CN110935478A - Preparation method of methanol synthesis catalyst - Google Patents

Preparation method of methanol synthesis catalyst Download PDF

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CN110935478A
CN110935478A CN201811114237.7A CN201811114237A CN110935478A CN 110935478 A CN110935478 A CN 110935478A CN 201811114237 A CN201811114237 A CN 201811114237A CN 110935478 A CN110935478 A CN 110935478A
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catalyst
aging
mixed solution
copper
slurry
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CN110935478B (en
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王继锋
王海涛
徐学军
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
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/182—Phosphorus; Compounds thereof with silicon
    • B01J35/60—
    • 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 methanol synthesis 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) dripping the mixed solution B and a sodium carbonate solution into the aged slurry I in parallel, carrying out gelling reaction to obtain slurry II, and then aging; (3) carrying out solid-liquid separation on the material obtained in the step (2), and drying, roasting and forming a solid phase to obtain a catalyst; wherein the mixed solution A is an aqueous solution containing soluble copper salt, soluble zinc salt and a compound containing element A, and the mixed solution B is an aqueous solution containing soluble copper salt, soluble aluminum salt and a compound containing element A; the element A is one or more of boron, phosphorus or silicon, and the catalyst prepared by the method has uniform distribution of active metals and large quantity of active metal active centers, so that the activity, selectivity and thermal stability of the methanol synthesis catalyst are improved, and the service life of the catalyst is prolonged.

Description

Preparation method of methanol synthesis catalyst
Technical Field
The invention relates to a preparation method of a methanol synthesis catalyst, in particular to a preparation method of a methanol synthesis catalyst with high activity, high selectivity and good heat resistance.
Background
Methanol is increasingly regarded as a basic chemical raw material and a new energy source, is widely applied to organic synthesis, dye, fuel, medicine, coating and national defense industries, and along with the continuous increase of the demand and the production capacity of methanol along with the development of the industries in recent years, the position of methanol in national economy is more important, so that the production technology and the catalyst performance of the methanol are required to be further improved in order to further promote the development of the methanol industry.
Industrially, methanol generally contains H2、CO、CO2The 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 catalyst2O3The three components have different functions, CuO is used as a main active component, ZnO and Al2O3Is an auxiliary agent. The addition of ZnO can make the catalyst form Cu/Zn synergetics, greatly raise activity and selectivity of catalyst, Al2O3Not only plays a role of a framework in the catalyst, but also can disperse active components in the catalyst to enable CO to be generated2The adsorption and conversion rate are improved, and a proper amount of Al is added into the copper-based catalyst2O3Can improve catalyst CO2Selectivity of synthesizing methanol by hydrogenation.
Cu/ZnO/Al2O3The 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, and the interaction between Cu and ZnOEnhancement, carbon monoxide conversion and methanol selectivity increase. 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/Al2O3The 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. The catalyst has different preparation methods, different dispersity of the obtained copper, different synergistic effect between the metal active center copper and the auxiliary agent, and larger difference of the performance of the obtained catalyst.
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 kept at 60-150 ℃ for 1-6 h in a high-pressure reaction kettle, and then is slowly cooled to room temperature to obtain white precipitate, 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, and a small amount of surfactant OP is added in the preparation process of a coprecipitation method. CN 101733109A copper-based methanol synthesis catalyst is prepared by adding an auxiliary agent (one or more of ethylene glycol, diethylamine, glycerol, magnesium stearate, and activated carbon) during precipitation. 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 the active component copper, the auxiliary agent zinc and the carrier aluminum, but the method is complex, and precipitates prepared by three-step precipitation are mixed, so that the composition and the structure of the product are uneven, and the performance of the catalyst is influenced.
CN103801302A discloses a preparation method of a copper-zinc-containing catalyst. Introducing CO into soluble salt solution A containing zinc2Gas, reacting to generate zinc compound deposit. Introducing CO into the sodium metaaluminate solution2Gas 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 synthetic methanol catalyst, which comprises the steps of adding a sodium metaaluminate alkaline solution and a soluble salt solution containing Cu into a reaction tank filled with purified water in a concurrent flow manner to carry out gelling reaction to generate slurry I, then dropwise adding the sodium metaaluminate alkaline solution into a soluble salt solution containing Zn to carry out gelling reaction to generate slurry II, uniformly mixing the slurry I and the slurry II, carrying out aging and filtering to obtain a material, carrying out hydrothermal treatment on the obtained material by using water vapor, adding urea during the hydrothermal treatment, and then washing, filtering, drying, roasting, tabletting and forming 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-based catalyst preparation process or adds the auxiliary agent on the basis of the copper-based catalyst preparation process to change the copper dispersibility on the reduced catalyst and improve the activity of the catalyst, but in the process of improving the copper component dispersibility, other physicochemical properties of the catalyst are influenced, and the effect of improving the active component dispersibility is not obvious.
Disclosure of Invention
In view of the above-mentioned deficiencies in the prior art, the present invention provides a method for preparing a catalyst for synthesizing methanol. The catalyst prepared by the method has the advantages of uniform distribution of active metal copper and auxiliary agent zinc, good synergistic effect, large number of active metal active centers, and improvement of the activity, selectivity and thermal stability of the methanol synthesis catalyst and the service life of the catalyst.
The preparation method of the methanol synthesis 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 flow manner, carrying out gelling reaction to obtain slurry II, and then aging; (3) carrying out solid-liquid separation on the material obtained in the step (2), and drying, roasting and forming a solid phase to obtain a catalyst; wherein the mixed solution A is an aqueous solution containing soluble copper salt, soluble zinc salt and a compound containing element A, and the mixed solution B is an aqueous solution containing soluble copper salt, soluble aluminum salt and a compound containing element A; the element A is one or more of boron, phosphorus or silicon, and the compound containing the element A can be one or more of boric acid, sodium silicate, silica sol, phosphoric acid, ammonium hydrogen phosphate and ammonium dihydrogen phosphate.
In the mixed solution A in the step (1), the concentration of the soluble copper salt is Cu2+1.0 to 5.0mol/L, preferably 1.5 to 4.0mol/L, and the concentration of the soluble zinc salt is Zn2+0.5 to 6.0mol/L, preferably 1.0 to 4.0mol/L, and the weight concentration of the element A oxide is 1 to 30g/L, preferably 5 to 25 g/L. The copper content in the mixed solution A is 40-80%, preferably 55-75% of the copper content in the catalyst, and the content of the element A oxide in the mixed solution A is 20-80%, preferably 35-65% of the element A oxide in the catalyst. The soluble copper salt is nitrate and/or acetate containing copper, and the soluble zinc salt is nitrate and/or acetate containing zinc.
The concentration of the sodium metaaluminate solution in the step (1) is Al2O3The amount is 10 to 90g/L, preferably 15 to 70 g/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 30-80 ℃, preferably 40-70 ℃, the reaction time is 0.2-2.0 hours, preferably 0.5-1.5 hours, and the pH value is 6.0-9.0, preferably 6.5-8.5.
The aging conditions of the slurry I in the step (1) are as follows: the aging temperature is 40-90 ℃, preferably 50-80 ℃, the pH value is 6.0-8.0, preferably 6.5-7.5, and the aging 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 100-300 rpm, preferably 150-250 rpm.
In the mixed solution B in the step (2), the concentration of the soluble copper salt is Cu2+0.5 to 4.0mol/L, preferably 1.0 to 3.0mol/L, of soluble aluminumSalt concentration as Al3+0.5 to 5.0mol/L, preferably 1.0 to 3.5mol/L, and the weight concentration of the element A oxide is 1 to 25g/L, preferably 5 to 20 g/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 material in the step (2), the molar ratio of the amount of the sodium carbonate to the total amount of copper and zinc is 0.5-4.0, preferably 1.0-3.0.
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 that of the gelling reaction in the step (1), preferably at least 1.5 higher.
The aging conditions of the slurry II in the step (2) are as follows: the aging temperature is 40-90 ℃, preferably 50-80 ℃, the aging time is 1.5-6.0 hours, preferably 2.0-5.0 hours, the pH value is 7.5-11.0, preferably 8.0-10.0, and the pH value is at least 0.5 higher than the pH value aged in the step (1), preferably at least 1.0 higher. The aging is carried out under stirring, the preferred stirring conditions being as follows: the stirring speed is 300-500 rpm, preferably 300-450 rpm.
The solid-liquid separation process in the step (3) generally comprises conventional washing and filtering processes, the washing is generally washed by 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 temperature in the step (3) is 50-150 ℃, preferably 60-120 ℃, and the drying time is 0.5-24 hours, preferably 1-16 hours. The roasting temperature is 300-360 ℃, and the roasting time is 1-16 hours, preferably 2-10 hours.
The molding in the step (3) is generally tabletting molding, and the molding can be directly performed without adding conventional molding aids such as peptizing acid, extrusion aids and the like in the molding process.
The methanol synthesis catalyst prepared by the method comprises the following components by weight: 20 to 62 percent of CuO, preferably 25 to 57 percent of CuO, 15 to 35 percent of ZnO, preferably 15 to 30 percent of ZnO, and Al2O35 to 25 percent, preferably 6 to 23 percent, and 2 to 20 percent, preferably 7 to 17 percent of element A oxide; wherein the element A is one or more of boron, phosphorus or silicon.
The properties of the methanol synthesis catalyst are as follows: the specific surface area is 100-550 m2The 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% of the total pore volume, the pore volume of the pores with the diameter of 10-15 nm accounts for 58-85% of the total pore volume, the pore volume of the pores with the diameter of more than 15nm accounts for 1-15% of the total pore volume, and the preferable pore size distribution is as follows: the pore volume of the pores with the diameter of less than 10nm accounts for 7-23% of the total pore volume, the pore volume of the pores with the diameter of 10-15 nm accounts for 65-80% of the total pore volume, and the pore volume of the pores with the diameter of more than 15nm accounts for 5-13% of the total pore volume.
The specific surface area of the metal copper in the reduced catalyst is 35-120 m2Preferably 40 to 100 m/g2(ii) in terms of/g. The dispersion degree of the metallic copper is 13 to 45 percent, and preferably 18 to 40 percent.
The synthetic methanol catalyst prepared by the method is applied to the synthetic methanol reaction, and the general process conditions are as follows: the reaction temperature is 210-320 ℃, and preferably 230-280 ℃; the pressure is 2-10 MPa, preferably 2-7 MPa; the volume airspeed is 2000-15000 h-1Preferably 4000 to 12000 h-1。
Compared with the prior art, the active metal of the catalyst prepared by the method is more dispersed, the Cu-ZnO synergistic effect is good, the pore distribution of the catalyst is concentrated (mainly concentrated at 10-15 nm), and the catalyst has the characteristics of high activity, high selectivity and heat resistance.
The method comprises the steps of precipitating step by step, firstly carrying out co-current flow of a mixed solution containing partial Cu and Zn and a sodium metaaluminate solution for coprecipitation reaction, carrying out primary aging on Cu, Zn and Al and the mixture slurry to generate a primary precipitate containing oxides of Cu, Zn and Al with larger particles, then adding the residual mixed solution of Cu and Al and a sodium carbonate solution into the aged slurry in a co-current flow manner, and then carrying out deep aging to prepare the copper, zinc and aluminumAnd mixing the precipitate with aluminum to finally prepare the copper-zinc catalyst. By regulating and controlling the preparation steps and preparation conditions, in the process of growing up copper, zinc and aluminum mixed precipitate particles, active metal in the previously deposited metal oxide precursor has a certain anchoring effect on the subsequently deposited active metal, different active metals are orderly deposited in the catalyst, the growth speed of the metal oxide particles and the probability of mutual contact 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 simultaneously used2O3Has 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 activity of the catalyst, the selectivity of methanol and the thermal stability.
By adopting the preparation method of the catalyst, the intermediate formed between the component A and the active metal is beneficial to improving the matching effect between the auxiliary agent and the active metal, further improving the dispersion degree of copper, improving the caking property of the formed product, being capable of directly forming without adding a forming auxiliary agent (graphite), and simultaneously being more reasonable in pore structure distribution and beneficial to further improving the activity, methanol selectivity and thermal stability of the catalyst.
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 measuredCu) And degree of dispersion (D)Cu) By using N2Determined by O-chemisorption. v% is volume fraction and wt% is mass fraction.
Example 1
Dissolving copper nitrate, zinc nitrate and ammonium dihydrogen phosphate in deionized water to prepare a mixed solution A, Cu2+The concentration is 2.8mol/L, Zn2+The concentration is 2.5mol/L, P2O5The weight concentration of (A) is 25 g/L. Dissolving copper nitrate, aluminum chloride and ammonium dihydrogen phosphate in deionized water to prepare a mixed solution B, Cu2+Concentration of 1.8mol/L, Al3+The concentration is 2.0mol/L, P2O5The weight concentration of (b) is 18 g/L. Adding deionized water into the reaction tank, and adding sodium metaaluminate solution (containing Al)2O342 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. And ageing the slurry I under stirring, wherein the stirring speed is 180 revolutions per minute, the ageing temperature is 76 ℃, the pH value is 6.8, and the ageing time is 0.7 hour. After the aging is finished, adding the mixed solution B and a sodium carbonate solution into the aged slurry I 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 the stirring condition, wherein the stirring speed is 430 revolutions/minute, the aging temperature is 77 ℃, the pH value is 8.8, and the aging time is 3.0 hours, filtering the aged slurry II, 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, and pressing the roasted material into a sheet, so as to obtain the catalyst A. The composition, pore distribution and main properties are shown in table 1.
Example 2
According to the method of example 1, copper nitrate, zinc nitrate and boric acid were dissolved in deionized water to prepare a mixed solution a, and copper nitrate, aluminum nitrate and boric acid were dissolved in deionized water to prepare a mixed solution B, in accordance with the component content ratio of catalyst B in table 1. Adding deionized water into the reaction tank, and adding sodium metaaluminate solution (containing Al)2O349 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 7.4, and the gelling time is 1.3 hours, thus obtaining slurry I. And ageing the slurry I under stirring, wherein the stirring speed is 190 rpm, the ageing temperature is 75 ℃, 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 cocurrent manner, wherein the molar ratio of the amount of sodium carbonate to the total amount of copper and zinc is 2.1, the gelling temperature is 55 ℃, the pH value is 9.9, the gelling time is 2.7 hours, so as to obtain slurry II, aging the slurry II under the stirring condition, the stirring speed is 410 revolutions per minute, the aging temperature is 76 ℃, the aging pH value is 9.0, and the aging time is 3.6 hours, filtering the aged slurry II, washing a filter cake with deionized water for 3 times, and placing the filter cake in a container with deionized water for 3 timesDrying at 90 ℃ for 14 hours, roasting at 340 ℃ for 5 hours, and pressing the roasted material into a sheet to obtain the catalyst B. The composition, pore distribution and main properties are shown in table 1.
Example 3
According to the method of example 1, copper nitrate, zinc nitrate and a water glass solution are dissolved in deionized water to prepare a mixed solution A, and copper nitrate, aluminum sulfate and ammonium dihydrogen phosphate are dissolved in deionized water to prepare a mixed solution B according to the component content ratio of the catalyst C in Table 1. Adding deionized water into the reaction tank, and adding sodium metaaluminate solution (containing Al)2O352 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 0.9 hour, thus obtaining slurry I. And ageing the slurry I under stirring, wherein the stirring speed is 195 rpm, the ageing temperature is 77 ℃, the ageing pH value is 7.3, and the ageing time is 0.6 hour. After the aging is finished, adding the mixed solution B and a sodium carbonate solution into the slurry I in a cocurrent 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 53 ℃, the gelling pH value is 10.1, 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 425 revolutions per minute, the aging temperature is 79 ℃, the aging pH value is 9.6, and the aging time is 3.8 hours, filtering the aged slurry II, washing a filter cake with deionized water for 4 times, drying the filter cake at 100 ℃ for 9 hours, roasting at 350 ℃ for 6 hours, and slicing the roasted material, so as to obtain the catalyst C. The composition, pore distribution and main properties are shown in table 1.
Example 4
According to the method of example 1, copper nitrate, zinc nitrate and a water glass solution are dissolved in deionized water to prepare a mixed solution A, and copper nitrate, aluminum chloride and a water glass solution are dissolved in deionized water to prepare a mixed solution B according to the component content proportion of the catalyst D in Table 1. Adding deionized water into the reaction tank, and adding sodium metaaluminate solution (containing Al)2O365 g/L) and the mixed solution A are added into a reaction tank in parallel, the gelling temperature is 48 ℃, the pH value is 7.8, and the gelling time is 1.4 hours, thus obtaining slurry I. And ageing the slurry I under stirring, wherein the stirring speed is 240 rpm, the ageing temperature is 73 ℃, the ageing pH value is 6.9, and the ageing time is 0.6 hour.After the aging is finished, adding the mixed solution B and a sodium carbonate solution into the slurry I in a cocurrent manner, controlling the molar ratio of the amount of sodium carbonate to the total amount of copper and zinc to be 2.0, the gelling temperature to be 50 ℃, the gelling pH value to be 9.8 and the gelling time to be 2.2 hours to obtain slurry II, aging the slurry II under the stirring condition, controlling the stirring speed to be 405 r/min, the aging temperature to be 75 ℃, controlling the pH value to be 9.1 and the aging time to be 3.7 hours, filtering the aged slurry II, washing a filter cake with deionized water for 4 times, drying the filter cake at 80 ℃ for 15 hours, roasting at 335 ℃ for 5 hours, and pressing the roasted material into a tablet to obtain the 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 13)2·3H2O、Zn(NO3)2·6H2Dissolving O in deionized water to obtain mixed solution A, and dissolving Cu (NO)3)2·3H2O and Al2(SO4)3·18H2Dissolving O in deionized water to prepare a mixed solution B. Adding deionized water into the reaction tank, and adding sodium metaaluminate solution (containing Al)2O352 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. The composition, pore distribution and main properties are shown in table 1.
Comparative example 1
Mixing Cu (NO) according to the component content of the catalyst F in the table 13)2·3H2O、Zn(NO3)2·6H2O and AlCl3·6H2Dissolving 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 13)2·3H2O and Zn (NO)3)2·6H2Dissolving O in deionized water to prepare a mixed solution. Adding deionized water into a reaction tank, and adding sodium metaaluminate solution (containing Al)2O342 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
Mixing Cu (NO) according to the component content of catalyst H in the table 13)2·3H2Dissolving O in deionized water to prepare solution A. Adding Zn (NO)3)2·6H2Dissolving O in deionized water to prepare solution B. Deionized water is added into the reaction tank 1, and sodium metaaluminate solution (containing Al) is added2O342 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 the reaction tank 2, and sodium metaaluminate solution (containing Al) is added2O342 g/L) and the solution B are added into a reaction tank 2 in a parallel flow mode, the gelling temperature is 60 ℃, the gelling pH value is 9.2, the gelling time is 2.0 hours, slurry II is obtained, 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 ℃, roasting is carried out for 3 hours at 360 ℃, a proper amount of graphite and water pressure are added into the roasted material for forming a sheet, and a catalyst H is obtained. 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 13)2·3H2O and AlCl3·6H2Dissolving O in deionized water to obtain mixed solution A, and dissolving Zn (NO)3)2·6H2O and AlCl3·6H2Dissolving 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 13)2·3H2O、Zn(NO3)2·6H2Dissolving O in deionized water to prepare a mixed solution A. Adding Cu (NO)3)2·3H2O and AlCl3·6H2Dissolving O in deionized water to prepare a mixed solution B. Adding deionized water into the reaction tank, and adding sodium metaaluminate solution (containing Al)2O342 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, the gelling time is 2.0 hours, so as to obtain slurry II, aging the slurry II under the stirring condition, the aging temperature is 75 ℃, the aging pH value is 7.8, and 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 at 100 ℃ for 10 hours, roasting at 360 ℃ for 3 hours, adding a proper amount of graphite into the roasted material, pressing the roasted material into sheets by water, and thus obtaining a catalyst J. The composition, pore distribution and main properties are shown in table 1.
Comparative example 6
A reference reagent K having the same composition as the catalyst of example 1 was prepared according to the method disclosed in CN201610773534.7, and the procedure was as follows:
cu (NO) with the catalyst composition of example 13)2·3H2Dissolving O in deionized water to prepare solution A. Adding Zn (NO)3)2·6H2Dissolving O in deionized water to prepare a mixed solution B. Adding deionized water into the reaction tank, and adding sodium metaaluminate solution (containing Al)2O342 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, so that copper-containing and aluminum-containing precipitate slurry I is obtained. Sodium metaaluminate solution (containing Al)2O342 g/L) is added into the solution B under stirring, the gelling temperature is kept at 60 ℃, the pH value is controlled at 7.5 when the gelling is finished, and the gelling time is controlled at 2 hours, thereby generating zinc and aluminum containing precipitate slurry II. Will be provided withThe two types of slurry containing the precipitate are mixed. The aging is started under the condition of stirring, the pH value is 7.8 during the aging, the temperature is 75 ℃, the aging is carried out for 3.7 hours, the materials are filtered after the aging, the filter cake is subjected to hydrothermal treatment under the water vapor containing urea, and the conditions of the hydrothermal treatment are as follows: the mol ratio of the total amount of the urea and the active metal atoms is 7:1, 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 the roasted material is added with a proper amount of graphite and pressed into sheets to obtain the catalyst K. 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 use2/N2And (vol) = 3/97) reducing the mixed gas of hydrogen and nitrogen for 16-25 h, wherein the maximum reduction temperature is 235 ℃. The activity of the catalyst was evaluated on a miniature fixed bed reactor. The loading of the catalyst is 5ml, and the composition of the raw material gas is CO/H2/CO2/N2=12/70/6/12 (volume ratio), reaction pressure is 5.0MPa, space velocity is 10000h-1The reaction temperature was 250 ℃ and CO were measured2The 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 CO2The conversion of (b) is activity after heat treatment, i.e., heat resistance. The product was analyzed by gas chromatography to give a space-time yield of g.mL of methanol-1·h-1I.e., grams of methanol produced per milliliter of catalyst per hour, the results are shown in table 2.
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, more concentrated pore structure distribution, mainly concentrated in 10nm to 15nm, and high activity and selectivity of the catalyst in the pore distribution range.
TABLE 1 catalyst composition and Properties
Figure DEST_PATH_IMAGE001
TABLE 1 (continuation)
Figure 124478DEST_PATH_IMAGE002
TABLE 2 degree of dispersion and specific surface area of metallic copper
Figure DEST_PATH_IMAGE003
SCuIs the specific surface area of copper, DCuIs degree of dispersion of copper
TABLE 3 evaluation of catalyst Activity and Heat resistance test results
Figure 228569DEST_PATH_IMAGE004

Claims (13)

1. The preparation method of the methanol synthesis 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) dropwise adding the mixed solution B and a sodium carbonate solution into the aged slurry I obtained in the step (1) in a parallel flow manner, carrying out gelling reaction to obtain slurry II, and then aging; (3) carrying out solid-liquid separation on the material obtained in the step (2), and drying, roasting and forming a solid phase to obtain a catalyst; wherein the mixed solution A is an aqueous solution containing soluble copper salt, soluble zinc salt and a compound containing element A, and the mixed solution B is an aqueous solution containing soluble copper salt, soluble aluminum salt and a compound containing element A; the element A is one or more of boron, phosphorus or silicon.
2. The method of claim 1, wherein: in the mixed solution A in the step (1), the concentration of the soluble copper salt is Cu2+Calculated as 1.0-5.0 mol/L, and the concentration of soluble zinc salt is Zn2+0.5-6.0 mol/L, and the weight concentration of the element A oxide is 1-30 g/L; the copper content in the mixed solution A is in the catalyst40% -80% of copper content; the content of the element A oxide in the mixed solution A is 20-80% of the element A oxide in the catalyst.
3. The method of claim 1, wherein: the element A-containing compound is selected from one or more of boric acid, sodium silicate, silica sol, phosphoric acid, ammonium hydrogen phosphate and ammonium dihydrogen phosphate.
4. The method of claim 1, wherein: the concentration of the sodium metaaluminate solution in the step (1) is Al2O3The amount is 10-90 g/L.
5. 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.
6. 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.
7. The method of claim 1, wherein: in the mixed solution B in the step (2), the concentration of the soluble copper salt is Cu2+0.5 to 4.0mol/L in terms of Al, and a concentration of soluble aluminum salt3+0.5-5.0 mol/L, and the weight concentration of the element A oxide is 1-25 g/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.
8. 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 copper and zinc is 0.5-4.0.
9. 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).
10. 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, and the pH value is 7.5-11.0 which is at least 0.5 higher than the pH value of the aging in the step (1).
11. A synthetic methanol catalyst prepared according to the method of any one of claims 1 to 10, characterized in that: based on the weight of the catalyst, the catalyst comprises the following components: 20 to 62 percent of CuO, 15 to 35 percent of ZnO and Al2O35% -25%, element A oxide 2% -20%; wherein the element A is one or more of boron, phosphorus or silicon.
12. The methanol synthesis catalyst of claim 1, wherein: the properties of the methanol synthesis catalyst are as follows: the specific surface area is 100-550 m2The 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% of the total pore volume, the pore volume of the pores with the diameter of 10-15 nm accounts for 58-85% of the total pore volume, and the pore volume of the pores with the diameter of more than 15nm accounts for 1-15% of the total pore volume.
13. The methanol synthesis catalyst of claim 1, wherein: the specific surface area of the metal copper in the reduced catalyst is 35-120 m2The dispersity of the metal copper is 13-45 percent.
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