CN112264025B - Simple, energy-saving and environment-friendly preparation method of methanol synthesis catalyst - Google Patents

Simple, energy-saving and environment-friendly preparation method of methanol synthesis catalyst Download PDF

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CN112264025B
CN112264025B CN202011292800.7A CN202011292800A CN112264025B CN 112264025 B CN112264025 B CN 112264025B CN 202011292800 A CN202011292800 A CN 202011292800A CN 112264025 B CN112264025 B CN 112264025B
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salt solution
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赵安民
周菊发
蔡洪城
孙晨
贺安平
黄晨
张向辉
王蕾
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Southwest Research and Desigin Institute of Chemical Industry
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    • 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
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
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    • B01J37/08—Heat treatment
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    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention belongs to the technical field of catalysts, relates to preparation of a methanol synthesis catalyst, and particularly relates to a simple, energy-saving and environment-friendly preparation method of the methanol synthesis catalyst. The method adopts a solution direct decomposition method or a slurry direct decomposition method to prepare a composite oxide, and then a graphite auxiliary agent is added for tabletting and forming to obtain the synthetic methanol catalyst. When the catalyst is prepared by adopting the method, the problems of large salt-containing wastewater treatment capacity and high energy consumption can be solved, the preparation method is simple, the preparation process is environment-friendly, and the prepared synthetic methanol catalyst has the characteristics of good low-temperature activity, good thermal stability and good high-temperature selection.

Description

Simple, energy-saving and environment-friendly preparation method of methanol synthesis catalyst
Technical Field
The invention belongs to the technical field of catalysts, relates to preparation of a methanol synthesis catalyst, and particularly relates to a simple, energy-saving and environment-friendly preparation method of the methanol synthesis catalyst.
Background
Methanol is an important basic chemical raw material and is widely applied in the field of traditional chemical industry, and the methanol is usually synthesized in Cu/ZnO/Al through synthesis gas2O3Under the action of catalyst. At present, the catalyst in a domestic large methanol device is at the operation temperature of more than 280 ℃ or even 300 ℃ for a long time, so that the catalyst is required to have the necessary low-temperature activation performance, thermal stability and high-temperature selectivity. Current commercial catalystsSuch catalysts are generally prepared by a two-step co-precipitation process, i.e. slurrying by mixing a suspension obtained from the precipitation of aluminium with a suspension obtained from the precipitation of copper and zinc.
When a conventional two-step precipitation method is adopted, a large amount of water is needed to wash the precipitate to remove alkali metal ions in the precipitate, so that a large amount of salt-containing wastewater is generated, and along with the increasingly strict national requirements on sewage treatment, the wastewater has the problems of large treatment capacity and high treatment energy consumption, so that a preparation method of a methanol synthesis catalyst capable of reducing the generation of the salt-containing wastewater under the condition of meeting industrial application is urgently required.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a simple, energy-saving and environment-friendly preparation method of a methanol synthesis catalyst. The catalyst prepared by the method can be used as a methanol synthesis catalyst for industrial application, the preparation process is environment-friendly and energy-saving, and the generation amount of salt-containing wastewater can be effectively reduced.
In order to achieve the above purpose, the specific technical scheme of the invention is as follows:
a simple, energy-saving and environment-friendly preparation method of a synthetic methanol catalyst is characterized in that the catalyst is prepared into a composite oxide by adopting a solution or slurry direct decomposition method, and then a graphite auxiliary agent is added for tabletting and forming to obtain the synthetic methanol catalyst; the catalyst comprises the following components in percentage by mass: 65-75% of CuO, 15-20% of ZnO and Al2O35-13 percent of MgO, and the balance of MgO, wherein the sum of the total mass percentage is 100 percent.
In a preferred embodiment of the present invention, the amount of the graphite additive is 2 to 5% by mass based on the mass of the catalyst.
The method for preparing the composite oxide of copper, zinc, aluminum and magnesium has two modes:
(1) solution direct decomposition method
Dissolving copper nitrate, zinc nitrate, aluminum nitrate and magnesium nitrate in water to form a copper-zinc-magnesium-aluminum mixed solution A, atomizing the solution A and spraying the solution A into a high-temperature furnace at a certain temperature, and after the solution is sprayed, continuously preserving the temperature in the furnace for a period of time and then cooling; to obtain the composite oxide of copper, zinc, aluminum and magnesium.
(2) Direct decomposition method of slurry
Dissolving magnesium nitrate and aluminum nitrate in water to form a magnesium-aluminum mixed salt solution B, dissolving zinc nitrate, aluminum nitrate, copper nitrate and magnesium nitrate in water to form a copper-zinc-magnesium-aluminum mixed salt solution C, dissolving sodium carbonate in water to form an alkali solution D, simultaneously dripping the salt solution B and the alkali solution D into a reaction tank containing deionized water under the stirring action, controlling the pH value and the temperature to react to generate precipitates, stopping dripping the alkali solution D after the dripping of the salt solution B is finished, continuing to age for a certain time, and after the ageing is finished, filtering and washing the precipitate, dispersing a filter cake obtained by filtering into a mixed salt solution C to form highly dispersed slurry E, atomizing and spraying the slurry E into a high-temperature furnace at a certain temperature, and continuing to keep the temperature in the furnace for a period of time and then cooling after the slurry E is sprayed, thereby obtaining the composite oxide of copper, zinc, aluminum and magnesium.
As a preferred embodiment in this application, Mg in salt solution B2+Accounts for the total Mg in the salt solution B and the salt solution C2+More than 70% of (C), Al in the salt solution B3+Accounts for the total Al in the salt solution B and the salt solution C3+More than 70 percent of the total amount of the active ingredients.
As a better implementation mode in the application, the pH value of the reaction product when generating the precipitate is controlled to be 7.0-8.5, and the temperature is controlled to be 70-80 ℃; the aging time is controlled to be 30-60 min.
As a better embodiment in the application, the preset temperature in the high-temperature furnace is 300-400 ℃, and the holding time is 4-5 h.
In the invention, the tail gas of the high-temperature furnace is connected into a nitrogen oxide treatment device for environmental protection of the process.
Compared with the prior art, the invention has the following beneficial effects:
when the catalyst is prepared by adopting a direct decomposition method, nitrogen oxides generated in the preparation process are treated by an oxynitride treatment device, and the energy consumption for treating the nitrogen oxides is lower than that for treating salt-containing wastewater generated in the preparation of the catalyst with the same quality.
And (II) when the catalyst is prepared by adopting a slurry direct decomposition method, a small amount of salt-containing wastewater is generated only during washing the first-step precipitation, and the amount of the generated salt-containing wastewater is obviously smaller than that of the salt-containing wastewater generated during preparing the catalyst by adopting a traditional precipitation method.
And (III) when the catalyst is prepared by adopting a direct decomposition method, drying is not needed, and compared with the traditional precipitation method for preparing the catalyst, the method for preparing the catalyst is simpler.
(IV) dispersing a part of the precipitate into Cu by adopting a step-by-step method2+After the solution is directly decomposed, the first-step precipitate plays a role in supporting a carrier, and the thermal stability of the catalyst is improved;
(V) dispersing a part of precipitate into Cu by adopting a step-by-step method2+In solution of (2), part of Cu is favored2+Entering pores of the first precipitation step, and partial Cu2+And the catalyst is deposited in pores in the first-step sediment, and the first-step sediment contains MgO, so that the high-temperature selectivity of the catalyst is improved.
Drawings
FIG. 1 is a schematic view of the solution or slurry direct decomposition process of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in the attached figure 1, the device used in the direct solution or slurry decomposition process comprises a high-temperature furnace, an atomizer arranged above the high-temperature furnace and a nitrogen compound treatment device, wherein tail gas of the high-temperature furnace is connected into the nitrogen oxide treatment device.
The percentages referred to in the following examples are by mass, i.e., wt%, unless otherwise specified.
Example 1:
the embodiment provides a preparation method for preparing a methanol synthesis catalyst by a solution direct decomposition method, which specifically comprises the following steps:
322.16g of Cu (NO)3)2·3H2O，110.76g Zn(NO3)2·6H2O，89.19g Al(NO3)3·9H2O and 19.43g Mg (NO)3)2.6H2O was dissolved in 700ml of deionized water and stirred to dissolve it sufficiently to form a salt solution A.
Atomizing and spraying the salt solution A into a high-temperature furnace at the temperature of 400 ℃, and after the salt solution A is sprayed, preserving the temperature in the furnace for 4 hours and then cooling to obtain a copper-zinc-aluminum-magnesium composite oxide; and adding graphite into the obtained oxide, uniformly mixing to obtain a mixture, wherein the using amount of the graphite is 2% of the mass of the mixture, and forming to obtain the catalyst, wherein the number of the catalyst is sample 1.
Example 2:
the embodiment provides a preparation method for preparing a methanol synthesis catalyst by a solution direct decomposition method, which specifically comprises the following steps:
345.17g of Cu (NO)3)2·3H2O，99.69g Zn(NO3)2·6H2O，55.75g Al(NO3)3·9H2O and 19.43g Mg (NO)3)2.6H2O was dissolved in 700ml of deionized water and stirred to dissolve it sufficiently to form a salt solution A.
Atomizing and spraying the salt solution A into a high-temperature furnace at the temperature of 400 ℃, after the salt solution A is sprayed, preserving the temperature in the furnace for 4 hours, and then cooling to obtain a copper-zinc-aluminum-magnesium composite oxide, adding graphite into the obtained oxide, uniformly mixing to obtain a mixture, wherein the using amount of the graphite is 2% of the mass of the mixture, and forming to obtain a catalyst, wherein the number of the catalyst is sample 2.
Example 3:
the embodiment provides a preparation method for preparing a methanol synthesis catalyst by a slurry direct decomposition method, which specifically comprises the following steps:
13.6g Mg (NO)3)2.6H2O and 101.46g Al (NO)3)3·9H2O is dissolved in 600ml of deionized water and stirred to be sufficiently dissolved, thereby forming a salt solution B. 299.14g of Cu (NO)3)2·3H2O，110.76g Zn(NO3)2·6H2O，43.48g Al(NO3)3·9H2O and 5.83g Mg (NO)3)2.6H2O is dissolved in 600ml of deionized water and stirred to dissolve it sufficiently to form a salt solution C. 160.59g NaCO3Dissolving in 1000ml deionized water and stirring to dissolve fully to form alkali solution D for precipitation.
Preheating a salt solution B, a salt solution C and an alkali solution D, dropwise adding the salt solution B and the alkali solution D into a reaction tank containing a certain amount of deionized water simultaneously under strong stirring after the preheating temperature reaches 70 ℃, stopping dropwise adding the alkali D after dropwise adding the solution B, controlling the reaction temperature to be 80 ℃, and controlling the pH value to be 7.0-7.5. Aging at 80 deg.C for 30min, filtering, and washing with deionized water until no Na is detected+. And (3) dispersing the filter cake of the precipitate in the first step into the mixed salt solution C by using a circulating emulsification pump to form highly dispersed suspension slurry E.
And atomizing and spraying the slurry E into a high-temperature furnace at the temperature of 300 ℃, preserving the temperature in the furnace for 5 hours after the slurry E is sprayed, cooling to obtain a copper-zinc-aluminum-magnesium composite oxide, adding graphite into the obtained oxide, uniformly mixing to obtain a mixture, wherein the using amount of the graphite is 2% of the mass of the mixture, and forming to obtain a catalyst, wherein the number of the catalyst is sample 3.
Example 4:
the embodiment provides a preparation method for preparing a methanol synthesis catalyst by a slurry direct decomposition method, which specifically comprises the following steps:
13.6g Mg (NO)3)2.6H2O and 101.46g Al (NO)3)3·9H2O is dissolved in 600ml of deionized water and stirred to be sufficiently dissolved, thereby forming a salt solution B. 299.14g of Cu (NO)3)2·3H2O，110.76g Zn(NO3)2·6H2O，43.48g Al(NO3)3·9H2O and 5.83g Mg (NO)3)2.6H2O is dissolved in 600ml of deionized water and stirred to dissolve it sufficiently to form a salt solution C. 160.59g NaCO3Dissolving in 1000ml deionized water, stirring to dissolve completely to form alkali solution for precipitationD。
Preheating a salt solution B, a salt solution C and an alkali solution D, dropwise adding the salt solution B and the alkali solution D into a reaction tank containing a certain amount of deionized water simultaneously under strong stirring after the preheating temperature reaches 80 ℃, stopping dropwise adding the alkali D after dropwise adding the solution B, controlling the reaction temperature to be 80 ℃, and controlling the pH value to be 8.0-7.5. The constant temperature ageing at 80 ℃ is continued for 60min, followed by filtration and washing with deionized water until no Na is detected+. And (3) dispersing the filter cake of the precipitate in the first step into the mixed salt solution C by using a circulating emulsification pump to form highly dispersed suspension slurry E.
And atomizing and spraying the slurry E into a high-temperature furnace at the temperature of 400 ℃, preserving the temperature in the furnace for 4 hours after the slurry E is sprayed, cooling to obtain a copper-zinc-aluminum-magnesium composite oxide, adding graphite into the obtained oxide, uniformly mixing to obtain a mixture, wherein the using amount of the graphite is 5% of the mass of the mixture, and forming to obtain a catalyst, wherein the number of the catalyst is sample 4.
Example 5:
the embodiment provides a preparation method for preparing a methanol synthesis catalyst by a slurry direct decomposition method, which specifically comprises the following steps:
13.6g Mg (NO)3)2.6H2O and 62.43g Al (NO)3)3·9H2O is dissolved in 600ml of deionized water and stirred to be sufficiently dissolved, thereby forming a salt solution B. 345.17g of Cu (NO)3)2·3H2O，83.07g Zn(NO3)2·6H2O，26.76g Al(NO3)3·9H2O and 5.83g Mg (NO)3)2.6H2O is dissolved in 600ml of deionized water and stirred to dissolve it sufficiently to form a salt solution C. 160.59g NaCO3Dissolving in 1000ml deionized water and stirring to dissolve fully to form alkali solution D for precipitation.
Preheating a salt solution B, a salt solution C and an alkali solution D, dropwise adding the salt solution B and the alkali solution D into a reaction tank containing a certain amount of deionized water simultaneously under strong stirring when the preheating temperature reaches 80 ℃, stopping dropwise adding the alkali D after dropwise adding the solution B, controlling the reaction temperature to be 80 ℃, and controlling the pH value to be 7.0-7.5. Aging at 80 deg.C for 30min, filtering, and washing with deionized water until no Na is detected+. And (3) dispersing the filter cake of the precipitate in the first step into the mixed salt solution C by using a circulating emulsification pump to form highly dispersed suspension slurry E.
And atomizing and spraying the slurry E into a high-temperature furnace at the temperature of 300 ℃, preserving the temperature in the furnace for 5 hours after the slurry E is sprayed, cooling to obtain a copper-zinc-aluminum-magnesium composite oxide, adding graphite into the obtained oxide, uniformly mixing to obtain a mixture, wherein the using amount of the graphite is 2% of the mass of the mixture, and forming to obtain a catalyst, wherein the number of the catalyst is sample 5.
Example 6:
the embodiment provides a preparation method for preparing a methanol synthesis catalyst by a slurry direct decomposition method, which specifically comprises the following steps:
19.43g of Mg (NO)3)2.6H2O and 89.19g Al (NO)3)3·9H2O is dissolved in 600ml of deionized water and stirred to be sufficiently dissolved, thereby forming a salt solution B. 345.17g of Cu (NO)3)2·3H2O and 83.07g Zn (NO)3)2·6H2O is dissolved in 600ml of deionized water and stirred to dissolve it sufficiently to form a salt solution C. 160.59g NaCO3Dissolving in 1000ml deionized water and stirring to dissolve fully to form alkali solution D for precipitation.
Preheating a salt solution B, a salt solution C and an alkali solution D, dropwise adding the salt solution B and the alkali solution D into a reaction tank containing a certain amount of deionized water simultaneously under strong stirring after the preheating temperature reaches 70 ℃, stopping dropwise adding the alkali D after dropwise adding the solution B, controlling the reaction temperature to be 80 ℃, and controlling the pH value to be 8.0-8.5. Aging at 80 deg.C for 30min, filtering, and washing with deionized water until no Na is detected+. And (3) dispersing the filter cake of the precipitate in the first step into the mixed salt solution C by using a circulating emulsification pump to form highly dispersed suspension slurry E.
And atomizing and spraying the slurry E into a high-temperature furnace at the temperature of 400 ℃, preserving the temperature in the furnace for 4 hours after the slurry E is sprayed, cooling to obtain a copper-zinc-aluminum-magnesium composite oxide, adding graphite into the obtained oxide, uniformly mixing to obtain a mixture, wherein the using amount of the graphite is 5% of the mass of the mixture, and forming to obtain a catalyst, wherein the number of the catalyst is sample 6.
Example 7:
the embodiment provides a preparation method for preparing a methanol synthesis catalyst by a slurry direct decomposition method, which specifically comprises the following steps:
19.43g of Mg (NO)3)2.6H2O and 144.94g Al (NO)3)3·9H2O is dissolved in 600ml of deionized water and stirred to be sufficiently dissolved, thereby forming a salt solution B. 299.14g of Cu (NO)3)2·3H2O and 110.76g Zn (NO)3)2·6H2O was dissolved in 550ml of deionized water and stirred to dissolve it sufficiently to form a salt solution C. 160.59g NaCO3Dissolving in 1000ml deionized water and stirring to dissolve fully to form alkali solution D for precipitation.
Preheating a salt solution B, a salt solution C and an alkali solution D, dropwise adding the salt solution B and the alkali solution D into a reaction tank containing a certain amount of deionized water simultaneously under strong stirring after the preheating temperature reaches 80 ℃, stopping dropwise adding the alkali D after dropwise adding the solution B, controlling the reaction temperature to be 80 ℃, and controlling the pH value to be 7.0-7.5. Aging at 80 deg.C for 30min, filtering, and washing with deionized water until no Na is detected+. And (3) dispersing the filter cake of the precipitate in the first step into the mixed salt solution C by using a circulating emulsification pump to form highly dispersed suspension slurry E.
And atomizing and spraying the slurry E into a high-temperature furnace at the temperature of 300 ℃, preserving the temperature in the furnace for 5 hours after the slurry E is sprayed, cooling to obtain a copper-zinc-aluminum-magnesium composite oxide, adding graphite into the obtained oxide, uniformly mixing to obtain a mixture, wherein the using amount of the graphite is 5% of the mass of the mixture, and forming to obtain a catalyst, wherein the number of the catalyst is sample 7.
Example 8:
this example is a comparative example, and this example adopts a traditional two-step precipitation method to prepare a catalyst, the composition of the catalyst by mass group is the same as that of example 3, and the preparation method specifically is as follows:
144.94g of Al (NO)3)3·9H2O is dissolved in 600ml of deionized water and stirred to be sufficiently dissolved, thereby forming a salt solution B. 299.14g of Cu (NO)3)2·3H2O，110.76g Zn(NO3)2·6H2O and 19.43g Mg (NO)3)2.6H2O was dissolved in 1300ml of deionized water and stirred to dissolve it sufficiently to form a salt solution C. 256.95g NaCO3Dissolved in 2000ml of deionized water and stirred to dissolve it sufficiently to form the alkali solution D required for precipitation.
Preheating a salt solution B, a salt solution C and an alkali solution D, and dropwise adding the salt solution C and the alkali solution D into a first reaction tank filled with a certain amount of deionized water simultaneously under strong stirring after the preheating temperature reaches 80 ℃; meanwhile, under the condition of strong stirring, the salt solution C and the alkali solution D are simultaneously dripped into a second reaction tank filled with a certain amount of deionized water, the pH values of the first reaction tank and the second reaction tank are 7.0-7.5, and the reaction temperatures of the first reaction tank and the second reaction tank are 80 ℃.
And stopping dropping the alkali D after the solution B and the solution C are dropped. Then the precipitates of the first reaction tank and the second reaction tank are quickly mixed in a mixing tank for pulping, and the mixture is aged for 60min at the constant temperature of 80 ℃ in the mixing tank.
After aging, the mixture is filtered and washed by deionized water until no Na is detected+Drying the obtained precipitate for 24 hours at the temperature of 110 ℃, finally roasting the dried product for 5 hours at the temperature of 300 ℃, adding graphite into the roasted product, uniformly mixing to obtain a mixture, wherein the using amount of the graphite is 5% of the mass of the mixture, and forming to obtain a comparative sample catalyst, wherein the serial number of the comparative sample catalyst is comparative sample 8.
Example 9:
this example provides a method for evaluating the catalysts of examples 1-8, as follows:
sample particle size: 16-40 meshes. Loading amount: 4mL (2mL catalyst +2mL inert support).
Activating a sample: samples were run with low concentrations of hydrogen (H) before being active and heat resistant2/N25/95 (volume ratio)) for 10-12 hThe maximum reduction temperature was 220 ℃.
And (3) activity test: the raw material gas composition is as follows: 13.0-14.0% of CO, CO2＝4.0-5.0％，N210%, the remainder is H2The reaction pressure is 5.0MPa, and the space velocity is 10000h-1The reaction temperature is 235-245 ℃, and the CO conversion rate and CH before heat resistance are measured3OH space time yield (amount of methanol produced per mL of catalyst per hour).
High-temperature selectivity test: and after the initial activity is measured, raising the reaction temperature to 295-300 ℃, and measuring the content of main impurities in the liquid-phase product.
Activity test after heat resistance: after the high-temperature selectivity is measured, the pressure is reduced to 0.1MPa, the reaction temperature is increased to 400 ℃, and the air velocity is reduced to 3000h-1Post heat treatment for 10h, then returning to the activity test condition, and measuring CO conversion rate and CH after heat resistance3OH space-time yield.
The thermal stability of the catalyst is expressed as the ratio of the methanol space-time yield after the heat resistance test to the initial methanol space-time yield.
The catalyst of examples 1 to 8 was subjected to activity evaluation before and after heat resistance by the above-mentioned test method, and the results are shown in table 1, and the relative values of the impurity contents of the respective samples were obtained by taking the impurity contents of the respective comparative samples 8 as the reference and dividing the impurity contents of the other samples by the impurity contents corresponding to the comparative samples 8 by the reference value, so that the impurity contents of the respective samples were visually reflected, and the results are shown in table 2.
TABLE 1 catalyst Heat resistant Pre-and post-catalyst activity data
Figure BDA0002784301120000111
TABLE 2 high temperature Selectivity of the catalyst
Ethanol N-propanol Isobutanol N-butanol
Sample 1 101 100 99 101
Sample 2 99 98 99 99
Sample 3 99 101 106 108
Sample No. 4 101 100 106 108
Sample No. 5 103 106 109 110
Sample No. 6 100 101 105 107
Sample 7 96 99 98 98
Comparative sample 8 100 100 100 100
As can be seen from table 1, samples 1, 3 and 4 achieved the fresh activity and thermal stability of comparative sample 8, and samples 2 and 7 achieved the fresh activity exceeding that of comparative sample 8, with thermal stability comparable to that of comparative sample 8; it can be seen from table 2 that the impurity contents of sample 1, sample 3 and sample 4 are not much different from the impurity content of comparative sample 8, and the impurity contents of sample 2 and sample 7 are slightly lower than the impurity content of comparative sample 8, which indicates that the catalyst prepared by the present invention can achieve low temperature performance, thermal stability and high temperature selectivity compared with the catalyst prepared by the conventional method, and the catalyst prepared by the present invention has the advantages of simple preparation method, reduced generation of a large amount of salt-containing wastewater, and more energy saving and environmental protection in the post-treatment of water.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (7)

1. A simple, energy-saving and environment-friendly preparation method of a methanol synthesis catalyst is characterized by comprising the following steps: the catalyst is prepared into composite oxide by adopting a slurry direct decomposition method, and then graphite auxiliary agent is added for tabletting and forming to obtain the catalyst; the catalyst comprises the following components in percentage by mass: 65-75% of CuO, 15-20% of ZnO and Al2O35-13 percent of MgO, and the balance of MgO, wherein the sum of the total mass percentage is 100 percent;
the method for directly decomposing the slurry comprises the following specific steps:
dissolving magnesium nitrate and aluminum nitrate in water to form a magnesium-aluminum mixed salt solution B, dissolving zinc nitrate, aluminum nitrate, copper nitrate and magnesium nitrate in water to form a copper-zinc-magnesium-aluminum mixed salt solution C, and dissolving sodium carbonate in water to form an alkali solution D; under the stirring action, simultaneously dripping a salt solution B and an alkali solution D into a reaction tank containing deionized water, reacting to generate a precipitate under the conditions of controlling a certain pH value and temperature, stopping dripping the alkali solution D after finishing dripping the salt solution B, continuing aging for a certain time, filtering and washing the precipitate after finishing aging, dispersing a filter cake obtained by filtering into a mixed salt solution C to form highly dispersed slurry E, atomizing and spraying the slurry E into a high-temperature furnace with a preset certain temperature, and continuing preserving heat in the high-temperature furnace for a period of time and then cooling after finishing spraying the slurry E; obtaining a composite oxide of copper, zinc, aluminum and magnesium; adding graphite into the obtained oxide, uniformly mixing to obtain a mixture, and forming the mixture to obtain the catalyst.
2. The method for preparing a catalyst for synthesizing methanol according to claim 1, wherein: the addition amount of the graphite is 2-5% of the mass of the catalyst.
3. The method for preparing a catalyst for synthesizing methanol according to claim 1, wherein: in the salt solution B, Mg2+Accounts for the total Mg in the salt solution B and the salt solution C2+More than 70% of (C), Al in the salt solution B3+Accounts for the total Al in the salt solution B and the salt solution C3+More than 70 percent of the total amount of the active ingredients.
4. The method for preparing a catalyst for synthesizing methanol according to claim 1, wherein: the pH value of the reaction product during the generation of the precipitate is controlled to be 7.0-8.5, and the temperature is controlled to be 70-80 ℃.
5. The method for preparing a catalyst for synthesizing methanol according to claim 1, wherein: the aging time is controlled to be 30-60 min.
6. The method for preparing a catalyst for synthesizing methanol according to claim 1, wherein: the preset temperature in the high-temperature furnace is 300-400 ℃, and the heat preservation time is 4-5 h.
7. A synthetic methanol catalyst prepared according to any one of claims 1 to 6 wherein: the catalyst is used for synthesizing methanol, and effectively reduces the generation of salt-containing wastewater.
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