
According to a specific embodiment of the preparation method of the present invention, the calcination conditions in step a include: the temperature is 600 ℃ and the time is 5 h.
According to some embodiments of the method of manufacturing of the present invention, the firing conditions in step C include: the temperature is 200-1000 ℃, and the time is 2-10 h.
According to a preferred embodiment of the preparation method of the present invention, the firing conditions in step C include: the temperature is 400-700 ℃, and the time is 4-8 h.
According to a specific embodiment of the preparation method of the present invention, the firing conditions in step C include: the temperature is 600 ℃ and the time is 5 h.
In a third aspect, the present invention provides a catalyst obtained according to the above-mentioned preparation method.
According to some embodiments of the catalyst of the present invention, the mechanical strength of the catalyst is > 30N/pellet as measured using a particle strength tester.
The fourth aspect of the invention provides a method for purifying and treating tail gas of methane oxidative coupling reaction, which comprises the following steps: the exhaust gas is passed through the above-mentioned catalyst.
According to some embodiments of the purification treatment method of the present invention, the composition of the methane oxidative coupling reaction off-gas is: the volume ratio of methane to carbon monoxide to hydrogen is 12-18: 2-5: 1.
according to a preferred embodiment of the purification treatment method of the present invention, the composition of the methane oxidative coupling reaction off-gas is: the volume ratio of methane to carbon monoxide to hydrogen is 15-17: 2-4: 1.
according to some embodiments of the purification process of the present invention, the conditions of the purification process include: the space velocity is 10-200L/h.g catalyst, and the temperature is 200-700 ℃. In the present invention, "L/h.g.catalyst" means "L/(h.g.catalyst)".
According to a preferred embodiment of the purification treatment method of the present invention, the conditions of the purification treatment method include: the space velocity is 13-150L/h.g catalyst, and the temperature is 350-600 ℃.
According to a preferred embodiment of the method for purifying and treating off-gas of the present invention, the conversion rate of carbon monoxide in the off-gas is greater than 85%, the conversion rate of hydrogen is greater than 90%, and the conversion rate of methane is less than 3%.
The purification treatment process is data of the tail gas after passing through the catalyst bed layer once, and in different embodiments of the invention, the tail gas can be selected to pass through the catalyst bed layer for multiple times according to different purification requirements.
The fifth aspect of the invention provides an application of the catalyst and the preparation method thereof in the treatment of the tail gas of the oxidative coupling reaction of methane, and more preferably in the removal of carbon monoxide and hydrogen in the tail gas of the oxidative coupling reaction of methane. But is not limited thereto.
The catalyst can better remove carbon monoxide and hydrogen in the tail gas of the methane oxidative coupling reaction. When the tail gas of the oxidative coupling reaction of methane passes through the catalyst bed layer once, the conversion rate of carbon monoxide in the tail gas of the reaction is more than 85 percent, the conversion rate of hydrogen is more than 90 percent, and the conversion rate of methane is less than 3 percent.
The invention has the beneficial effects that:
the catalyst prepared by the invention has enough mechanical strength and can better remove carbon monoxide and hydrogen in the tail gas of the methane oxidative coupling reaction. After the tail gas of the oxidative coupling reaction of methane passes through the catalyst bed layer once, the conversion rate of carbon monoxide in the tail gas is more than 85 percent, the conversion rate of hydrogen is more than 90 percent, and the conversion rate of methane is less than 3 percent, so that the methane which is not completely reacted can be conveyed to the reaction kettle for continuous reaction.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
The test method and the equipment used in the test are as follows:
(1) the method for testing the conversion of carbon monoxide, methane and hydrogen is gas chromatography.
(2) The extruder is a twin-screw extruder with the production model of F-26, which is purchased from manufacturing companies of science and technology industry headquarters of south China university.
(3) The particle strength meter is a digital display particle strength meter with the model of KC-2A, which is purchased from manufacturing companies of analytical instruments in Jiangsu Jiangyan.
The various starting reagents used in the present invention are commercially available.
[ example 1 ]
10.5g of copper nitrate hexahydrate was weighed and dissolved in water, and 50g of Ce prepared by coprecipitation method was added thereto0.1Zr0.9O2Stirred at room temperature for 5 h. The resulting solution was evaporated to dryness in a water bath at 80 ℃ and then dried overnight at 120 ℃. After drying, the mixture is heated to 600 ℃ at the speed of 5 ℃/min in the air and roasted for 5h to obtain the catalyst powder.
50g of catalyst powder, 3.05g of sesbania powder, 5.99g of pseudo-boehmite and 14.99g of nitric acid with the mass concentration of 5.1% were kneaded in a bar extruder for 20min, and then extruded through a 2mm phi orifice plate to obtain a wet molded article in the form of a long strip.
And drying the wet formed body in the air, raising the temperature to 600 ℃ at the speed of 5 ℃/min, and roasting for 5h to obtain the catalyst.
The mechanical strength of 50 catalysts having a length of 3mm and a diameter of 2mm was measured by a particle strength meter, and the average mechanical strength was calculated to be 39.4N/particle.
A quartz glass tube reactor having an inner diameter of 8mm was charged with 0.21g of the catalyst. Moreover, 20-40 meshes of quartz sand is filled in the upper part and the lower part of the catalyst. Introducing nitrogen gas with flow rate of 40ml/min and oxygen gas with flow rate of 4ml/min, heating to 600 deg.C at rate of 10 deg.C/min, and maintaining for 30min to activate the catalyst.
The nitrogen and the oxygen are switched into byproduct reaction gas for catalytic conversion. Wherein the byproduct reaction gas contains CO 15 vol% and H25 vol%, and the balance being methane. After the catalytic conversion reaction was carried out for 60min, the CO conversion and CH were measured by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
[ example 2 ]
14.9g of copper nitrate hexahydrate were weighed out and dissolved in water, and 50g of Ce prepared by the sol-gel method was added thereto0.3Zr0.7O2Stirred at room temperature for 5 h. The resulting solution was evaporated to dryness in a water bath at 80 ℃ and then dried overnight at 120 ℃. After drying, the mixture is heated to 600 ℃ at the speed of 5 ℃/min in the air and roasted for 5h to obtain the catalyst powder.
50g of catalyst powder, 3.07g of sesbania powder, 4.11g of pseudo-boehmite and 15.01g of nitric acid with the mass concentration of 5.1% were kneaded in a plodder for 20min, and then extruded through a 2mm phi orifice plate to obtain a wet molded article in the form of a long strand.
And drying the wet formed body in the air, raising the temperature to 600 ℃ at the speed of 5 ℃/min, and roasting for 5h to obtain the catalyst.
The mechanical strength of 50 catalysts having a length of 3mm and a diameter of 2mm was measured by a particle strength meter, and the average mechanical strength was calculated to be 30.7N/particle.
A quartz glass tube reactor having an inner diameter of 8mm was charged with 0.20g of the catalyst. Moreover, 20-40 meshes of quartz sand is filled in the upper part and the lower part of the catalyst. Introducing nitrogen gas with flow rate of 40ml/min and oxygen gas with flow rate of 4ml/min, heating to 600 deg.C at rate of 10 deg.C/min, and maintaining for 30min to activate the catalyst.
The nitrogen and the oxygen are switched into byproduct reaction gas for catalytic conversion. Wherein the byproduct reaction gas contains CO 15 vol% and H2 5vol％And the balance being methane. After the catalytic conversion reaction was carried out for 60min, the CO conversion and CH were measured by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
[ example 3 ]
7.9g of copper nitrate hexahydrate were weighed out and dissolved in water, and 50g of hydrothermal Ce was added thereto0.5Zr0.5O2Stirred at room temperature for 5 h. The resulting solution was evaporated to dryness in a water bath at 80 ℃ and then dried overnight at 120 ℃. After drying, the mixture is heated to 600 ℃ at the speed of 5 ℃/min in the air and roasted for 5h to obtain the catalyst powder.
50g of catalyst powder, 2.98g of sesbania powder, 8.03g of pseudo-boehmite and 15.03g of nitric acid with the mass concentration of 5.1% were kneaded in a bar extruder for 20min, and then extruded through a 2mm phi orifice plate to obtain a wet molded article in the form of a long strip.
And drying the wet formed body in the air, raising the temperature to 600 ℃ at the speed of 5 ℃/min, and roasting for 5h to obtain the catalyst.
The mechanical strength of 50 catalysts having a length of 3mm and a diameter of 2mm was measured by a particle strength meter, and the average mechanical strength was calculated to be 45.8N/particle.
A quartz glass tube reactor having an inner diameter of 8mm was charged with 0.22g of the catalyst. Moreover, 20-40 meshes of quartz sand is filled in the upper part and the lower part of the catalyst. Introducing nitrogen gas with flow rate of 40ml/min and oxygen gas with flow rate of 4ml/min, heating to 600 deg.C at rate of 10 deg.C/min, and maintaining for 30min to activate the catalyst.
The nitrogen and the oxygen are switched into byproduct reaction gas for catalytic conversion. Wherein the byproduct reaction gas contains CO 15 vol% and H25 vol%, and the balance being methane. After the catalytic conversion reaction was carried out for 60min, the CO conversion and CH were measured by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
[ example 4 ]
14.9g of copper nitrate hexahydrate were weighed out and dissolved in water, and 50g of Ce prepared by the sol-gel method was added thereto0.4Zr0.6O2Stirred at room temperature for 5 h. 1mol/L ammonia water is dripped into the obtained solutionThe solution was stirred for a further 30min to a solution pH of 10, filtered and the filter cake was washed with distilled water and then dried at 120 ℃ overnight. After drying, the mixture is heated to 600 ℃ at the speed of 5 ℃/min in the air and roasted for 5h to obtain the catalyst powder.
50g of catalyst powder, 1.56g of sesbania powder, 4.03g of pseudo-boehmite and 16.73g of nitric acid with the mass concentration of 2.9% were kneaded in a plodder for 20min, and then extruded through a 2mm phi orifice plate to obtain a wet molded article in the form of a long strand.
And drying the wet formed body in the air, raising the temperature to 600 ℃ at the speed of 5 ℃/min, and roasting for 5h to obtain the catalyst.
The mechanical strength of 50 catalysts having a length of 3mm and a diameter of 2mm was measured by a particle strength meter, and the average mechanical strength was calculated to be 30.7N/particle.
A quartz glass tube reactor having an inner diameter of 8mm was charged with 0.21g of the catalyst. Moreover, 20-40 meshes of quartz sand is filled in the upper part and the lower part of the catalyst. Introducing nitrogen gas with flow rate of 40ml/min and oxygen gas with flow rate of 4ml/min, heating to 600 deg.C at rate of 10 deg.C/min, and maintaining for 30min to activate the catalyst.
The nitrogen and the oxygen are switched into byproduct reaction gas for catalytic conversion. Wherein the byproduct reaction gas contains CO 15 vol% and H25 vol%, and the balance being methane. After the catalytic conversion reaction was carried out for 60min, the CO conversion and CH were measured by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
[ example 5 ]
14.9g of copper nitrate hexahydrate was weighed out and dissolved in water, and 50g of Ce prepared by coprecipitation method was added thereto0.1Zr0.9O2Stirred at room temperature for 5 h. The resulting solution was evaporated to dryness in a water bath at 80 ℃ and then dried overnight at 120 ℃. After drying, the mixture is heated to 600 ℃ at the speed of 5 ℃/min in the air and roasted for 5h to obtain the catalyst powder.
50g of catalyst powder, 3.77g of sesbania powder, 4.08g of pseudo-boehmite and 13.15g of nitric acid with the mass concentration of 7.7% were kneaded in a plodder for 20min, and then extruded through a 2mm phi orifice plate to obtain a wet molded article in the form of a long strand.
And drying the wet formed body in the air, raising the temperature to 600 ℃ at the speed of 5 ℃/min, and roasting for 5h to obtain the catalyst.
The mechanical strength of 50 catalysts having a length of 3mm and a diameter of 2mm was measured by a particle strength meter, and the average mechanical strength was calculated to be 30.1N/particle.
A quartz glass tube reactor having an inner diameter of 8mm was charged with 0.20g of the catalyst. Moreover, 20-40 meshes of quartz sand is filled in the upper part and the lower part of the catalyst. Introducing nitrogen gas with flow rate of 40ml/min and oxygen gas with flow rate of 4ml/min, heating to 600 deg.C at rate of 10 deg.C/min, and maintaining for 30min to activate the catalyst.
The nitrogen and the oxygen are switched into byproduct reaction gas for catalytic conversion. Wherein the byproduct reaction gas contains CO 15 vol% and H25 vol%, and the balance being methane. After the catalytic conversion reaction was carried out for 60min, the CO conversion and CH were measured by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
Comparative example 1
14.9g of copper nitrate hexahydrate was weighed out and dissolved in water, and 50g of Ce prepared by coprecipitation method was added thereto0.1Zr0.9O2Stirred at room temperature for 5 h. The resulting solution was evaporated to dryness in a water bath at 80 ℃ and then dried overnight at 120 ℃. After drying, the mixture is heated to 600 ℃ at the speed of 5 ℃/min in the air and roasted for 5h to obtain the catalyst powder.
50g of catalyst powder, 1.30g of sesbania powder, 3.54g of pseudo-boehmite and 17.12g of nitric acid with the mass concentration of 2.5% were kneaded in a bar extruder for 20min, and then extruded through a 2mm phi orifice plate to obtain a wet molded article in the form of a long strip.
And drying the wet formed body in the air, raising the temperature to 600 ℃ at the speed of 5 ℃/min, and roasting for 5h to obtain the catalyst.
The mechanical strength of 50 catalysts having a length of 3mm and a diameter of 2mm was measured by a particle strength meter, and the average mechanical strength was calculated to be 23.7N/particle.
A quartz glass tube reactor having an inner diameter of 8mm was charged with 0.21g of the catalyst. Moreover, 20-40 meshes of quartz sand is filled in the upper part and the lower part of the catalyst. Introducing nitrogen gas with flow rate of 40ml/min and oxygen gas with flow rate of 4ml/min, heating to 600 deg.C at rate of 10 deg.C/min, and maintaining for 30min to activate the catalyst.
The nitrogen and the oxygen are switched into byproduct reaction gas for catalytic conversion. Wherein the byproduct reaction gas contains CO 15 vol% and H25 vol%, and the balance being methane. After the catalytic conversion reaction was carried out for 60min, the CO conversion and CH were measured by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
Comparative example 2
3.0g of copper nitrate hexahydrate was weighed out and dissolved in water, and 50g of Ce prepared by coprecipitation method was added thereto0.1Zr0.9O2Stirred at room temperature for 5 h. The resulting solution was evaporated to dryness in a water bath at 80 ℃ and then dried overnight at 120 ℃. After drying, the mixture is heated to 600 ℃ at the speed of 5 ℃/min in the air and roasted for 5h to obtain the catalyst powder.
50g of catalyst powder, 4.50g of sesbania powder, 10.21g of pseudo-boehmite and 10.91g of nitric acid with the mass concentration of 9.7% were kneaded in a plodder for 20min, and then extruded through a 2mm phi orifice plate to obtain a wet molded article in the form of a long strand.
And drying the wet formed body in the air, raising the temperature to 600 ℃ at the speed of 5 ℃/min, and roasting for 5h to obtain the catalyst.
The mechanical strength of 50 catalysts having a length of 3mm and a diameter of 2mm was measured by a particle strength meter, and the average mechanical strength was calculated to be 57.2N/particle.
A quartz glass tube reactor having an inner diameter of 8mm was charged with 0.21g of the catalyst. Moreover, 20-40 meshes of quartz sand is filled in the upper part and the lower part of the catalyst. Introducing nitrogen gas with flow rate of 40ml/min and oxygen gas with flow rate of 4ml/min, heating to 600 deg.C at rate of 10 deg.C/min, and maintaining for 30min to activate the catalyst.
The nitrogen and the oxygen are switched into byproduct reaction gas for catalytic conversion. Wherein the byproduct reaction gas contains CO 15 vol% and H25 vol%, and the balance being methane. After the catalytic conversion reaction was carried out for 60min, the CO conversion and CH were measured by gas chromatography4Conversion and H2The conversion, the test results are shown in Table 1.
TABLE 1
Figure BDA0002702424150000111
The embodiment and the comparative example show that the catalyst prepared by the invention has high mechanical strength, high conversion rate for carbon monoxide and hydrogen in the tail gas of the oxidative coupling reaction of methane, and low conversion rate for methane, so that the unreacted methane in the tail gas can be used as the raw material gas for continuous reaction.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent variations and modifications can be made by those skilled in the art based on the technical teaching provided by the present invention, and the protection scope of the present invention should be considered.

Claims (10)

1. A catalyst, characterized in that the raw materials for preparing the catalyst comprise:
Figure FDA0002702424140000011
the mass concentration of the peptizing agent is 2.9-8%.
2. The catalyst of claim 1 wherein the catalyst powder is prepared by reaction at CexZr1-xO2Loading active components on the powder and roasting to obtain the active component; preferably, the active component accounts for 5-10 wt% of the catalyst powder; and/or the presence of a gas in the gas,
the active component is selected from at least one of VB group metal oxide, VIB group metal oxide, VIIB group metal oxide, VIII group metal oxide and IB group metal oxide; preferably, the active component is selected from at least one of iron oxide, copper oxide, manganese oxide, cobalt oxide, nickel oxide, and chromium oxide; more preferably, the active component is selected from at least one of iron oxide, manganese oxide and copper oxide; more preferably, the active component is copper oxide.
3. The catalyst according to claim 2, wherein the Ce isxZr1-xO2The powder is prepared from water-soluble cerium salt and water-soluble zirconium salt by a coprecipitation method, a sol-gel method or a hydrothermal method;
preferably, the water-soluble cerium salt is selected from at least one of cerium nitrate, ammonium cerium nitrate, cerium sulfate and cerium chloride; preferably, the water-soluble zirconium salt is selected from at least one of zirconium oxychloride, zirconium chloride, zirconium sulfate and zirconium nitrate; and/or the presence of a gas in the gas,
preferably, CexZr1-xO2Wherein x is 0.1-0.7; more preferably, x is 0.1 to 0.5.
4. The catalyst according to any one of claims 1 to 3, wherein the extrusion aid is selected from at least one of talc, graphite, stearic acid, stearate, starch and sesbania powder; and/or the presence of a gas in the gas,
the adhesive is selected from at least one of water glass, silica sol and aluminum sol; preferably, the binder is an alumina sol, more preferably pseudo-boehmite; and/or the presence of a gas in the gas,
the peptizing agent is at least one selected from hydrochloric acid, nitric acid, formic acid, acetic acid, citric acid, malonic acid and trichloroacetic acid.
5. A preparation method of a catalyst is characterized by comprising the following steps:
step A, kneading catalyst powder, extrusion aid, adhesive and peptizing agent to obtain a mixture;
step B, extruding and molding the mixture to obtain a wet molding body;
and step C, drying the wet formed body, and then roasting to obtain the catalyst.
6. The method according to claim 5, wherein the step A further comprises: at CexZr1-xO2Loading active components on the powder and roasting to obtain the catalyst powder;
preferably, the active component accounts for 5-10 wt% of the catalyst powder, and is selected from at least one of group VB metal oxide, group VIB metal oxide, group VIIB metal oxide, group VIII metal oxide and group IB metal oxide; preferably, the active component is selected from at least one of iron oxide, copper oxide, manganese oxide, cobalt oxide, nickel oxide, and chromium oxide; more preferably, the active component is selected from at least one of iron oxide, manganese oxide and copper oxide; more preferably, the active component is copper oxide; and/or the presence of a gas in the gas,
preferably, CexZr1-xO2Wherein x is 0.1-0.7; more preferably, x is 0.1 to 0.5; and/or the presence of a gas in the gas,
the weight ratio of the catalyst powder, the extrusion aid, the adhesive and the peptizing agent is 100: 0.5-8: 5-20: 24-38; preferably, the weight ratio of the catalyst powder, the extrusion aid, the adhesive and the peptizing agent is 100: 2-6: 8-16: 26 to 34; and/or the presence of a gas in the gas,
the roasting conditions in the step A comprise: the temperature is 400-700 ℃, and the time is 4-8 h; and/or the presence of a gas in the gas,
the roasting conditions in the step C comprise: the temperature is 400-700 ℃, and the time is 4-8 h.
7. A catalyst obtained by the production method according to claim 5 or 6.
8. A method for purifying and treating tail gas of methane oxidative coupling reaction comprises the following steps: passing the exhaust gas over a catalyst as claimed in any one of claims 1 to 4 and claim 7;
preferably, the composition of the tail gas of the oxidative coupling reaction of methane is as follows: the volume ratio of methane to carbon monoxide to hydrogen is 12-18: 2-5: 1; more preferably, the composition of the tail gas of the oxidative coupling reaction of methane is as follows: the volume ratio of methane to carbon monoxide to hydrogen is 15-17: 2-4: 1; and/or the presence of a gas in the gas,
preferably, the conditions of the purification treatment method include: the space velocity is 10-200L/h.g catalyst, and the temperature is 200-700 ℃;
more preferably, the conditions of the purification treatment method include: the space velocity is 13-150L/h.g catalyst, and the temperature is 350-600 ℃.
9. The method according to claim 8, wherein the conversion rate of carbon monoxide in the tail gas is more than 85%, the conversion rate of hydrogen is more than 90%, and the conversion rate of methane is less than 3%.
10. Use of the catalyst according to any one of claims 1 to 4 and 7, or the method for preparing the catalyst according to claim 5 or 6, in the treatment of the tail gas of the oxidative coupling of methane, more preferably in the removal of carbon monoxide and hydrogen from the tail gas of the oxidative coupling of methane.
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