CN114602449A - ZnZrO2Surface solid solution catalyst and preparation method and application thereof - Google Patents

ZnZrO2Surface solid solution catalyst and preparation method and application thereof Download PDF

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CN114602449A
CN114602449A CN202011439063.9A CN202011439063A CN114602449A CN 114602449 A CN114602449 A CN 114602449A CN 202011439063 A CN202011439063 A CN 202011439063A CN 114602449 A CN114602449 A CN 114602449A
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catalyst
zro
solid solution
znzro
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CN114602449B (en
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李�灿
汤驰洲
王集杰
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Dalian Institute of Chemical Physics of CAS
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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
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • 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
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Abstract

The application discloses a ZnZrO2Surface solid solution catalyst, preparation method and application thereof, wherein the catalyst comprises ZrO2Bulk phase and the ZrO2Solid solution formed on the surface of the bulk phase; the solid solution is dissolved in ZrO by Zn2And (4) forming a surface. ZnZrO provided by the application2The surface solid solution catalyst has the characteristics of high methanol selectivity, large specific surface area, good stability, strong heat resistance and the like, and can effectively improve the conversion rate of carbon dioxide and the space-time yield of methanol when being used for the reaction of synthesizing methanol by hydrogenating carbon dioxide.

Description

ZnZrO2Surface solid solution catalyst and preparation method and application thereof
Technical Field
The application relates to ZnZrO2A surface solid solution catalyst, a preparation method and application thereof, belonging to the field of catalysts.
Background
From CO2A series of environmental problems such as greenhouse effect, ocean acidification and the like have attracted extensive attention all over the world. CO 22Emission reduction is imminent.
Hydrogen production by renewable energy sources and CO reuse2Catalytic hydrogenation technology synthesisChemicals and fuels, not only reducing CO2CO may also be emitted2The carbon resource can be effectively utilized, so that the method achieves two purposes. Methanol can be used as fuel, is one of the most important chemical raw materials, and can be further synthesized into various organic chemicals. By using CO2The hydro-synthesis of methanol is the most efficient strategy to achieve the above route.
For CO2The catalyst for synthesizing methanol by hydrogenation is mostly a Cu-based catalyst, and most of researches are to synthesize a CuZnAl catalyst by a coprecipitation method and add an auxiliary agent into the catalyst for modification. In view of the present research results, the best results are Zr or Ti modified CuZnAl catalysts (petrochemical, 2009,38(5), 482; journal of fuel chemistry, 2011,39(12), 912). However, methanol selectivity over Cu-based catalysts is generally not higher than 60%, which reduces feedstock utilization. In addition, the hydrogenation of carbon dioxide to methanol is an exothermic reaction, and a large amount of heat is released during the reaction, and the Cu-based catalyst is poor in heat resistance, generates water, and promotes the sintering of Cu in the presence of water. There are also many In2O3Study as active ingredient, however, In2O3The catalyst is easy to reduce into metal In, and the melting point of the metal In is very low, so that the catalyst can be subjected to reduction sintering under the hydrogenation condition, the service life of the catalyst cannot be ensured, and the selectivity of the byproduct methane is also high. Chinese patent CN109420486A, discloses a method for CO2ZnZrO of hydrogenation synthesis of methanolxSolid solution catalyst, preparation of ZnZrO by precipitation methodxThe solid solution catalyst can effectively inhibit reverse water gas shift reaction so as to improve the selectivity of methanol, and has the advantages of strong heat resistance, sintering resistance, good stability and the like. However, the co-precipitation method requires multiple washing of the catalyst, resulting in a large amount of wastewater. Meanwhile, in order to maintain the structure of the solid solution, the conditions need to be accurately controlled in the processes of precipitation and roasting, higher roasting temperature is needed, and the steps are complicated. In addition, the small specific surface of the solid solution catalyst limits the conversion of the reaction and the space-time yield of methanol. There are also reports in the literature of direct ZrO2Supported ZnO/ZrO prepared by impregnating zinc nitrate on carrier2Catalyst but due to ZrO2Has formed a crystal structure that Zn cannot be inserted into ZrO by impregnation and low-temperature firing2The crystal lattice forms solid solution, the synergistic effect of Zn and Zr is greatly weakened, and thus the supported ZnO/ZrO2Catalyst performance is generally poor.
Disclosure of Invention
According to one aspect of the present application, there is provided a ZnZrO2The surface solid solution catalyst has the advantages of large specific surface area, good stability, high carbon dioxide conversion rate and high methanol space-time yield.
The catalyst comprises ZrO2Bulk phase and the ZrO2Solid solution formed on the surface of the bulk phase;
the solid solution is dissolved in ZrO by Zn2And (4) forming a surface.
Optionally, in the catalyst, the content of Zn in the solid solution is 0.1-30%;
wherein Zn is calculated by the mass of ZnO.
Specifically, the lower limit of the mass fraction of ZnO in the catalyst may be independently selected from 0.1%, 1%, 5.2%, 9.1%, 10%; the upper limit of the mass fraction of ZnO in the catalyst can be independently selected from 13%, 15%, 20%, 26% and 30%.
According to still another aspect of the present application, there is provided the above ZnZrO2A method for producing a surface solid solution catalyst, the method comprising any one of method one, method two, and method three:
the method comprises the following steps: synthesizing the ZnZrO by adopting an impregnation method2Surface solid solution catalyst
1-1) obtaining a precursor containing Zn and ZrO2Suspension I of the precursor;
1-2) removing the solvent in the suspension I in the step 1-1), and roasting the residual solid phase to obtain the ZnZrO2A surface solid solution catalyst;
the second method comprises the following steps: ZnZrO synthesis by deposition precipitation method2Surface solid solution catalyst
2-1) obtaining a precursor containing Zn and ZrO2Suspension of precursorA turbid liquid II;
2-2) obtaining a solution III containing a precipitating agent;
2-3) mixing the suspension II in the step 2-1) with the solution III in the step 2-2), and filtering to obtain a precipitate;
2-4) roasting the precipitate to obtain the ZnZrO2A surface solid solution catalyst;
the third method comprises the following steps:
3-1) to contain ZrO2Introducing a gas-phase Zn precursor into the dry material of the precursor, and operating to deposit Zn in the Zn precursor on ZrO2Precursor surface to obtain intermediate;
3-2) roasting the intermediate to obtain the ZnZrO2A surface solid solution catalyst.
Optionally, the Zn precursor is ZrO based on the mass of ZnO2Precursor with ZrO2The Zn precursor and ZrO2The mass ratio of the precursor is 1: 999-3: 7;
preferably, the Zn precursor is at least one of zinc nitrate, zinc acetate, zinc halide, diethyl zinc and metallocene zinc;
preferably, ZrO2The precursor is zirconium carbonate, zirconium hydroxide, basic zirconium carbonate and oxygen-containing defective zirconium oxide ZrO2At least one of (a).
In particular, Zn precursor and ZrO2The lower limit of the mass ratio of the precursor can be independently selected from 1:999, 1:99, 5:95, 1:9 and 12: 88; zn precursor and ZrO2The lower and upper limits of the mass ratio of the precursors can be independently selected from 15:85, 17:83, 2:8, 25:75 and 3: 7.
Optionally, the roasting temperature is 300-800 ℃.
Preferably, the firing is performed under a protective atmosphere, and further preferably, the protective atmosphere is at least one of nitrogen and argon.
Preferably, the roasting time is 3-5 h.
Optionally, the reaction product is dried before roasting, and the drying temperature is 100-150 ℃.
Specifically, the lower limit of the roasting temperature can be independently selected from 300 ℃, 350 ℃, 400 ℃, 450 ℃ and 500 ℃; the upper limit of the calcination temperature may be independently selected from 550 deg.C, 600 deg.C, 650 deg.C, 700 deg.C, 800 deg.C.
Optionally, in the first method, the content of the Zn precursor in the suspension i is 0.01 to 10 mol/L.
Specifically, the lower limit of the content of the Zn precursor can be independently selected from 0.01mol/L, 0.5mol/L, 1mol/L, 3.2mol/L and 5 mol/L; the upper limit of the content of the Zn precursor can be independently selected from 6mol/L, 7mol/L, 8mol/L, 9mol/L and 10 mol/L.
In the impregnation method (i.e., method one), the Zn precursor is preferably at least one of zinc nitrate, zinc acetate, zinc halide, and diethyl zinc.
Optionally, in the second method, the content of the Zn precursor in the suspension II is 0.01-7 mol/L;
in the solution III, the content of a precipitator is 0.01-14 mol/L;
preferably, the precipitant is at least one of ammonia water, ammonium carbonate, ammonium bicarbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, and potassium hydroxide.
Preferably, adding a precipitator to regulate the pH value of a reaction system to 6.0-8.0;
preferably, in the solution I, the solution II and the solution III, the solvent is water, methanol, ethanol and the like;
in the deposition precipitation method (i.e. method two), preferably, the Zn precursor is at least one of zinc nitrate, zinc acetate, zinc halide, and diethyl zinc.
Specifically, the lower limit of the concentration of the Zn precursor solution can be independently selected from 0.01mol/L, 0.5mol/L, 1mol/L, 3.2mol/L and 5 mol/L; the concentration upper limit of the Zn precursor solution can be independently selected from 6mol/L, 7mol/L, 8mol/L, 9mol/L and 7 mol/L.
Specifically, the lower limit of the content of the precipitant can be independently selected from 0.01mol/L, 0.1mol/L, 1mol/L, 3mol/L, 5 mol/L; the upper limit of the content of the precipitant can be independently selected from 7mol/L, 9mol/L, 10mol/L, 12mol/L and 14 mol/L.
Optionally, step 3-1) is: ZrO 2 is mixed with2Heating the precursor in a reaction furnace at 25-300 ℃, and introducing gas phaseZn precursor, operating to deposit Zn in the Zn precursor on ZrO2And (4) coating the precursor to obtain an intermediate.
Preferably, the heating temperature is 25-300 ℃;
specifically, the lower limit of the heating temperature can be independently selected from 25 ℃, 50 ℃, 75 ℃, 100 ℃ and 125 ℃; the upper limit of the heating temperature may be independently selected from the group consisting of 150 deg.C, 175 deg.C, 200 deg.C, 250 deg.C, and 300 deg.C.
Optionally, in step 3-1), the operation is: depositing Zn on ZrO by decomposing or reacting a gas-phase Zn precursor by controlling the temperature or introducing a substance capable of reacting with the gas-phase Zn precursor2The precursor surface.
Optionally, the decomposition control temperature is 50-500 ℃;
preferably, the reaction conditions are: the reaction temperature is 100-200 ℃.
Preferably, the substance capable of reacting with the gas-phase Zn precursor is O2、H2O、O3At least one of (1).
Specifically, the lower limit of the decomposition control temperature may be independently selected from 50 ℃, 100 ℃, 150 ℃,200 ℃, 250 ℃; the upper limit of the decomposition control temperature can be independently selected from 300 ℃, 350 ℃, 400 ℃, 450 ℃ and 500 ℃.
Specifically, the lower limit of the reaction temperature may be independently selected from 100 ℃, 110 ℃, 120 ℃, 130 ℃, 150 ℃; the upper limit of the reaction temperature may be independently selected from 160 deg.C, 170 deg.C, 180 deg.C, 190 deg.C, 200 deg.C.
In a specific embodiment of the present application, ZrO is added to the reaction furnace2Heating the precursor to 25-300 ℃, introducing the gasified Zn precursor through inert gas, controlling the reaction temperature to be 50-500 ℃, and reacting for 0.1-30 min to decompose the Zn precursor to obtain a product.
For deposition of gas-phase Zn precursor on ZrO2The reaction temperature on the surface of the precursor is higher than the gasification temperature of the Zn precursor. The specific reaction temperature varies depending on the vaporization temperature of different kinds of Zn precursors.
In another embodiment of the present invention, ZrO is added to the reaction furnace2Precursor ofHeating the precursor to 25-300 ℃, introducing a gasified Zn precursor through inert gas, vacuumizing, introducing inert gas containing substances capable of reacting with the gas-phase Zn precursor, controlling the reaction temperature to be 50-500 ℃, reacting for 0.1-30 min, and depositing Zn on ZrO through the reaction of the gas-phase Zn precursor and oxidizing substances2And (3) coating the surface of the precursor to obtain a product.
In order to completely react the gas-phase Zn precursor, the substance capable of reacting with the gas-phase Zn precursor should be introduced in excess. The person skilled in the art will be able to select the amount of the introduced substance that is reactive with the Zn precursor in the gas phase, depending on the specific amount of Zn precursor in the gas phase.
In the present application, "ZnZrO2"is merely a representation of materials, not representative of actual chemical proportions;
the "vapor phase Zn precursor" refers to a gaseous Zn precursor formed by heating and vaporizing a Zn precursor.
According to yet another aspect of the present application, there is provided ZnZrO2The application of the surface solid solution catalyst is used for synthesizing methanol by hydrogenating carbon dioxide.
A method for synthesizing methanol by carbon dioxide hydrogenation takes carbon dioxide and hydrogen as raw materials, and the raw materials react in the presence of a catalyst to obtain methanol;
the catalyst is at least one of the catalysts described above or the catalysts prepared by any of the methods described above.
Optionally, the reaction temperature is 280-400 ℃, the reaction pressure is 1-10 MPa, the space velocity is 3000-80000 mL/(g.h), n (H)2):n(CO2) The molar ratio is 1 to 8.
Preferably, the reaction temperature is 290-360 ℃.
Specifically, the lower limit of the reaction temperature can be independently selected from 280 ℃, 300 ℃, 320 ℃, 340 ℃ and 345 ℃; the upper limit of the reaction temperature may be independently selected from 350 ℃, 360 ℃, 370 ℃, 380 ℃ and 400 ℃.
Specifically, the lower limit of the reaction pressure can be independently selected from 1MPa, 2MPa, 3MPa, 4MPa and 5 MPa; the upper limit of the reaction pressure may be independently selected from 6MPa, 7MPa, 8MPa, 9MPa, 10 MPa.
Specifically, the lower limit of the reaction space velocity can be independently selected from 3000 mL/(g.h), 5000 mL/(g.h), 10000 mL/(g.h), 24000 mL/(g.h), 40000 mL/(g.h); the upper limit of the reaction pressure may be independently selected from 50000 mL/(g.h), 57000 mL/(g.h), 65000 mL/(g.h), 70000 mL/(g.h), 80000 mL/(g.h).
Specifically, n (H)2):n(CO2) The lower limit of the molar ratio can be independently selected from 1, 1.5, 2, 3 and 3.5; n (H)2):n(CO2) The lower limit of the molar ratio can be independently selected from 4, 5, 6, 7, 8.
The beneficial effects that this application can produce include:
1) ZnZrO provided by the application2The surface solid solution catalyst has the characteristics of high methanol selectivity, large specific surface area, good stability and strong heat resistance, can be used for continuously converting carbon dioxide with high conversion rate and high selectivity and obtaining methanol in the reaction of synthesizing methanol by hydrogenating carbon dioxide, and effectively improves the conversion rate of carbon dioxide and the space-time yield of methanol.
2) ZnZrO provided by the application2The preparation method of the surface solid solution catalyst is simple, the wastewater discharge in the preparation process is less, and the high-performance ZnZrO can be synthesized in an environment-friendly manner2A surface solid solution catalyst.
3) ZnZrO provided by the application2The preparation method of the surface solid solution catalyst selects zirconium carbonate, zirconium hydroxide, basic zirconium carbonate, oxygen-defective zirconium oxide and other high-activity zirconium oxide precursors, and the defect sites and structural changes of the zirconium oxide precursors and generated in the heating decomposition process can help Zn to migrate on the surface of the zirconium oxide precursors, so that the surface solid solution is formed, and the synergistic effect between Zn and Zr is greatly enhanced.
Drawings
FIG. 1 is an X-ray diffraction pattern of the catalysts obtained in example 5 and comparative example 3 of the present application;
FIG. 2 is an electron paramagnetic resonance spectrum of the catalyst obtained in example 6 of the present application;
FIG. 3 is a graph showing the stability test of the catalyst participating in the reaction obtained in example 4 of the present application.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials in the examples of the present application were all purchased commercially, wherein the oxygen-deficient zirconia ZrO was usedxCorresponding to zirconium oxide (ZrO)2) White, which is usually brown, obtained by calcining zirconium hydroxide, zirconium carbonate, zirconium basic carbonate in hydrogen or in an inert atmosphere (nitrogen or argon).
The analysis method in the examples of the present application is as follows:
analysis of specific surface area of catalyst by specific surface area and pore size distribution analyzer (model: Quantachrome NOVA)
The oxygen defect analysis of the catalyst was carried out using electron paramagnetic resonance spectrometer (model Bruker a 200).
The structural analysis of the catalyst was carried out using an X-ray diffractometer (model Rigaku D/Max 2500/PC).
In one embodiment of the present application, ZnZrO2The preparation of the surface solid solution catalyst adopts an impregnation method. The method comprises the following steps: preparing Zn precursor solution with the concentration of 0.01-10 mol/L, and adding ZrO2A precursor; volatilizing the solvent by heating or ultrasonic treatment; then roasting at 300-800 ℃ to obtain ZnZrO2A surface solid solution catalyst. The Zn precursor is one or more than two of zinc nitrate, zinc acetate, zinc halide and diethyl zinc; ZrO used2The precursor is one or more than two of zirconium carbonate, zirconium hydroxide, basic zirconium carbonate and oxygen-containing defective zirconium oxide.
In one embodiment of the present application, ZnZrO2The preparation of the surface solid solution catalyst adopts a deposition precipitation method. The method comprises the following steps: preparing Zn precursor solution with the concentration of 0.01-7 mol/L, and adding ZrO2A precursor; preparing a precipitator solution with the concentration of 0.01-7 mol/L; adding a precipitant solution into a Zn precursor solution; filtering and washing the obtained precipitate; then drying at 60-130 ℃ and roasting at 300-800 ℃ to obtain ZnZrO2A surface solid solution catalyst. The Zn precursor is zinc nitrate, zinc acetate,One or more of zinc halide and diethyl zinc; ZrO used2The precursor is one or more than two of zirconium carbonate, zirconium hydroxide, basic zirconium carbonate and oxygen-containing defective zirconium oxide. The precipitant is one or more of ammonia water, ammonium carbonate, ammonium bicarbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide and potassium hydroxide.
In one embodiment of the present application, ZnZrO2The preparation of the surface solid solution catalyst adopts a vapor deposition method. The method comprises the following steps: placing ZrO in a reaction furnace2Controlling the temperature of the precursor to be 25-300 ℃; introducing a gas-phase Zn precursor into the reaction furnace; deposition of Zn on ZrO by decomposition or reaction of gas-phase Zn precursor by controlling temperature or introduction of a substance capable of reacting with the gas-phase Zn precursor2A precursor surface; then roasting at 300-800 ℃ to obtain ZnZrO2A surface solid solution catalyst. The gas-phase Zn precursor is one or more than two of zinc chloride, diethyl zinc and metallocene zinc; the substance used for the reaction with the gas-phase Zn precursor is O2、H2O、O3One or more than two of them. The beneficial effect is that the high-performance ZnZrO can be simply and conveniently synthesized in an environment-friendly way2A surface solid solution catalyst.
In the application, the activity evaluation of the catalyst on the reaction of synthesizing the methanol by hydrogenating the carbon dioxide is carried out on a pressurized fixed bed continuous flow reactor-GC combined system. Before the reaction, pure hydrogen or nitrogen, argon or hydrogen diluted by nitrogen and argon is activated for 0.5 to 12 hours at the temperature of 280 to 400 ℃. The conditions for synthesizing methanol by hydrogenating carbon dioxide are as follows: the reaction pressure is 1-10 MPa, the reaction temperature is 280-400 ℃, and the airspeed is 3000-80000 h–1，n(H2):n(CO2) The molar ratio is 1 to 8. The reaction tail gas is discharged to normal pressure through a back pressure valve, sampling is carried out through a ten-way valve of gas chromatography at the temperature of 150 ℃, and online analysis is carried out by combining a Thermal Conductivity Detector (TCD) and a hydrogen flame detector (FID) of an Agilent GC-7890B type gas chromatograph. The former chromatographic column is a combination of 5A molecular sieve and Propark Q (Agilent), the column length is 3m, and H is used2Used as carrier gas, working at 85 deg.C, for separating and detecting CO2Ar, CO; the latter chromatographic column is TG-BOND Q capillaryColumn (Saimeishiehr) with specification of 30m × 0.32mm × 10 μm, using N2Used as carrier gas for separating and detecting low carbon hydrocarbon and alcohol. CO 22The conversion and C-based selectivity and space-time yield to carbon-containing products such as CO, alcohols, hydrocarbons, etc. are calculated by C-based normalization.
Example 1
0.2ml of 3.2mol/L Zn (NO) was taken3)4·6H2Diluting O water solution in a20 mL beaker with 2mL of water, adding 1g of zirconium carbonate, ultrasonically evaporating to dryness, drying in a 110 ℃ oven, and roasting in air at 400 ℃ for 4 hours to obtain a catalyst, namely ZnZrO with the concentration of 5.2%2-1。
Example 2
0.35ml of 3.2mol/L Zn (NO) was taken3)4·6H2Diluting O water solution in a20 mL beaker with 2mL of water, adding 1g of oxygen-defect-containing zirconium oxide, ultrasonically evaporating to dryness, drying in a 110 ℃ oven, roasting in 400 ℃ nitrogen for 4 hours to obtain a catalyst, and recording as 9.1% ZnZrO2-2。
Example 3
1ml of 3.2mol/L Zn (NO) was taken3)4·6H2Diluting O water solution with 2mL of water in a20 mL beaker, adding 1g of basic zirconium carbonate, ultrasonically evaporating to dryness, drying in a 110 ℃ drying oven, roasting in 400 ℃ nitrogen for 4 hours to obtain a catalyst, and recording as 26% ZnZrO2-3。
Example 4
0.38ml of 3.2mol/L Zn (NO) was taken3)4·6H2Diluting O water solution in a20 mL beaker with 2mL of water, adding 1g of zirconium hydroxide, ultrasonically evaporating to dryness, drying in a 110 ℃ oven, roasting in 500 ℃ air for 4h to obtain a catalyst, and recording as 10% ZnZrO2-4。
Example 5
0.38ml of 3.2mol/L Zn (NO) was taken3)4·6H2Diluting O aqueous solution in a20 mL beaker by adding 100mL of water, adding 1g of zirconium hydroxide, gradually dropping 0.1mol/L of ammonia water solution while stirring until the pH value is 7.0, filtering and washing the obtained precipitate, drying the precipitate in a 110 ℃ oven, and roasting the precipitate in 500 ℃ air for 4 hours to obtain a catalyst, which is recorded as 10% ZnZrO2-5。
Example 6
Putting 1g of zirconia containing oxygen defects into a reaction furnace, heating to 200 ℃, introducing nitrogen containing diethyl zinc, vacuumizing, introducing nitrogen containing water for reaction at the reaction temperature of 150 ℃ for 5min, drying in a drying oven at the temperature of 110 ℃, and roasting in air at the temperature of 500 ℃ for 4h to obtain a catalyst, wherein the catalyst is ALD-5% of ZnZrO2-6。
Comparative example 1 preparation of ZnZrOxSolid solution catalyst
ZnZrOxSolid solution catalyst, weighing 2mmol Zn (NO)3)2·6H2O and 15.0 mmoleZr (NO)3)4·5H2O100 mL of an aqueous solution was prepared and placed in a 500mL beaker, and 32.1mmol (NH) of the solution was weighed4)2CO3100mL of an aqueous solution was prepared. Dropwise adding the prepared ammonium carbonate solution into a mixed aqueous solution of zinc nitrate and zirconium nitrate at 70 ℃, wherein the dropwise adding speed is about 3mL/min, and the stirring speed is 600r/min until (NH)4)2CO3After the solution is consumed, obtaining a precipitation mother solution, aging the precipitation mother solution for 2 hours at the temperature of 70 ℃, cooling, naturally filtering, washing the precipitation mother solution for 3 times by deionized water, filtering, drying the obtained filter cake at the temperature of 60 ℃, roasting the filter cake in air at the temperature of 500 ℃ for 3 hours to obtain a catalyst, and recording the catalyst as 13 percent ZnZrOx。
Comparative example 2
Commercial copper zinc aluminum catalyst, noted CuZnAl.
Comparative example 3
0.38ml of 3.2mol/L Zn (NO) was taken3)4·6H2Diluting O water solution in 20mL beaker with 2mL water, adding 1g zirconium oxide, drying by ultrasonic evaporation, oven drying at 110 deg.C, calcining at 500 deg.C in air for 4h to obtain catalyst, and recording as 10% ZnO/ZrO2。
Catalyst evaluation
1. The specific surface area of the catalyst prepared in the examples of the present application was measured by a specific surface area measuring instrument, and it was found that each catalyst sample prepared by the method of the present application has a large specific surface area. The specific surface area of the catalyst obtained in the present application is compared with that of the catalyst sample obtained in the comparative example, typically illustrated by the samples obtained in examples 1, 2, 4 and comparative example 1, and the results are shown in table 1:
TABLE 1 specific surface results for the examples and comparative catalysts
Catalyst and process for preparing same Specific surface area (m)2/g)
Example 1 5.2％ZnZrO2-1 46.2
Example 2 9.1％ZnZrO2-2 98.7
Example 4 10％ZnZrO2-4 68.6
Comparative example 1 13％ZnZrOx 29.7
It can be seen that compared to the ZnZrO prepared by coprecipitationxThe specific surface area of the catalyst is obviously improved.
2. The catalyst samples obtained in examples 1 to 6 were examined by X-ray diffractometryIn an experiment, the solid solution structure is formed on the surface of the catalyst. Typically, the sample obtained in example 4 is used as an example to compare with the catalyst sample in comparative example 3, as shown in FIG. 1, to compare a conventional supported catalyst (10% ZnO/ZrO)2) It can be found that 10% ZnZrO2The zirconia diffraction peak of-4 was slightly shifted to a high angle, and the diffraction peak of zinc oxide did not appear at a ZnO content of 10%. Indicating that the catalyst is likely to form a solid solution structure on the surface of the catalyst, and the interaction of the zinc oxide and the zirconium oxide is enhanced.
3. The oxygen-deficient zirconia used in example 6 was subjected to electron paramagnetic resonance (ESR) testing, and the results are shown in FIG. 2. in comparison with conventional zirconia, oxygen deficiency, which contributes to Zn in ZrO during production, causes a large number of unpaired electrons in zirconia and shows a strong ESR signal2Thereby forming a solid solution.
4. Determination of catalytic Activity
And tabletting the catalyst sample, crushing, and screening by 40-80 meshes for evaluation.
The activity evaluation method comprises the following steps: weighing 0.1g of the screened catalyst sample, filling the catalyst sample into a reaction tube with the inner diameter of 6mm, and purifying the catalyst sample with pure H at normal pressure2Reducing at medium temperature of 320 ℃ for 2H at the flow rate of 30mL/min, and introducing a raw material gas n (H)2):n(CO2) The reaction was carried out as 3.
In the evaluation method, pure H is carried out at normal pressure for the Cu-Zn-Al catalyst in comparative example 22The reaction solution is reduced for 2h at the temperature of 250 ℃, and other evaluation steps are the same as the method.
The evaluation results are shown in table 2.
Table 2 evaluation results of catalysts of examples and comparative examples
Figure BDA0002821665610000111
5. Catalyst stability determination
According to the above evaluation method, 10% ZnZrO was added24 catalyst samples were tested for stability over time. The results are shown in FIG. 3. Stability test in 200 hoursThe methanol yield remained unchanged at 405mg/g h. And the high temperature stability of the catalyst was investigated by raising the temperature to 400 ℃ during the reaction. After reducing the reaction temperature from 400 ℃ back to 320 ℃, the methanol yield is returned to 405mg/g h. The catalyst not only has long-term stability, but also has excellent high-temperature sintering resistance.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. ZnZrO2Surface solid solution catalyst, characterized in that the catalyst comprises ZrO2Bulk phase and the ZrO2Solid solution formed on the surface of bulk phase;
the solid solution is dissolved in ZrO by Zn2And (4) forming a surface.
2. The catalyst according to claim 1, wherein the content of Zn in solid solution in the catalyst is 0.1-30%;
wherein Zn is calculated by the mass of ZnO.
3. ZnZrO according to claim 1 or 22A method for producing a surface solid solution catalyst, characterized in that the production method comprises any one of the first method, the second method, and the third method:
the method comprises the following steps: synthesizing the ZnZrO by adopting an impregnation method2Surface solid solution catalyst
1-1) obtaining a precursor containing Zn and ZrO2Suspension I of the precursor;
1-2) removing the solvent in the suspension I in the step 1-1), and roasting the residual solid phase to obtain the ZnZrO2A surface solid solution catalyst;
the second method comprises the following steps: ZnZrO synthesis by deposition precipitation method2Surface solid solution catalyst
2-1) obtaining a precursor containing Zn and ZrO2Suspension II of the precursor;
2-2) obtaining a solution III containing a precipitating agent;
2-3) mixing the suspension II in the step 2-1) with the solution III in the step 2-2), and filtering to obtain a precipitate;
2-4) roasting the precipitate to obtain the ZnZrO2A surface solid solution catalyst;
the third method comprises the following steps:
3-1) to contain ZrO2Introducing a gas-phase Zn precursor into the dry material of the precursor, and operating to deposit Zn in the Zn precursor on ZrO2Precursor surface to obtain intermediate;
3-2) roasting the intermediate to obtain the ZnZrO2A surface solid solution catalyst.
4. A method according to claim 3, characterized in that the Zn precursor is ZrO based on the mass of Zn2The precursor is calculated by the mass of Zr, the Zn precursor and ZrO2The mass ratio of the precursor is 1: 999-3: 7;
preferably, the Zn precursor is at least one of zinc nitrate, zinc acetate, zinc halide, diethyl zinc and metallocene zinc;
preferably, the ZrO2The precursor is at least one of zirconium carbonate, zirconium hydroxide, zirconium basic carbonate and oxygen-containing defective zirconium oxide.
5. The method according to claim 3, wherein the roasting temperature is 300 to 800 ℃.
6. The method as claimed in claim 3, wherein in the first method, the content of Zn precursor in the suspension I is 0.01-10 mol/L;
preferably, in the second method, the content of the Zn precursor in the suspension II is 0.01-7 mol/L;
in the solution III, the content of a precipitator is 0.01-14 mol/L;
further preferably, the precipitant is at least one of ammonia, ammonium carbonate, ammonium bicarbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, and potassium hydroxide.
7. The method according to claim 3, wherein step 3-1) is: ZrO 2 is mixed with2Heating the precursor in a reaction furnace at 25-300 ℃, introducing a gas-phase Zn precursor, and depositing Zn in the Zn precursor on ZrO2Precursor surface to obtain intermediate;
preferably, in step 3-1), the operation is: depositing Zn on ZrO by decomposing or reacting a gas-phase Zn precursor by controlling the temperature or introducing a substance capable of reacting with the gas-phase Zn precursor2The precursor surface.
8. The method according to claim 7, wherein the decomposition control temperature is 50 to 500 ℃;
preferably, the reaction conditions are: the reaction temperature is 100-200 ℃.
Preferably, the substance capable of reacting with the gas-phase Zn precursor is O2、H2O、O3At least one of (1).
9. A method for synthesizing methanol by carbon dioxide hydrogenation is characterized in that carbon dioxide and hydrogen are used as raw materials and react in the presence of a catalyst to obtain methanol;
the catalyst is at least one of the catalyst of claim 1 or 2, or the catalyst prepared by the method of any one of claims 3 to 8.
10. The method according to claim 9, wherein the reaction temperature is 280-400 ℃, the reaction pressure is 1-10 MPa, the space velocity is 3000-80000 mL/(g-H), and n (H) is2):n(CO2) The molar ratio is 1 to 8.
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