CN111686738B - Preparation method of copper-zinc catalyst - Google Patents

Preparation method of copper-zinc catalyst Download PDF

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CN111686738B
CN111686738B CN201910182534.3A CN201910182534A CN111686738B CN 111686738 B CN111686738 B CN 111686738B CN 201910182534 A CN201910182534 A CN 201910182534A CN 111686738 B CN111686738 B CN 111686738B
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acid
catalyst
copper
aging
mixed solution
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CN111686738A (en
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王海涛
徐学军
王继锋
刘东香
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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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
    • B01J35/394—
    • B01J35/615—
    • B01J35/633—
    • B01J35/635—
    • B01J35/643—
    • B01J35/647—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
    • 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
    • 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

Abstract

The invention discloses a preparation method of a copper-zinc catalyst, which comprises the following steps: (1) Carrying out parallel flow gelling reaction on the mixed solution A and a sodium metaaluminate solution to obtain slurry I, and then aging; (2) Dropwise adding the mixed solution B and a sodium carbonate solution into the aged slurry I obtained in the step (1) in a parallel manner, carrying out gelling reaction to obtain slurry II, and then aging; (3) Filtering and drying the material obtained in the step (2), and then treating the material by using a mixed aqueous solution containing aluminum salt and organic acid; (4) preparing the material obtained in the step (3) into a catalyst product; the mixed solution A is an aqueous solution containing soluble copper salt, soluble zinc salt and organic auxiliary agent, and the mixed solution B is an aqueous solution containing soluble copper salt and soluble aluminum salt. The catalyst prepared by the method has the advantages of uniform distribution of active metals, good synergistic effect, large number of active metal active centers, improvement of the activity, selectivity and thermal stability of the catalyst, and good application prospect.

Description

Preparation method of copper-zinc catalyst
Technical Field
The invention relates to a preparation method of a copper-zinc catalyst, in particular to a preparation method of a copper-zinc catalyst with high activity, high selectivity and good heat resistance.
Background
Industrially, methanol generally contains H 2 、CO、CO 2 The synthesis gas of (a) is produced under conditions of pressure, temperature and presence of a catalyst. At present, methanol is synthesized by adopting a medium-pressure and low-pressure gas phase method in the world, and the used catalyst is basically mixed oxide of copper, zinc and aluminum. CuO, znO and Al in synthetic methanol catalyst 2 O 3 The three components have different functions, cuO is used as a main active component, znO and Al 2 O 3 Is an auxiliary agent. The addition of ZnO can enable the catalyst to form Cu/Zn synergetics, greatly improve the activity and selection of the catalystSelectivity, al 2 O 3 Not only has skeleton function in the catalyst, but also can disperse active components in the catalyst to make CO 2 The adsorption and conversion rate are improved, and a proper amount of Al is added into the copper-based catalyst 2 O 3 Can improve catalyst CO 2 Selectivity of synthesizing methanol by hydrogenation.
Cu/ZnO/Al 2 O 3 The activity of the catalyst is closely related to the distribution and the morphology of metals, and when the composition and the content of the catalyst are not changed, the Cu-ZnO synergistic effect and the Cu dispersibility in the catalyst play an important role in the catalytic activity and the selectivity. The catalytic theory considers that the Cu/ZnO catalyst has double active points, the oxygen vacancy on ZnO also has important influence on the catalytic performance of the catalyst (Cu-ZnO synergistic effect), the number of the oxygen vacancy is increased, the interaction between Cu and ZnO is enhanced, and the conversion rate of carbon monoxide and the selectivity of methanol are increased. The dispersion performance and oxygen vacancy of the Cu/ZnO catalyst are closely related to the composition and preparation method of the catalyst, and how to improve the dispersion degree of active components of the catalyst in the preparation process of the catalyst achieves the purposes of improving the synergistic effect between the Cu and ZnO catalysts and increasing the reaction active center, so that the activity of the catalyst is improved, and the selectivity of the catalyst is improved, and the Cu/ZnO catalyst is a research focus of a copper-based catalyst.
At present, cu/ZnO/Al 2 O 3 The synthesis method of the catalyst comprises a precipitation method, an impregnation method and a sol-gel method, and in general, in industry, a coprecipitation method (including a parallel flow method, a reverse addition method and a forward addition coprecipitation method) is firstly used for generating mixed basic carbonate of copper and zinc, then aluminum hydroxide is added in the pulping process, and the generated pulp is washed by water, dried, roasted and tabletted to form. At present, the improvement of catalyst preparation is generally in the aspects of adding auxiliary agents, selecting carriers, investigating different preparation methods, optimizing reaction conditions and the like, and the problems of poor thermal stability, low selectivity and short service life of a copper-based catalyst are solved by changing the proportion and the dispersion degree of catalyst components and the size of crystal grains, increasing the number of active sites in the catalyst, optimizing the synergistic effect of the active components and the auxiliary agents and increasing the specific surface area of the catalyst to improve the activity of the catalyst. Different preparation methods of the catalyst, different dispersion degrees of the obtained copper and metal activityThe synergistic effect between the sexual center copper and the auxiliary agent is different, and the performance of the obtained catalyst is greatly different.
CN107185543 discloses a catalyst for synthesizing methanol by carbon dioxide hydrogenation, the catalyst is a mixture of Cu and ZnO in filiform or cylindrical form, soluble zinc salt and mineralizer are dissolved in deionized water, the solution is put in a high-pressure reaction kettle, the temperature is kept at 60-150 ℃ for 1-6 h, then the solution is slowly cooled to room temperature, white precipitate is obtained, and ZnO in different forms is obtained after drying; adding soluble copper salt and prepared ZnO into deionized water, adding a reducing agent for reaction, washing and drying to obtain the Cu/ZnO catalyst.
CN 1660490A discloses a preparation method of a methanol synthesis catalyst, wherein a small amount of surfactant OP is added in the preparation process of a coprecipitation method. CN101733109, a method for preparing a copper-based methanol synthesis catalyst, adding an auxiliary agent (one or more of ethylene glycol, diethylamine, glycerol, magnesium stearate, and activated carbon) during the precipitation process. In the method, the organic reagent is added in the precipitation process to improve the Cu-ZnO synergistic effect, but the improvement of the dispersion of the catalyst metal by the organic reagent is limited, and the Cu-ZnO synergistic effect is not obviously improved.
CN101327431 discloses a preparation method of a synthetic methanol catalyst, which comprises the steps of firstly preparing a copper-zinc coprecipitate, secondly preparing a zinc-aluminum coprecipitate with a spinel structure, thirdly preparing a copper-aluminum coprecipitate, then mixing and aging the three coprecipitates, then washing, drying, roasting, adding graphite tablets into the roasted material, and thus obtaining the synthetic methanol catalyst. The method mainly aims to improve the dispersibility of an active component copper, an auxiliary agent zinc and a carrier aluminum, but is complex, and precipitates prepared by three-step precipitation are mixed, so that the composition and the structure of a product are uneven, and the performance of a catalyst is influenced.
CN103801302A discloses a preparation method of a copper-containing zinc catalyst. Introducing CO into a zinc-containing soluble salt solution A 2 Gas, reactionA zinc-containing compound precipitate is generated. Introducing CO into the sodium metaaluminate solution 2 Gas to generate aluminum-containing precipitate, aging under stirring, adding basic copper carbonate during aging, washing, filtering, drying, roasting, tabletting and forming to obtain the copper-containing catalyst. The method improves the surface area of the catalyst, but the pore structure is not concentrated, and the material obtained by precipitation has poor cohesiveness and is not easy to be tabletted and molded.
CN103172607 discloses a copper-based catalyst for synthesizing methanol by carbon dioxide hydrogenation, a preparation method and an application thereof, wherein a precipitation solution containing zinc, aluminum and zirconium is firstly generated, a copper-containing salt solution is added into the precipitation solution, and after Cu in the precipitation solution is precipitated, aging, washing, drying and roasting are carried out to obtain the copper-containing catalyst. The method still adopts the conventional process conditions in the preparation process, improves the distribution of the active metal of the catalyst only by adding zirconium and adopting polyvinylpyrrolidone and polyethylene glycol as stabilizing agents, but does not obviously increase the number of active centers.
CN201610773534.7 discloses a preparation method of a catalyst for synthesizing methanol, comprising adding an alkaline solution of sodium metaaluminate and a soluble salt solution containing Cu into a reaction tank containing purified water simultaneously in parallel for carrying out gelling reaction to generate a slurry I, adding dropwise the alkaline solution of sodium metaaluminate into the soluble salt solution containing Zn for carrying out gelling reaction to generate a slurry II, mixing the slurry I and the slurry II uniformly, aging and filtering to obtain a material, carrying out hydrothermal treatment with water vapor, wherein urea is added during hydrothermal treatment, and then washing, filtering, drying, roasting, tabletting and forming are carried out to obtain the catalyst. Although the content of active metal copper in the surface phase of the catalyst prepared by the method is high, the synergistic effect of copper and zinc in the catalyst is reduced under the action of water vapor pressure and the impact of water molecules.
The method changes the copper dispersibility of the reduced catalyst by changing the preparation process of the copper-based catalyst or adding an auxiliary agent on the basis of the preparation process to improve the activity of the catalyst, but influences other physical and chemical properties of the catalyst in the process of improving the dispersibility of the copper component, and has no obvious effect of improving the dispersion effect of the active component.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a copper-zinc catalyst. The catalyst prepared by the method has the advantages of uniform distribution of active metal copper, good synergistic effect, large number of active metal active centers, improvement of the activity, selectivity and thermal stability of the copper-zinc catalyst, and good application prospect.
The preparation method of the copper-zinc catalyst comprises the following steps: (1) Carrying out parallel flow gelling reaction on the mixed solution A and a sodium metaaluminate solution to obtain slurry I, and then aging; (2) Dropwise adding the mixed solution B and a sodium carbonate solution into the aged slurry I obtained in the step (1) in a parallel manner, carrying out gelling reaction to obtain slurry II, and then aging; (3) Filtering and drying the material obtained in the step (2), and then treating the material by using a mixed aqueous solution containing aluminum salt and organic acid; (4) preparing the material obtained in the step (3) into a catalyst product; wherein the mixed solution A is an aqueous solution containing soluble copper salt, soluble zinc salt and organic auxiliary agent, and the mixed solution B is an aqueous solution containing soluble copper salt and soluble aluminum salt.
In the mixed solution A in the step (1), the concentration of the soluble copper salt is Cu 2+ 1.0 to 5.0mol/L, preferably 1.5 to 4.0mol/L, and the concentration of the soluble zinc salt is Zn 2+ The amount is 0.5 to 6.0mol/L, preferably 1.0 to 4.0mol/L. The copper content in the mixed solution A is 40-80% of the copper content in the catalyst, and preferably 55-75%. The soluble copper salt is nitrate and/or acetate containing copper, and the soluble zinc salt is nitrate and/or acetate containing zinc.
In the mixed solution A in the step (1), the organic auxiliary agent is a carboxylic acid polymer and/or an organic phosphonic acid compound. The molecular weight of the carboxylic acid polymer is 400-5000, and the carboxylic acid polymer is selected from one or more of polyacrylic acid, polymethacrylic acid, polymaleic acid, polyaspartic acid, polyepoxysuccinic acid, acrylic acid-hydroxypropyl acrylate copolymer and maleic acid-acrylic acid copolymer, and preferably one or more of polyacrylic acid, polymethacrylic acid, polymaleic acid, polyaspartic acid and polyepoxysuccinic acid. The organic phosphonic compound may be selected from one or more of ethylenediamine tetramethylene phosphonic acid, hydroxyethylene diphosphonic acid, polyol phosphonate, polyaminopolyether methylene phosphonic acid, 1,2, 4-tricarboxylic acid-2-phosphonobutane, hydroxyphosphonoacetic acid, aminotrimethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid, preferably from one or more of ethylenediamine tetramethylene phosphonic acid, hydroxyethylene diphosphonic acid, aminotrimethylene phosphonic acid. The molar ratio of the added amount of the organic auxiliary agent to the Cu in the mixed solution A is 0.2:1 to 3.0:1, preferably 0.3:1 to 2.5:1.
the concentration of the sodium metaaluminate solution in the step (1) is Al 2 O 3 The amount is 10 to 90g/L, preferably 15 to 70g/L.
The gelling reaction in the step (1) is generally carried out in a reaction tank, and the gelling reaction conditions are as follows: the reaction temperature is 30 to 80 ℃, preferably 40 to 70 ℃, the reaction time is 0.2 to 2.0 hours, preferably 0.5 to 1.5 hours, and the pH value is 6.0 to 9.0, preferably 6.5 to 8.5.
The aging conditions of the slurry I in the step (1) are as follows: the ageing temperature is 40-90 ℃, preferably 50-80 ℃, the pH value is 6.0-8.0, preferably 6.5-7.5, and the ageing time is 0.2-1.0 hour, preferably 0.3-0.8 hour. The aging is carried out under stirring, the preferred stirring conditions being as follows: the stirring speed is 100 to 300 rpm, preferably 150 to 250 rpm.
In the mixed solution B in the step (2), the concentration of the soluble copper salt is Cu 2+ 0.5 to 4.0mol/L, preferably 1.0 to 3.0mol/L, and the concentration of the soluble aluminum salt is calculated as Al 3+ The amount is 0.5 to 5.0mol/L, preferably 1.0 to 3.5mol/L. The soluble copper salt is nitrate and/or acetate containing copper, and the soluble aluminum salt is one or more selected from aluminum nitrate, aluminum sulfate, aluminum chloride or aluminum acetate. The copper content in the mixed solution B is 20-60% of the copper content in the catalyst, and preferably 25-45%; the aluminum content in the mixed solution B is 15-55%, preferably 20-45% of the aluminum content in the catalyst.
In the reaction mass of step (2), the molar ratio of the amount of sodium carbonate to the total amount of copper and zinc is between 0.5 and 4.0, preferably between 1.0 and 3.0.
The gelling reaction conditions in the step (2) are as follows: the reaction temperature is 30-90 ℃, preferably 40-80 ℃, the reaction time is 1.5-4.0 hours, preferably 1.5-3.5 hours, the pH value is 8.5-12.0, preferably 9.0-11.0, and the pH value is at least 1.0 higher than the pH value of the gelling reaction in step (1), preferably at least 1.5 higher.
The aging conditions of the slurry II in the step (2) are as follows: the ageing temperature is 40 to 90 ℃, preferably 50 to 80 ℃, the ageing time is 1.5 to 6.0 hours, preferably 2.0 to 5.0 hours, the pH value is 7.5 to 11.0, preferably 8.0 to 10.0, and the pH value is at least 0.5, preferably at least 1.0 higher than the pH value of the ageing in step (1). The aging is carried out under stirring, the preferred stirring conditions being as follows: the stirring speed is 300 to 500 rpm, preferably 300 to 450 rpm.
In the step (3), the treatment is carried out with a mixed aqueous solution of an aluminum salt and an organic acid, wherein the aluminum salt (as Al) is contained in the mixed aqueous solution of the aluminum salt and the organic acid 3+ In terms of oxide) to metallic copper in the catalyst in a molar ratio of 0.3 to 7.0, preferably 0.5 to 5.0. The molar ratio of the organic acid to the metallic copper in the catalyst, calculated as oxide, is between 0.3 and 6.0, preferably between 0.5 and 4.0. The volume ratio of the mixed aqueous solution of the aluminum salt and the organic acid to the material after the first drying is 1. Wherein the aluminum salt can be one or more of aluminum chloride, aluminum nitrate and aluminum sulfate; the organic acid may be selected from carboxylic acids having 2 to 8 carbon atoms, and further selected from one or more of malic acid, citric acid, isocitric acid, tartaric acid, oxalic acid, succinic acid, salicylic acid, lactic acid, β -hydroxybutyric acid, maleic acid, nitrilotriacetic acid, glycine, glutamic acid, glutaric acid, adipic acid, benzoic acid, and malonic acid, and preferably selected from one or more of malic acid, citric acid, tartaric acid, oxalic acid, succinic acid, salicylic acid, maleic acid, and glycine. The treatment conditions are as follows: the temperature is 30 to 100 ℃, preferably 40 to 70 ℃, and the time is 1 to 25 hours, preferably 2 to 20 hours.
The drying conditions in step (3) were as follows: drying at 40-250 deg.c for 1-48 hr, preferably at 50-180 deg.c for 4-36 hr.
The catalyst preparation process described in step (4) generally comprises conventional filtration, washing, drying, calcination and molding processes. The washing is generally carried out by using deionized water, and the washing temperature is controlled to be 30-80 ℃, preferably 35-65 ℃. The number of washing is 1 to 8, preferably 2 to 6. The drying conditions were as follows: drying at 40-250 deg.c for 1-48 hr, preferably under the following conditions: drying at 50-180 deg.c for 4-36 hr, roasting at 300-360 deg.c for 1-16 hr, preferably 2-10 hr.
The copper-zinc catalyst prepared by the method comprises the following components by weight: 20 to 65 percent of CuO, preferably 25 to 60 percent of CuO, 15 to 40 percent of ZnO, preferably 15 to 35 percent of ZnO, and Al 2 O 3 5 to 40 percent, preferably 10 to 35 percent.
The properties of the copper-zinc catalyst are as follows: the specific surface area is 100 to 550m 2 The pore volume is 0.20-0.80 ml/g, and the pore diameter distribution is as follows: the pore volume of the pores with the diameter of less than 10nm accounts for 3-27 percent of the total pore volume, the pore volume of the pores with the diameter of 10-15 nm accounts for 58-85 percent of the total pore volume, the pore volume of the pores with the diameter of more than 15nm accounts for 1-15 percent of the total pore volume, and the preferable pore diameter distribution is as follows: the pore volume of the pores with the diameter of less than 10nm accounts for 7-23 percent of the total pore volume, the pore volume of the pores with the diameter of 10-15 nm accounts for 70-80 percent of the total pore volume, and the pore volume of the pores with the diameter of more than 15nm accounts for 5-13 percent of the total pore volume.
The specific surface area of the metallic copper in the reduced catalyst is 35-120 m 2 A ratio of 40 to 100 m/g is preferred 2 (ii) in terms of/g. The dispersion degree of the metallic copper is 13 to 45 percent, and preferably 18 to 40 percent.
The catalyst prepared by the method is applied to the reaction of synthesizing methanol, and the general process conditions are as follows: the reaction temperature is 210-320 ℃, preferably 230-280 ℃; the pressure is 2-10 MPa, preferably 2-7 MPa; the volume space velocity is 2000-15000 h -1 Preferably 4000 to 12000 h -1 。
Compared with the prior art, the catalyst prepared by the method has the characteristics of more dispersed active metal, good synergistic effect among Cu-ZnO, concentrated catalyst pore distribution (mainly concentrated at 10-15 nm), high activity, high selectivity and heat resistance.
The method comprises the steps of carrying out co-current flow of a mixed solution containing part of Cu and Zn and a sodium metaaluminate solution for coprecipitation reaction, and carrying out primary aging on Cu, zn and Al and the mixed slurry to generate oxygen containing Cu, zn and AlAnd (3) adding the residual mixed solution of Cu and Al and sodium carbonate solution into the aged slurry in a concurrent flow manner, and then carrying out deep aging to prepare a copper, zinc and aluminum mixed precipitate to finally prepare the copper-zinc catalyst. The former precipitation is carried out under the condition that partial Cu and Zn are used as an aluminum source and a precipitator in an alkaline solution of sodium metaaluminate and organic auxiliaries are added, active metal and the organic auxiliaries are chelated to form a macromolecular reticular complex, so that the metal in the precipitate containing Cu, zn and Al after the first primary aging is orderly combined, the particle size of the precipitate is uniform, then the active metal in the former deposited metal oxide precursor has certain anchoring effect on the later deposited active metal in the process of growing the particles of the mixed precipitate of copper, zinc and aluminum by regulating and controlling the preparation steps and the preparation conditions, different active metals are orderly deposited in the catalyst, the growth speed of the metal oxide particles and the mutual contact probability among the active metals are controlled, the dispersion degree of copper is improved, the Cu-ZnO synergistic effect is increased, the active center is greatly improved, and Al generated by different aluminum sources in the precipitation process is greatly improved 2 O 3 Has good skeleton effect, leads the main active component copper and the auxiliary agent zinc to be dispersed more evenly, and is beneficial to improving the selectivity and the thermal stability of the methanol. According to the method, the dried material is treated by the mixed aqueous solution of the aluminum salt and the organic acid, so that the metal copper can be further dispersed on the alumina framework, the active centers are further increased, and the activity of the catalyst is improved. Meanwhile, after the mixed aqueous solution of the aluminum salt and the organic acid is treated, the pore structure of the catalyst is further optimized, the pore distribution is more reasonable, and the specific surface area and the pore volume of the catalyst are improved.
Detailed Description
The embodiments and effects of the present invention are further illustrated by the following examples. In the present invention, the specific surface area, pore volume and pore distribution are measured by a low-temperature liquid nitrogen adsorption method, and the specific surface area (S) of the catalyst metal Cu after reduction is measured Cu ) And degree of dispersion (D) Cu ) By using N 2 Determined by O chemisorption. v% is a volume fraction and wt% is a mass fraction.
Example 1
Adding Cu (NO) 3 ) 2 ·3H 2 O、Zn(NO 3 ) 2 ·6H 2 Dissolving O in deionized water, adding 142 g of hydroxyethylidene diphosphonic acid, and mixing uniformly to prepare a mixed solution A, cu 2+ The concentration is 2.8mol/L, zn 2+ The concentration was 2.5mol/L. Adding Cu (NO) 3 ) 2 ·3H 2 O and AlCl 3 ·6H 2 Dissolving O in deionized water to prepare mixed solution B, cu 2+ Concentration of 1.8mol/L, al 3+ The concentration was 2.0mol/L. Adding deionized water into the reaction tank, and adding sodium metaaluminate solution (containing Al) 2 O 3 42 g/L) and the mixed solution A are added into a reaction tank in parallel, the gelling temperature is 60 ℃, the gelling pH value is 7.5, and the gelling time is 0.9 hour, thus obtaining slurry I. And ageing the slurry I under stirring, wherein the stirring speed is 210 rpm, the ageing temperature is 75 ℃, the pH value is 7.0, and the ageing time is 0.6 hour. After aging is finished, adding a mixed solution B and a sodium carbonate solution into an aged slurry I in a concurrent flow manner, wherein the molar ratio of the amount of sodium carbonate to the total amount of copper and zinc is 2.0, the gelling temperature is 60 ℃, the pH value is 9.2, and the gelling time is 2.0 hours, so as to obtain a slurry II, aging the slurry II under stirring conditions, wherein the stirring speed is 420 r/min, the aging temperature is 75 ℃, the pH value is 8.5, and the aging time is 3.1 hours, filtering the aged slurry II, drying a filter cake at 120 ℃ for 8 hours, adding 198 g of anhydrous aluminum chloride and 172 g of malic acid into deionized water to prepare an aluminum salt and organic acid treatment aqueous solution, placing the dried material into a treatment solution, treating the treated material at a liquid-solid volume ratio of 2 to 48 ℃ for 12 hours, washing the filter cake with deionized water for 3 times, drying the filter cake at 100 ℃ for 10 hours, roasting the filter cake at 360 ℃ for 3 hours, adding a proper amount of graphite and pressing the roasted material into a sheet, so as to obtain a catalyst A. The composition, pore distribution and main properties are shown in table 1.
Example 2
Cu (NO) was added in the amount shown in Table 1 according to the catalyst B in example 1 3 ) 2 ·3H 2 O、Zn(NO 3 ) 2 ·6H 2 Dissolving O in deionized water, adding 155 g polymaleic acid (molecular weight 500) and 97 g hydroxyethylidene diphosphonic acid, mixing, and making into mixtureMixing the solution A with Cu (NO) 3 ) 2 ·3H 2 O and Al 2 (SO 4 ) 3 ·18H 2 Dissolving O in deionized water to prepare a mixed solution B. Adding deionized water into the reaction tank, and adding sodium metaaluminate solution (containing Al) 2 O 3 50 g/L) and the mixed solution A are added into a reaction tank in parallel, the gelling temperature is 55 ℃, the gelling pH value is 7.8, and the gelling time is 1.3 hours, thus obtaining slurry I. The slurry I was aged under stirring at a stirring speed of 210 rpm, an aging temperature of 74 ℃ and an aging pH of 6.9 for 0.7 hour. After aging, adding the mixed solution B and a sodium carbonate solution into the slurry I in a concurrent flow manner, wherein the molar ratio of the amount of sodium carbonate to the total amount of copper and zinc is 2.5, the gelling temperature is 55 ℃, the pH value is 9.5, and the gelling time is 2.2 hours, so as to obtain slurry II, aging the slurry II under stirring at a stirring speed of 390 r/min, an aging temperature of 74 ℃, an aging pH value of 9.5, and an aging time of 4.5 hours, filtering the aged slurry II, drying a filter cake at 120 ℃ for 8 hours, adding 400 g of aluminum sulfate and 190 g of citric acid into deionized water to prepare an aluminum salt and organic acid treatment aqueous solution, placing the dried material into a treatment solution, wherein the liquid-solid volume ratio is 2.5, treating at 42 ℃ for 8 hours, washing the filter cake with deionized water for 3 times, drying the filter cake at 90 ℃ for 12 hours, roasting at 360 ℃ for 3 hours, and adding a proper amount of graphite and water pressure into the roasted material to obtain the catalyst B. The composition, pore distribution and main properties are shown in table 1.
Example 3
Cu (NO) was added in the same ratio as the component content of catalyst C in Table 1 in accordance with the method of example 1 3 ) 2 ·3H 2 O、Zn(NO 3 ) 2 ·6H 2 Dissolving O in deionized water, adding 280 g of ethylenediamine tetramethylene phosphonic acid, mixing to prepare a mixed solution A, and adding Cu (NO) 3 ) 2 ·3H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving O in deionized water to prepare a mixed solution B. Adding deionized water into the reaction tank, and adding sodium metaaluminate solution (containing Al) 2 O 3 45 g/L) and the mixed solution A are added into a reaction tank in a cocurrent manner, the gelling temperature is 50 ℃, the pH value is 7.6, and the gelling time isFor 1.1 hours, slurry I was obtained. And ageing the slurry I under stirring, wherein the stirring speed is 230 rpm, the ageing temperature is 75 ℃, the ageing pH value is 7.2, and the ageing time is 0.8 hour. After aging, adding the mixed solution B and a sodium carbonate solution into the slurry I in a concurrent flow manner, wherein the molar ratio of the amount of sodium carbonate to the total amount of copper and zinc is 1.8, the gelling temperature is 55 ℃, the gelling pH value is 9.6, and the gelling time is 1.9 hours, so as to obtain slurry II, aging the slurry II under stirring at a stirring speed of 385 r/min at an aging temperature of 74 ℃, an aging pH value of 9.4, and an aging time of 3.8 hours, filtering the aged slurry II, drying the filter cake at 100 ℃ for 10 hours, adding 165 g of anhydrous aluminum chloride and 191 g of tartaric acid into deionized water to prepare an aluminum salt and organic acid treatment aqueous solution, placing the dried material into a treatment solution, treating at a liquid-solid volume ratio of 1.5, treating at a temperature of 52 ℃ for 16 hours, filtering, washing the filter cake with the deionized water for 4 times, drying the filter cake at 85 ℃ for 11 hours, roasting at 350 ℃ for 4 hours, adding a proper amount of graphite and pressing the roasted material into sheets, so as to obtain a catalyst C. The composition, pore distribution and main properties are shown in table 1.
Example 4
Cu (NO) was added in the same ratio as the catalyst D in Table 1 in accordance with the method of example 1 3 ) 2 ·3H 2 O、Zn(NO 3 ) 2 ·6H 2 Dissolving O in deionized water, adding 225 g of polyacrylic acid (molecular weight is 3000) and 142 g of hydroxyethylidene diphosphonic acid to prepare a mixed solution A, and dissolving Cu (NO) 3 ) 2 ·3H 2 O and AlCl 3 ·6H 2 Dissolving O in deionized water to prepare a mixed solution B. Adding deionized water into the reaction tank, and adding sodium metaaluminate solution (containing Al) 2 O 3 64 g/L) and the mixed solution A are added into a reaction tank in parallel, the gelling temperature is 50 ℃, the pH value is 7.4, and the gelling time is 1.0 hour, thus obtaining slurry I. And ageing the slurry I under stirring, wherein the stirring speed is 235 revolutions per minute, the ageing temperature is 78 ℃, the ageing pH value is 7.3, and the ageing time is 0.5 hour. After the aging is finished, adding the mixed solution B and a sodium carbonate solution into the slurry I in a concurrent flow manner, wherein the molar ratio of the amount of sodium carbonate to the total amount of copper and zinc is 1.9, the gelling temperature is 52 ℃, the gelling pH value is 10.3, and the gelling is finishedControlling the time to be 3.2 hours to obtain slurry II, aging the slurry II under the stirring condition, wherein the stirring speed is 440 r/min, the aging temperature is 74 ℃, the pH value is 9.1, and the aging time is 4.5 hours, filtering the aged slurry II, drying a filter cake at 120 ℃ for 8 hours, adding 482 g of aluminum nitrate nonahydrate and 148 g of salicylic acid into deionized water to prepare an aluminum salt and organic acid treatment aqueous solution, placing the dried material into the treatment solution, wherein the liquid-solid volume ratio is 3.5, treating at 48 ℃ for 13 hours, washing the filter cake with the deionized water for 4 times after filtering, drying the filter cake at 80 ℃ for 14 hours, roasting at 345 ℃ for 4 hours, adding a proper amount of graphite into the roasted material and pressing the material into sheets to obtain a catalyst D. The composition, pore distribution and main properties are shown in table 1.
Example 5
Cu (NO) was added in the amount shown in Table 1 according to the catalyst E in example 1 3 ) 2 ·3H 2 O、Zn(NO 3 ) 2 ·6H 2 Dissolving O in deionized water to obtain mixed solution A, and dissolving Cu (NO) 3 ) 2 ·3H 2 O and Al 2 (SO 4 ) 3 ·18H 2 Dissolving O in deionized water to prepare a mixed solution B. Adding deionized water into the reaction tank, and adding sodium metaaluminate solution (containing Al) 2 O 3 52 g/L) and the mixed solution A are added into a reaction tank in parallel, the gelling temperature is 45 ℃, the pH value is 7.8, and the gelling time is 1.2 hours, thus obtaining slurry I. And ageing the slurry I under stirring, wherein the stirring speed is 230 rpm, the ageing temperature is 73 ℃, the ageing pH value is 7.1, and the ageing time is 0.5 hour. After the aging is finished, adding the mixed solution B and a sodium carbonate solution into the slurry I in a concurrent flow manner, wherein the molar ratio of the amount of sodium carbonate to the total amount of copper and zinc is 1.8, the gelling temperature is 52 ℃, the gelling pH value is 9.7, the gelling time is 2.8 hours, so as to obtain slurry II, aging the slurry II under the stirring condition, wherein the stirring speed is 410 r/min, the aging temperature is 73 ℃, the aging pH value is 9.2, and the aging time is 4.0 hours, filtering the aged slurry II, washing a filter cake for 5 times with deionized water, drying the filter cake for 10 hours at 110 ℃, roasting at 340 ℃ for 4 hours, adding a proper amount of graphite into the roasted material, and pressing the material into sheets under water, so as to obtain a catalyst E. Composition, pore distribution and dominanceThe properties are shown in Table 1.
Comparative example 1
Proportioning the components of the catalyst F in the table 1 according to the proportion of Cu (NO) 3 ) 2 ·3H 2 O、Zn(NO 3 ) 2 ·6H 2 O and AlCl 3 ·6H 2 Dissolving O in deionized water to prepare a mixed solution. Adding deionized water into a reaction tank, adding the mixed solution and a sodium carbonate solution into the reaction tank in a cocurrent manner, wherein the molar ratio of the amount of sodium carbonate to the total amount of copper and zinc is 2.0, the gelling temperature is 60 ℃, the gelling time is 3 hours, and the reaction pH value is 7.6, so as to obtain reaction slurry. Aging the slurry under the condition of stirring, wherein the aging pH value is 7.8, the aging temperature is 75 ℃, the aging time is 3.7 hours, filtering the aged slurry, washing a filter cake for 3 times by deionized water, drying the filter cake for 10 hours at 100 ℃, roasting for 3 hours at 360 ℃, adding a proper amount of graphite into the roasted material, and pressing the mixture into sheets by water to obtain the catalyst F. The composition, pore distribution and main properties are shown in table 1.
Comparative example 2
Mixing Cu (NO) according to the component content of the catalyst G in the table 1 3 ) 2 ·3H 2 O and Zn (NO) 3 ) 2 ·6H 2 Dissolving O in deionized water to prepare a mixed solution. Adding deionized water into a reaction tank, and adding sodium metaaluminate solution (containing Al) 2 O 3 42 g/L) and the mixed solution are added into a reaction tank in parallel, the gelling temperature is 60 ℃, the gelling time is 3 hours, and the reaction pH value is 7.6, so as to obtain reaction slurry. Aging the slurry under the condition of stirring, wherein the aging pH value is 7.8, the aging temperature is 75 ℃, the aging time is 3.7 hours, filtering the aged slurry, washing a filter cake for 3 times by deionized water, drying the filter cake for 10 hours at 100 ℃, roasting for 3 hours at 360 ℃, adding a proper amount of graphite into the roasted material, and pressing the mixture into sheets by water to obtain the catalyst G. The composition, pore distribution and main properties are shown in table 1.
Comparative example 3
Proportioning the components of catalyst H in Table 1, adding Cu (NO) 3 ) 2 ·3H 2 Dissolving O in deionized water to prepare a solution A. Zn (NO) 3 ) 2 ·6H 2 Dissolving O in deionized waterTo prepare a solution B. Deionized water is added into the reaction tank 1, and sodium metaaluminate solution (containing Al) is added 2 O 3 42 g/L) and the solution A are added into a reaction tank 1 in parallel, the gelling temperature is 60 ℃, the gelling pH value is 7.5, and the gelling time is 1.0 hour, thus obtaining slurry I. Deionized water is added into a reaction tank 2, and sodium metaaluminate solution (containing Al) is added 2 O 3 42 g/L) and the solution B are added into a reaction tank 2 in a parallel flow manner, the gelling temperature is 60 ℃, the gelling pH value is 9.2, the gelling time is 2.0 hours, thus obtaining slurry II, the slurry I and the slurry II are mixed, the mixed slurry is aged under the condition of stirring, the aging pH value is 7.8, the aging temperature is 75 ℃, the aging time is 3.7 hours, the aged slurry is filtered, deionized water is used for washing a filter cake for 3 times, the filter cake is dried for 10 hours at 100 ℃, the filter cake is roasted for 3 hours at 360 ℃, a proper amount of graphite and water pressure are added into the roasted material for sheeting, thus obtaining a catalyst H. The composition, pore distribution and main properties are shown in table 1.
Comparative example 4
Mixing Cu (NO) according to the component content ratio of catalyst I in Table 1 3 ) 2 ·3H 2 O and AlCl 3 ·6H 2 Dissolving O in deionized water to obtain mixed solution A, and dissolving Zn (NO) 3 ) 2 ·6H 2 O and AlCl 3 ·6H 2 Dissolving O in deionized water to prepare a mixed solution B, adding the deionized water into a reaction tank 1, adding the mixed solution A and a sodium carbonate solution into the reaction tank in a cocurrent manner, wherein the molar ratio of the amount of sodium carbonate to the total amount of copper and zinc is 2.0, the gelling temperature is 60 ℃, the gelling pH value is 7.5, and the gelling time is 1.0 hour, thus obtaining slurry I. Adding deionized water into a reaction tank 2, adding a mixed solution B and a sodium carbonate solution into the reaction tank 2 in a cocurrent manner, wherein the molar ratio of the amount of sodium carbonate to the total amount of copper and zinc is 2.0, the gelling temperature is 60 ℃, the gelling pH value is 9.2, and the gelling time is 2.0 hours, so as to obtain a slurry II, mixing the slurry I and the slurry II, aging the mixed slurry under stirring, wherein the aging pH value is 7.8, the aging temperature is 75 ℃, the aging time is 3.7 hours, filtering the aged slurry, washing a filter cake for 3 times by using the deionized water, drying the filter cake for 10 hours at 100 ℃, roasting for 3 hours at 360 ℃, adding a proper amount of graphite into the roasted material, and pressing the mixture into sheets by using water, so as to obtain a catalyst I.The composition, pore distribution and main properties are shown in table 1.
Comparative example 5
Mixing Cu (NO) according to the component content ratio of catalyst J in Table 1 3 ) 2 ·3H 2 O、Zn(NO 3 ) 2 ·6H 2 Dissolving O in deionized water to prepare a mixed solution A. Adding Cu (NO) 3 ) 2 ·3H 2 O and AlCl 3 ·6H 2 Dissolving O in deionized water to prepare a mixed solution B. Adding deionized water into the reaction tank, and adding sodium metaaluminate solution (containing Al) 2 O 3 42 g/L) and the mixed solution A are added into a reaction tank in parallel, the gelling temperature is 60 ℃, the gelling pH value is 7.5, and the gelling time is 1.0 hour, thus obtaining slurry I. Adding the mixed solution B and a sodium carbonate solution into slurry I which is not aged in a cocurrent manner, wherein the molar ratio of the amount of sodium carbonate to the total amount of copper and zinc is 2.0, the gelling temperature is 60 ℃, the pH value is 9.2, and the gelling time is 2.0 hours, so as to obtain slurry II, aging the slurry II under stirring at the aging temperature of 75 ℃, the aging pH value is 7.8, and the aging time is 3.7 hours, filtering the aged slurry, washing a filter cake with deionized water for 3 times, drying the filter cake at 100 ℃ for 10 hours, roasting at 360 ℃ for 3 hours, adding a proper amount of graphite into the roasted material, and pressing the material into sheets by water, so as to obtain a catalyst J. The composition, pore distribution and main properties are shown in table 1.
Comparative example 6
The reference K, having the same composition as the catalyst of example 1, was prepared according to the method disclosed in CN201610773534.7, in the following way:
cu (NO) with the catalyst composition of example 1 3 ) 2 ·3H 2 Dissolving O in deionized water to prepare solution A. Adding Zn (NO) 3 ) 2 ·6H 2 Dissolving O in deionized water to prepare a mixed solution B. Adding deionized water into the reaction tank, and adding sodium metaaluminate solution (containing Al) 2 O 3 42 g/L) and the mixed solution A are added into a reaction tank in parallel, the gelling temperature is 60 ℃, the gelling pH value is 7.5, and the gelling time is 1.0 hour, thus obtaining slurry I. Sodium metaaluminate solution (containing Al) 2 O 3 42 g/L) of the solution B are added with stirring, the gelling temperature is maintained at 60 ℃, and the pH value is controlled at the endThe preparation is carried out at 7.5, the gelling time is controlled at 2 hours, and the zinc-containing and aluminum-containing precipitate slurry II is generated. The two types of slurry containing precipitates were mixed. Aging under stirring, wherein the pH value is 7.8, the temperature is 75 ℃, aging is carried out for 3.7 hours, the material is filtered after aging, and a filter cake is subjected to hydrothermal treatment under the steam containing urea, wherein the hydrothermal treatment conditions are as follows: the mol ratio of the total amount of the urea to the active metal atoms is 7, the temperature is 230 ℃, the pressure is 6.0MPa, the processing time is 4 hours, the filter cake is washed by deionized water for 3 times, the filter cake is dried for 10 hours at 100 ℃, roasted for 3 hours at 360 ℃, and a proper amount of graphite and water are added into the roasted material to press the material into sheets, so that the catalyst K is obtained. The composition, pore distribution and main properties are shown in table 1.
Example 6
Grinding the synthetic methanol catalyst to 16-40 mesh, and using low concentration hydrogen (H) before use 2 /N 2 And the volume ratio of the hydrogen and the nitrogen is 3/97) for 16 to 25 hours, and the highest reduction temperature is 235 ℃. The activity of the catalyst was evaluated on a miniature fixed bed reactor. The filling amount of the catalyst is 5ml, and the composition of the raw material gas is CO/H 2 /CO 2 /N 2 =12/70/6/12 (volume ratio), reaction pressure 5.0MPa, space velocity 10000h -1 The reaction temperature was 250 ℃ and CO were measured 2 The conversion of (a) is the initial activity of the catalyst. Then the catalyst is heat treated for 5h at 440 ℃ in the synthetic atmosphere, and then the temperature is reduced to 250 ℃ for measuring CO and CO 2 The conversion of (b) is activity after heat treatment, i.e., heat resistance. The product was analyzed by gas chromatography to determine the space-time yield g.mL of methanol -1 ·h -1 I.e., grams of methanol produced per milliliter of catalyst per hour, as shown in table 3.
As can be seen from tables 1 and 2, the catalyst of the present invention has good metal dispersion, thereby improving the synergistic effect between Cu and ZnO catalysts, more concentrated pore structure distribution, mainly concentrated in 10nm to 15nm, and high activity and selectivity of the catalyst in the pore distribution range, and from the test results (Table 3), the catalyst of the present invention for methanol synthesis has high activity, heat resistance and excellent selectivity.
TABLE 1 catalyst composition and Properties
Catalyst numbering A B C D E
CuO，wt% 55 50 52 53 50
ZnO，wt% 27 30 32 28 30
Al 2 O 3 ，wt% 18 20 16 19 20
Specific surface area, m 2 /g 186 182 178 173 165
Pore volume, mL/g 0.420 0.412 0.404 0.396 0.382
Hole distribution by%
＜10nm 14.92 15.13 15.59 15.82 22.45
10nm～15nm 76.85 76.46 76.21 76.15 69.01
＞15nm 8.23 8.41 8.20 8.03 8.54
TABLE 1 (continue)
Catalyst numbering F G H I J K
CuO，wt% 55 55 55 55 55 55
ZnO，wt% 27 27 27 27 27 27
Al 2 O 3 ，wt% 18 18 18 18 18 18
Specific surface area/m 2 ·g -1 90 118 121 92 112 172
Pore volume/cm 3 ·g -1 0.189 0.242 0.256 0.193 0.238 0.394
Hole distribution by%
＜10nm 75.56 67.32 65.59 72.84 64.21 40.69
10nm～15nm 16.26 23.14 25.27 18.99 25.52 47.47
＞15nm 8.18 9.54 9.14 8.17 10.27 11.84
TABLE 2 degree of dispersion and specific surface area of metallic copper
Catalyst and process for producing the same S Cu /m 2 ·g -1 D Cu ，%
A 74.1 36.8
B 73.6 35.9
C 73.1 35.1
D 72.8 34.6
E 61.9 24.2
F 28.5 10.2
G 29.9 10.8
H 32.4 11.9
I 30.1 11.1
J 33.6 12.4
K 49.3 15.9
S Cu Is the specific surface area of copper, D Cu The copper dispersion is shown.
TABLE 3 evaluation of catalyst Activity and Heat resistance test results
Catalyst and process for producing the same Initial activity,% of Initial activity of% Activity after heat resistance,% Activity after heat resistance% Methanol space time yield, (g. ML) -1 ·h -1 ） Methanol selectivity,% of
CO CO 2 CO CO 2
A 96.59 87.93 89.79 80.29 5.25 98.49
B 96.47 87.86 89.68 80.17 5.18 98.40
C 96.38 87.79 89.63 80.10 5.13 98.35
D 96.27 87.70 89.58 80.03 5.08 98.30
E 94.78 86.43 88.44 79.09 4.36 97.40
F 78.89 76.12 67.15 60.02 1.86 80.74
G 79.49 77.48 67.96 60.91 1.97 81.26
H 80.84 77.68 68.11 60.85 1.99 81.38
I 79.56 76.54 67.58 60.13 1.88 80.81
J 80.25 77.21 68.32 61.05 1.95 81.48
K 92.35 83.48 85.85 74.59 3.05 96.05

Claims (18)

1. The preparation method of the copper-zinc catalyst is characterized by comprising the following steps: (1) Carrying out parallel flow gelling reaction on the mixed solution A and a sodium metaaluminate solution to obtain slurry I, and then aging; (2) Dripping the mixed solution B and a sodium carbonate solution into the aged slurry I obtained in the step (1) in a parallel manner, carrying out gelling reaction to obtain slurry II, and then aging; (3) Filtering and drying the material obtained in the step (2), and then treating the material by using a mixed aqueous solution containing aluminum salt and organic acid; (4) preparing the material obtained in the step (3) into a catalyst product; wherein the mixed solution A is an aqueous solution containing soluble copper salt, soluble zinc salt and organic auxiliary agent, and the mixed solution B is an aqueous solution containing soluble copper salt and soluble aluminum salt; the organic auxiliary agent is a carboxylic acid polymer and/or an organic phosphonic acid compound; the organic acid is selected from C2-C8 carboxylic acid.
2. The method of claim 1, wherein: in the mixed solution A in the step (1), the concentration of the soluble copper salt is Cu 2+ Calculated as 1.0 to 5.0mol/L, and the concentration of soluble zinc salt is Zn 2+ Calculated as 0.5-6.0 mol/L; the copper content in the mixed solution A is 40-80% of the copper content in the catalyst.
3. The method of claim 1, wherein: the molecular weight of the carboxylic acid polymer is 400-5000, and the carboxylic acid polymer is selected from one or more of polyacrylic acid, polymethacrylic acid, polymaleic acid, polyaspartic acid, polyepoxysuccinic acid, acrylic acid-hydroxypropyl acrylate copolymer or maleic acid-acrylic acid copolymer; the organic phosphonic acid compound is selected from one or more of ethylenediamine tetramethylene phosphonic acid, hydroxyethylidene diphosphonic acid, polyalcohol phosphonate, polyaminopolyether methylene phosphonic acid, 1,2, 4-tricarboxylic acid-2-phosphonic butane, hydroxyphosphonoacetic acid, aminotrimethylene phosphonic acid or diethylenetriamine pentamethylene phosphonic acid.
4. The method of claim 1, wherein: the molar ratio of the added amount of the organic auxiliary agent to the Cu in the mixed solution A is 0.2:1 to 3.0:1.
5. the method of claim 1, wherein: the concentration of the sodium metaaluminate solution in the step (1) is Al 2 O 3 The weight is 10-90 g/L.
6. The method of claim 1, wherein: the gelling reaction conditions in the step (1) are as follows: the reaction temperature is 30-80 ℃, the reaction time is 0.2-2.0 hours, and the pH value is 6.0-9.0.
7. The method of claim 1, wherein: the aging conditions of the slurry I in the step (1) are as follows: the aging temperature is 40-90 ℃, the pH value is 6.0-8.0, and the aging time is 0.2-1.0 hour.
8. The method of claim 1, wherein: in the mixed solution B in the step (2), the concentration of the soluble copper salt is Cu 2+ Calculated as 0.5-4.0 mol/L, the concentration of soluble aluminum salt is calculated as Al 3+ Calculated as 0.5-5.0 mol/L; the copper content in the mixed solution B is 20-60% of the copper content in the catalyst; the aluminum content in the mixed solution B is 15-55% of the aluminum content in the catalyst.
9. The method of claim 1, wherein: in the reaction material in the step (2), the molar ratio of the amount of the sodium carbonate to the total amount of the copper and the zinc is 0.5-4.0.
10. The method of claim 1, wherein: the gelling reaction conditions in the step (2) are as follows: the reaction temperature is 30-90 ℃, the reaction time is 1.5-4.0 hours, the pH value is 8.5-12.0, and the pH value is at least 1.0 higher than that of the gelling reaction in the step (1).
11. The method of claim 1, wherein: the aging conditions of the slurry II in the step (2) are as follows: the aging temperature is 40-90 ℃, the aging time is 1.5-6.0 hours, the pH value is 7.5-11.0, and the pH value is at least 0.5 higher than the pH value aged in the step (1).
12. The method of claim 1, wherein: in the mixed aqueous solution of the aluminum salt and the organic acid described in the step (3), the aluminum salt is Al 3+ The molar ratio of the CuO in the catalyst to the CuO is 0.3-7.0; the mol ratio of the organic acid to the CuO in the catalyst is 0.3-6.0; the volume ratio of the aqueous solution containing the aluminum salt and the organic acid to the dried material is 1.
13. The method of claim 1, wherein: in the step (3), the aluminum salt is one or more of aluminum chloride, aluminum nitrate or aluminum sulfate.
14. The method of claim 1, wherein: in the step (3), the organic acid is selected from one or more of malic acid, citric acid, isocitric acid, tartaric acid, oxalic acid, succinic acid, salicylic acid, lactic acid, beta-hydroxybutyric acid, maleic acid, nitrilotriacetic acid, glycine, glutamic acid, glutaric acid, adipic acid, benzoic acid or malonic acid.
15. The method of claim 1, wherein: the treatment conditions in the step (3): the temperature is 30-100 ℃, and the time is 1-25 hours.
16. A copper zinc catalyst prepared by the process according to any one of claims 1 to 15, wherein: based on the weight of the catalyst, the catalyst comprises the following components: 20 to 65 percent of CuO, 15 to 40 percent of ZnO and Al 2 O 3 5 to 40 percent.
17. A copper zinc catalyst prepared by the process according to any one of claims 1 to 15, wherein: the properties of the catalyst are as follows: the specific surface area is 100 to 550m 2 The pore volume is 0.20-0.80 ml/g, and the pore size distribution is as follows: the pore volume of the pores with the diameter of less than 10nm accounts for 3-27 percent of the total pore volume, the pore volume of the pores with the diameter of 10-15 nm accounts for 58-85 percent of the total pore volume, and the pore volume of the pores with the diameter of more than 15nm accounts for 1-15 percent of the total pore volume.
18. A copper zinc catalyst prepared by the process according to any one of claims 1 to 15, wherein: the specific surface area of the metallic copper in the reduced catalyst is 35 to 120m 2 The dispersity of the metal copper is 13-45 percent.
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