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CN113083312B - Carbon monoxide conversion catalyst and preparation method thereof - Google Patents

Carbon monoxide conversion catalyst and preparation method thereof Download PDF

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Publication number
CN113083312B
CN113083312B CN201911335819.2A CN201911335819A CN113083312B CN 113083312 B CN113083312 B CN 113083312B CN 201911335819 A CN201911335819 A CN 201911335819A CN 113083312 B CN113083312 B CN 113083312B
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catalyst
temperature
solution
deionized water
catalyst according
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CN113083312A (en
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王金利
蔡进
朱艳芳
徐本刚
吴学其
张�杰
黄先亮
吴�琳
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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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
    • B01J23/002—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
    • B01J23/70—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
    • B01J23/80—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 zinc, cadmium or mercury
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1076—Copper or zinc-based catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1094—Promotors or activators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
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  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The invention belongs to the technical field of catalysts, and particularly relates to a carbon monoxide conversion catalyst and a preparation method thereof. The catalyst comprises Cu, zn, al and an auxiliary agent, wherein the auxiliary agent is one or a mixture of Li, na, K, rb and La. The catalyst comprises 30-40% of Cu, 1.2-1.5:1 of Cu-Zn mol ratio, 6.5-8.5% of Al and 10-12% of auxiliary agent. In the preparation of the catalyst, the structural auxiliary agent is added and a step-by-step precipitation method process is adopted, so that the catalyst has higher heat resistance and selectivity.

Description

Carbon monoxide conversion catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a carbon monoxide conversion catalyst and a preparation method thereof.
Background
Copper-based low-temperature shift catalysts were used for synthesis gas production in 1963, and are widely used in ammonia plants and hydrogen plants in the future with the development of gas purification technologies.
The existing copper-based shift catalyst mainly comprises copper, zinc and aluminum, is generally only suitable for shift reactions with low temperature (180-220 ℃) and low CO content (< 5 vol%) and has the defects of poor heat resistance and low selectivity for shift reactions with higher reaction temperature and higher CO content. Some researchers have also attempted to add other adjuvants to the system to improve the performance of the catalyst, especially to enhance its heat resistance and selectivity.
Chinese patent CN108114724a discloses a method for preparing a carbon monoxide water vapor shift low temperature catalyst. The catalyst comprises Cu-Zn/gamma-Al 2O3, the Cu content is 20-40wt%, the molar ratio of copper to zinc is 1:1, and the catalyst is prepared by adopting a fractional precipitation method, and is subjected to water vapor shift reaction in typical reformed gas, so that the catalyst has higher activity and stability.
Chinese patent CN105536803a discloses a copper-based carbon monoxide medium temperature shift catalyst and a preparation method thereof. The catalyst takes copper salt, zinc salt and aluminum salt as active components, and the preparation process adopts a coprecipitation method process and special equipment.
Chinese patent CN106179360a discloses a copper zinc aluminum catalyst and a method for preparing the same. The catalyst composition was CuO, znO, al 2 O 3 The difference compared with the traditional precipitation method is that the organic solvent is added in the dissolution of the precipitant.
Chinese patent CN101786000a discloses a carbon monoxide shift catalyst and a method for preparing the same. The catalyst composition is added with boron group element compounds on the basis of copper-zinc-aluminum series, and the catalyst is prepared by adopting a coprecipitation method.
In the existing research, the heat resistance of the catalyst is improved to a certain extent, but the selectivity of the catalyst is still low, so that the market popularization and the use of the catalyst product are influenced, and a shift catalyst with high heat resistance and high selectivity is urgently required to be developed to meet the shift reaction requirement.
Disclosure of Invention
The invention aims to provide a preparation method of a copper-based carbon monoxide conversion catalyst with relatively high heat resistance and high selectivity.
The catalyst composition is characterized in that other auxiliary agents are introduced on the basis of proper copper-zinc molar ratio, so that the heat resistance of the catalyst is enhanced, and the selectivity of the catalyst is enhanced by adopting fractional precipitation of each component.
The invention provides a carbon monoxide conversion catalyst, which comprises Cu, zn, al and an auxiliary agent; the auxiliary agent is one or a mixture of Li, na, K, rb and La.
The catalyst composition contains Cu 20-45 wt%, preferably 30-40 wt%, cu-Zn 1.0-1.7:1, preferably 1.2-1.5:1, al 5-10 wt%, preferably 6.5-8.5 wt%, and assistant 7-15 wt%, preferably 10-12 wt%.
The catalyst of the invention is prepared by adopting a distributed precipitation method, and the specific preparation steps are as follows:
(1) Adding copper nitrate solution into the prepared alkaline precipitant at a constant speed of 40-60ml/min for precipitation, neutralizing at 55-65 ℃, and aging for 0.2-0.4h at a final pH value of 7.0-7.1;
(2) Adding the mixed solution of zinc nitrate and auxiliary salt into the prepared alkaline precipitant at a constant speed of 50-70ml/min for neutralization precipitation, wherein the neutralization temperature is 55-65 ℃, the end point pH value is 7.1-7.3, and aging is carried out for 0.2-0.4h;
(3) Mixing the material obtained in the step (1) and the material obtained in the step (2), and stirring for 0.1-0.3h at 55-65 ℃;
(4) Naturally settling and washing the material obtained in the step (3) by deionized water, adding alumina powder, and pulping for 0.3-0.5h;
(5) And carrying out suction filtration, drying, grinding, granulating, roasting and tabletting on the pulped material to obtain the catalyst.
The auxiliary salt used in the preparation of the catalyst is one or a mixture of a plurality of nitrate, carbonate and hydroxide corresponding to the auxiliary.
In the catalyst preparation step, the copper nitrate solution in the step (1) is preferably added into the prepared alkaline precipitant at a constant speed of 55-60ml/min for neutralization precipitation.
In the catalyst preparation step, the mixed solution of the zinc nitrate and the auxiliary agent salt in the step (2) is preferably 65-70 percent
And adding the mixture into the prepared alkaline precipitant at a constant speed in ml/min for precipitation.
In the catalyst preparation step, the neutralization temperature in the step (1) is preferably 55-60 ℃.
In the catalyst preparation step, the neutralization temperature in the step (2) is preferably 60-65 ℃.
In the catalyst preparation step, the material obtained in the step (4) is subjected to natural sedimentation washing for 6 times by deionized water.
In the catalyst preparation step, the drying temperature in the step (5) is 95-110 ℃, the drying time is 6-10h, the roasting temperature is 290-330 ℃, and the roasting time is 2-3h.
The invention has the following effects: in the preparation process of the catalyst, the heat resistance and the selectivity of the catalyst are enhanced by adding other auxiliary agents and adopting a component fractional precipitation process.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments.
Example 1
(1) Putting 87.5g of sodium carbonate and 1.75L of deionized water into a reaction kettle A with a stirring paddle and water bath heating to prepare a solution with the temperature of 55 ℃, adding 140g of copper nitrate and deionized water to prepare 1L of copper nitrate solution with the temperature of 55 ℃, adding the copper nitrate solution into the solution of the reaction kettle A with the temperature of 55 ℃ at a constant speed of 55ml/min, stirring and ageing for 0.4h at the end point pH value of 7.0 and the temperature of 55 ℃;
(2) Putting 87.5g of sodium carbonate and 1.75L of deionized water into a reaction kettle B with stirring paddles and water bath heating to prepare a solution with the temperature of 60 ℃, preparing a mixed solution with the temperature of 60 ℃ from 11.2g of potassium hydroxide, 15.0g of auxiliary salt of lanthanum nitrate and 95g of zinc nitrate and deionized water, adding the mixed solution into the solution of the reaction kettle B with the temperature of 60 ℃ at a constant speed of 65ml/min, stirring and aging for 0.2h at the end point pH value of 7.3 under the condition of 60 ℃;
(3) Mixing the material obtained in the step (1) and the material obtained in the step (2), and stirring for 0.3h at 55 ℃;
(4) Washing the material obtained in the step (3) by deionized water for 6 times through natural sedimentation, and adding 25g of alumina powder to pulp for 0.3h;
(5) And (3) carrying out suction filtration on the pulped material, drying the pulped material in an oven with the temperature set to 105 ℃ for 7 hours, grinding the pulped material, granulating the pulped material, roasting the pulped material in a muffle furnace with the temperature set to 320 ℃ for 2.5 hours, and finally tabletting and forming the pulped material to obtain a catalyst sample 1.
Example 2
(1) Putting 87.5g of sodium carbonate and 1.75L of deionized water into a reaction kettle A with a stirring paddle and water bath heating to prepare a solution with the temperature of 58 ℃, adding 130g of copper nitrate and deionized water to prepare 1L of copper nitrate solution with the temperature of 58 ℃, adding the copper nitrate solution into the solution of the reaction kettle A with the temperature of 58 ℃ at a constant speed of 58ml/min, stirring and ageing for 0.3h at the end point pH value of 7.1 and the temperature of 58 ℃;
(2) Putting 87.5g of sodium carbonate and 1.75L of deionized water into a reaction kettle B with stirring paddles and water bath heating to prepare a solution with the temperature of 62 ℃, preparing a mixed solution with the temperature of 62 ℃ from 23.84g of lithium nitrate, 10.5g of auxiliary salt of potassium hydroxide and 100g of zinc nitrate and deionized water, adding the mixed solution into the solution of the reaction kettle B with the temperature of 62 ℃ at a constant speed of 70ml/min, stirring and aging for 0.3h at the end point pH value of 7.2 under the condition of 62 ℃;
(3) Mixing the material obtained in the step (1) and the material obtained in the step (2), and stirring for 0.2h at 58 ℃;
(4) Washing the material obtained in the step (3) by deionized water for 6 times through natural sedimentation, and adding 28g of alumina powder to pulp for 0.4h;
(5) And (3) carrying out suction filtration on the pulped material, drying the pulped material for 9 hours in an oven with the temperature set to be 100 ℃, grinding the material, granulating, roasting the material in a muffle furnace with the temperature set to be 325 ℃ for 2 hours, and finally tabletting and forming to obtain a catalyst sample 2.
Example 3
(1) Putting 87.5g of sodium carbonate and 1.75L of deionized water into a reaction kettle A with a stirring paddle and water bath heating to prepare a solution with the temperature of 60 ℃, adding 125g of copper nitrate and deionized water into 1L of copper nitrate solution with the temperature of 60 ℃, adding the copper nitrate solution into the solution of the reaction kettle A with the temperature of 60 ℃ at a constant speed of 60ml/min, stirring and ageing for 0.2h at the end point pH value of 7.1 and the temperature of 60 ℃;
(2) Putting 87.5g of sodium carbonate and 1.75L of deionized water into a reaction kettle B with a stirring paddle and water bath heating to prepare a solution with the temperature of 65 ℃, preparing 1L of mixed solution with the temperature of 65 ℃ from 10g of potassium hydroxide, 7.5g of lanthanum nitrate, 11.8g of auxiliary salt of cesium carbonate and 105g of zinc nitrate and deionized water, adding the mixed solution into the solution of the reaction kettle B with the temperature of 65 ℃ at a constant speed of 60ml/min, stirring and aging for 0.2h under the condition of 65 ℃ at the end point pH value of 7.3;
(3) Mixing the material obtained in the step (1) and the material obtained in the step (2), and stirring for 0.1h at 60 ℃;
(4) Washing the material obtained in the step (3) by deionized water for 6 times through natural sedimentation, and adding 30g of alumina powder to pulp for 0.3h;
(5) And (3) carrying out suction filtration on the pulped material, drying the pulped material in an oven with the temperature set to 110 ℃ for 6 hours, grinding the pulped material, granulating the pulped material, roasting the pulped material in a muffle furnace with the temperature set to 315 ℃ for 2.5 hours, and finally tabletting and forming the pulped material to obtain a catalyst sample 3.
Example 4
(1) Putting 87.5g of sodium carbonate and 1.75L of deionized water into a reaction kettle A with a stirring paddle and water bath heating to prepare a solution with the temperature of 62 ℃, adding 155g of copper nitrate and deionized water to prepare 1L of copper nitrate solution with the temperature of 62 ℃, adding the copper nitrate solution into the solution of the reaction kettle A with the temperature of 62 ℃ at a constant speed of 50ml/min, stirring and ageing for 0.3h at the end point pH value of 7.0 and the temperature of 62 ℃;
(2) Putting 87.5g of sodium carbonate and 1.75L of deionized water into a reaction kettle B with stirring paddles and water bath heating to prepare a solution with the temperature of 58 ℃, preparing a mixed solution with the temperature of 58 ℃ from 9.0g of potassium hydroxide, 12.0g of auxiliary salt of sodium carbonate and 102g of zinc nitrate and deionized water, adding the mixed solution into the solution of the reaction kettle B with the temperature of 58 ℃ at a constant speed of 60ml/min, stirring and aging for 0.3h at the end point pH value of 7.3 under the condition of 58 ℃;
(3) Mixing the material obtained in the step (1) and the material obtained in the step (2), and stirring for 0.3h at 58 ℃;
(4) Washing the material obtained in the step (3) by deionized water for 6 times through natural sedimentation, and adding 25g of alumina powder to pulp for 0.4h;
(5) And (3) carrying out suction filtration on the pulped material, drying the pulped material in an oven with the temperature set to 95 ℃ for 10 hours, grinding the pulped material, granulating the pulped material, roasting the pulped material in a muffle furnace with the temperature set to 330 ℃ for 2 hours, and finally tabletting and forming the pulped material to obtain a catalyst sample 4.
Example 5
(1) Putting 87.5g of sodium carbonate and 1.75L of deionized water into a reaction kettle A with a stirring paddle and water bath heating to prepare a solution with the temperature of 65 ℃, adding 110g of copper nitrate and deionized water into 1L of copper nitrate solution with the temperature of 65 ℃, adding the copper nitrate solution into the solution of the reaction kettle A with the temperature of 65 ℃ at a constant speed of 40ml/min, stirring and ageing for 0.4h at the end point pH value of 7.0;
(2) Putting 87.5g of sodium carbonate and 1.75L of deionized water into a reaction kettle B with stirring paddles and water bath heating to prepare a solution with the temperature of 55 ℃, preparing a mixed solution with the temperature of 55 ℃ from 15.5g of potassium nitrate, 12.5g of auxiliary salt of rubidium nitrate and 105g of zinc nitrate and deionized water, adding the mixed solution into the solution of the reaction kettle B with the temperature of 55 ℃ at a constant speed of 60ml/min, stirring and aging for 0.4h at the end point pH value of 7.3 under the condition of 55 ℃;
(3) Mixing the material obtained in the step (1) and the material obtained in the step (2), and stirring for 0.2h at 55 ℃;
(4) Washing the material obtained in the step (3) by deionized water for 6 times through natural sedimentation, and adding 35g of alumina powder to pulp for 0.3h;
(5) And (3) carrying out suction filtration on the pulped material, drying the pulped material in an oven with the temperature set to 110 ℃ for 6 hours, grinding the pulped material, granulating the pulped material, roasting the pulped material in a muffle furnace with the temperature set to 300 ℃ for 3 hours, and finally tabletting and forming the pulped material to obtain a catalyst sample 5.
Example 6
(1) Putting 87.5g of sodium carbonate and 1.75L of deionized water into a reaction kettle A with a stirring paddle and water bath heating to prepare a solution with the temperature of 58 ℃, adding 150g of copper nitrate and deionized water into 1L of copper nitrate solution with the temperature of 58 ℃, adding the copper nitrate solution into the solution of the reaction kettle A with the temperature of 58 ℃ at a constant speed of 53ml/min, stirring and ageing for 0.4h at the end point pH value of 7.0 and the temperature of 58 ℃;
(2) Putting 87.5g of sodium carbonate and 1.75L of deionized water into a reaction kettle B with stirring paddles and water bath heating to prepare a solution with the temperature of 58 ℃, preparing a mixed solution with the temperature of 58 ℃ from 12.5g of auxiliary salt of potassium hydroxide and 90g of zinc nitrate and deionized water, adding the mixed solution into the solution of the reaction kettle B with the temperature of 58 ℃ at a constant speed of 60ml/min, stirring and aging for 0.3h at the temperature of 58 ℃;
(3) Mixing the material obtained in the step (1) and the material obtained in the step (2), and stirring for 0.3h at 58 ℃;
(4) Washing the material obtained in the step (3) by deionized water for 6 times through natural sedimentation, and adding 25g of alumina powder to pulp for 0.5h;
(5) And (3) carrying out suction filtration on the pulped material, drying for 8 hours in an oven with the temperature set to 105 ℃, grinding and granulating, roasting for 2.5 hours in a muffle furnace with the temperature set to 315 ℃, and finally tabletting and forming to obtain a catalyst sample 6.
Example 7
(1) Putting 87.5g of sodium carbonate and 1.75L of deionized water into a reaction kettle A with a stirring paddle and water bath heating to prepare a solution with the temperature of 62 ℃, adding 120g of copper nitrate and deionized water to prepare 1L of copper nitrate solution with the temperature of 62 ℃, adding the copper nitrate solution into the solution of the reaction kettle A with the temperature of 62 ℃ at a constant speed of 60ml/min, stirring and ageing for 0.3h at the end point pH value of 7.0 and the temperature of 62 ℃;
(2) Putting 87.5g of sodium carbonate and 1.75L of deionized water into a reaction kettle B with stirring paddles and water bath heating to prepare a solution with the temperature of 60 ℃, preparing a mixed solution with the temperature of 60 ℃ from 15.0g of lanthanum nitrate, 10.6g of auxiliary salt of cesium carbonate and 95g of zinc nitrate and deionized water, adding the mixed solution into the solution of the reaction kettle B with the temperature of 60 ℃ at a constant speed of 60ml/min, stirring and aging for 0.3h at the end point pH value of 7.3 under the condition of 60 ℃;
(3) Mixing the material obtained in the step (1) and the material obtained in the step (2), and stirring for 0.3h at 60 ℃;
(4) Washing the material in the step (3) by deionized water for 6 times through natural sedimentation, and adding 35g of alumina powder to pulp for 0.5h;
(5) And (3) carrying out suction filtration on the pulped material, drying for 7.5 hours in an oven with the temperature set to 105 ℃, grinding and granulating, roasting for 3 hours in a muffle furnace with the temperature set to 295 ℃, and finally tabletting and forming to obtain a catalyst sample 7.
Example 8
(1) Putting 87.5g of sodium carbonate and 1.75L of deionized water into a reaction kettle A with a stirring paddle and water bath heating to prepare a solution with the temperature of 60 ℃, adding 160g of copper nitrate and deionized water to prepare 1L of copper nitrate solution with the temperature of 60 ℃, adding the copper nitrate solution into the solution of the reaction kettle A with the temperature of 60 ℃ at a constant speed of 50ml/min, stirring and ageing for 0.4h at the end point pH value of 7.1 and the temperature of 60 ℃;
(2) Putting 87.5g of sodium carbonate and 1.75L of deionized water into a reaction kettle B with stirring paddles and water bath heating to prepare a solution with the temperature of 62 ℃, preparing a mixed solution with the temperature of 62 ℃ from 12.0g of potassium nitrate, 26.2g of auxiliary salt of lanthanum nitrate and 110g of zinc nitrate and deionized water, adding the mixed solution into the solution of the reaction kettle B with the temperature of 62 ℃ at a constant speed of 60ml/min, stirring and aging for 0.3h at the end point pH value of 7.3 under the condition of 62 ℃;
(3) Mixing the material obtained in the step (1) and the material obtained in the step (2), and stirring for 0.3h at 60 ℃;
(4) Washing the material obtained in the step (3) by deionized water for 6 times through natural sedimentation, and adding 24g of alumina powder to pulp for 0.3h;
(5) And (3) carrying out suction filtration on the pulped material, drying for 8 hours in an oven with the temperature set to 100 ℃, grinding and granulating, roasting for 2.5 hours in a muffle furnace with the temperature set to 320 ℃, and finally tabletting and forming to obtain a catalyst sample 8.
Comparative example 1
Prepared as described in example 2 of patent CN108114724 a.
(1) 4.274g of sodium carbonate is weighed and put into a 100ml volumetric flask, distilled water is added for shaking up and volume fixing, and the sodium carbonate is used as a precipitant for standby. 1.155g of zinc sulfate (ZnSO) were weighed out 4 ·7H 2 O) is placed in a 100ml beaker, 50ml distilled water is added for dissolution, and then 0.105g of industrial grade gamma-aluminum oxide (gamma-Al) is added 2 O 3 ) Slowly dropwise adding a sodium carbonate solution into the solution containing the zinc salt at room temperature, continuously stirring until the end point is pH=9, stopping dropwise adding to obtain zinc hydroxide suspension, and continuously stirring for 40min after the dropwise adding is finished.
(2) 0.945g of copper nitrate ((Cu (NO) 3 ) 2 ·3H 2 O) was placed in a 100ml beaker and dissolved by adding 50ml distilled water. Slowly dripping a precipitator sodium carbonate solution and the Cu salt solution into zinc hydroxide suspension at the same time, continuously stirring in the process of dripping at the same time, and controlling the pH value to be about 8; continuously dropwise adding a precipitant sodium carbonate solution when the dropwise adding of the copper salt is finished, wherein the pH value of the precipitant sodium carbonate solution is 9; stirring the obtained suspension in a water bath at 60 ℃ for 2 hours, filtering, and washing with distilled water until the pH is 7; drying the solid in an oven at 80 ℃ for 12-24 hours to obtain a precipitate precursor; calcining the precipitate precursor in air atmosphere at 400 ℃ for 2 hours to obtain Cu-Zn/gamma-Al 2 O 3 (SP) control 1.
Comparative example 2
Prepared as described in example 1 of patent CN106179360 a.
Dissolving 73.5g of sodium carbonate in 800ml of water to obtain a solution I, adding 200ml of methanol into the solution I to obtain a solution II, and heating the solution II to 55 ℃; 72.9g of copper nitrate (Cu (NO) 3 ) 2 ﹒3H 2 O) and 73.1g of zinc nitrate (Zn (NO) 3 ) 2 ﹒6H 2 O) dissolving in 500ml of water, marking as a solution III, adding the solution III into the solution II, and stirring in a dropwise manner; after completion of precipitation, 9.2g of aluminum hydroxide (Al (OH) was added 3 ) Filtering, washing and drying, then burning for 5h at 350 ℃, and the roasted product is subjected toAfter granulation, 3% graphite was mixed again, and the mixture was tabletted to give comparative sample 1.
The results of the relevant performance tests of the samples prepared in 8 examples of the present invention and comparative examples are shown in the following table 1.
Catalyst performance test conditions:
a fixed bed reactor, catalyst crushing granularity of 0.85-2.0mm, catalyst loading of 40ml and feed gas composition (v/v%): CO 10%, CO 2 10%、H 2 65%、CH 4 15%, steam-gas ratio (steam/dry gas mole ratio) 0.40, reaction pressure 3.0MPa, airspeed 2500 h -1 The inlet temperature is 220-260 ℃. The catalyst needs to be reduced and activated before use: reducing atmosphere N 2 /H 2 Mixed gas (H) 2 Accounting for 10 percent and the balance of N 2 ) The method comprises the steps of carrying out a first treatment on the surface of the Reduction pressure: normal pressure; space velocity of reduction 800 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The temperature programming is slowly increased to 250 ℃ and stays for 2.0h (the temperature increasing rate is 1.5 ℃/3 min). Heat-resistant conditions: the atmosphere of the raw material gas is normal pressure, 400 ℃ and 5.0h.
The CO conversion calculation formula:
E=×100
wherein: phi 1 : CO volume fraction in the feed gas%
Φ 2 : the volume fraction of CO in the outlet gas (product gas)%.
Table 1 samples prepared in examples and comparative examples were heat resistant and CO conversion (%)
Sample of Heat-resistant at an inlet temperature of 220 DEG C After the inlet temperature is 220 DEG C Heat-resistant at an inlet temperature of 260 DEG C After the inlet temperature is 260 DEG C
Sample 1 93.4 92.0 92.5 90.8
Sample 2 93.5 91.9 93.1 90.6
Sample 3 94.0 91.8 93.2 91.1
Sample 4 91.0 89.2 90.8 88.5
Sample 5 90.2 88.9 89.6 88.5
Sample 6 91.5 88.8 91.2 88.6
Sample 7 91.0 89.0 90.9 88.7
Sample 8 90.2 88.5 89.9 88.2
Comparative sample 1 89.4 84.5 88.7 83.7
Comparative sample 2 86.2 83.5 85.8 82.1
Note that: heat-resistant conditions: the atmosphere of the raw material gas is normal pressure, 400 ℃ and 5.0h.
Table 2 impurity contents of samples prepared in examples and comparative examples
Note that: a1 and A2 are the methanol content in the liquid phase product of the comparative sample 2.
From the data in table 1, it can be seen that: the catalyst prepared by the invention has stronger heat resistance due to the addition of Li, na, K, rb, la and other auxiliary agents, and the CO conversion rate is higher than the level of a comparison sample no matter the CO conversion rate is as low as more than 89.5% before and after heat resistance within the range of 220-260 ℃.
From the data in table 2, it can be seen that: the catalyst prepared by the invention reduces the content of methanol impurity in the liquid phase product in the analysis of the catalyst sample by adopting a component distribution precipitation process, improves the selectivity of the catalyst, and has higher selectivity than the level of a comparison sample.
The present invention and its embodiments have been described in detail by way of illustration and not limitation, and it should be understood by those skilled in the art that the present invention is not limited to the embodiments and examples described herein without departing from the spirit and scope of the invention.

Claims (9)

1. A carbon monoxide conversion catalyst is characterized in that the catalyst comprises Cu, zn, al and an auxiliary agent, wherein the mass content of Cu in the catalyst is 25% -45%, the molar ratio of Cu to Zn is 1.0-1.7:1, the mass content of Al is 5% -10%, and the mass content of the auxiliary agent is 7% -15%; the auxiliary agent is one or a mixture of Li, na, K, rb and La;
the catalyst is prepared by adopting a fractional precipitation method, and the specific preparation steps are as follows:
(1) Adding copper nitrate solution into the prepared alkaline precipitant at a constant speed of 40-60mL/min for neutralization precipitation, wherein the neutralization temperature is 55-65 ℃, the end point pH value is 7.0-7.1, and aging is carried out for 0.2-0.4h;
(2) Adding the mixed solution of zinc nitrate and auxiliary agent salt into the prepared alkaline precipitant at a constant speed of 50-70mL/min for precipitation, neutralizing at 55-65 ℃, finishing pH value of 7.1-7.3, and aging for 0.2-0.4h;
(3) Mixing the material obtained in the step (1) and the material obtained in the step (2), and stirring for 0.1-0.3h at 55-65 ℃;
(4) Naturally settling and washing the material obtained in the step (3) by deionized water, adding alumina powder, and pulping for 0.3-0.5h;
(5) And carrying out suction filtration, drying, grinding, granulating, roasting and tabletting on the pulped material to obtain the catalyst.
2. The catalyst according to claim 1, wherein the mass content of Cu is 30-40%, the molar ratio of Cu to Zn is 1.2-1.5:1, the mass content of Al is 6.5-8.5%, and the mass content of auxiliary agent is 10-12%.
3. The catalyst according to claim 1, wherein the auxiliary salt is one or a mixture of nitrate, carbonate and hydroxide corresponding to the auxiliary.
4. The catalyst according to claim 1, wherein the copper nitrate solution in the step (1) is added into the prepared alkaline precipitant at a constant speed of 55-60mL/min for neutralization precipitation.
5. The catalyst according to claim 1, wherein the mixed solution of zinc nitrate and auxiliary salt in the step (2) is added into the prepared alkaline precipitant at a constant speed of 65-70mL/min for neutralization precipitation.
6. The catalyst according to claim 1, wherein the neutralization temperature in step (1) is 55-60 ℃.
7. The catalyst according to claim 1, wherein the neutralization temperature in step (2) is 60-65 ℃.
8. The catalyst according to claim 1, wherein the material obtained in step (4) is washed by 6 natural sedimentation with deionized water.
9. The catalyst according to claim 1, wherein in step (5) the drying temperature is 95-110 ℃, the drying time is 6-10 hours, the calcination temperature is 290-330 ℃, and the calcination time is 2-3 hours.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1493398A (en) * 2003-08-29 2004-05-05 南化集团研究院 Copper series carbon oxide low temperature conversion catalyst and its preparation method and use
CN101455965A (en) * 2009-01-04 2009-06-17 上海大学 Low water-gas ratio transformation catalyst in hydrogen rich gas and preparation method thereof
CN105854888A (en) * 2016-04-15 2016-08-17 西安向阳航天材料股份有限公司 Copper-based low-temperature conversion catalyst and preparation method thereof
CN107583650A (en) * 2016-07-07 2018-01-16 南京科技职业学院 A kind of copper-based carbon-oxide high-temperature conversion catalyst
CN107597125A (en) * 2017-10-25 2018-01-19 山东齐鲁科力化工研究院有限公司 A kind of Catalysts of Dehydrogenation Secondary Butand of the potassium containing solid-state and preparation method thereof
CN107774263A (en) * 2016-08-31 2018-03-09 中国石油化工股份有限公司 A kind of preparation method of catalst for synthesis of methanol
CN108114724A (en) * 2017-12-22 2018-06-05 安徽工业大学 The preparation method of carbon monoxide water-gas shift low temperature catalyst

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1493398A (en) * 2003-08-29 2004-05-05 南化集团研究院 Copper series carbon oxide low temperature conversion catalyst and its preparation method and use
CN101455965A (en) * 2009-01-04 2009-06-17 上海大学 Low water-gas ratio transformation catalyst in hydrogen rich gas and preparation method thereof
CN105854888A (en) * 2016-04-15 2016-08-17 西安向阳航天材料股份有限公司 Copper-based low-temperature conversion catalyst and preparation method thereof
CN107583650A (en) * 2016-07-07 2018-01-16 南京科技职业学院 A kind of copper-based carbon-oxide high-temperature conversion catalyst
CN107774263A (en) * 2016-08-31 2018-03-09 中国石油化工股份有限公司 A kind of preparation method of catalst for synthesis of methanol
CN107597125A (en) * 2017-10-25 2018-01-19 山东齐鲁科力化工研究院有限公司 A kind of Catalysts of Dehydrogenation Secondary Butand of the potassium containing solid-state and preparation method thereof
CN108114724A (en) * 2017-12-22 2018-06-05 安徽工业大学 The preparation method of carbon monoxide water-gas shift low temperature catalyst

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
La助剂对甲醇水蒸气转化制氢CuO-ZnO/Al_2O_3催化剂性能的影响;蔡迎春等;《石油化工》;20010620(第06期);全文 *
新型铜系低变催化剂在低汽气比条件下的性能研究;周莲凤等;《工业催化》;20060428(第04期);全文 *
沉淀方法对铜基甲醇合成催化剂性能影响的研究;国海光等;《浙江化工》;20040130(第01期);全文 *
沉淀法制备铜基甲醇合成催化剂的研究;郭彦鑫;《化工中间体》;20100715(第07期);全文 *
高选择性低汽气比一氧化碳低温变换催化剂的研究;吴结华等;《化学工业与工程技术》;20050630(第03期);全文 *

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