CN116351428A - Preparation and application of reverse water gas shift catalyst with sodium and potassium as auxiliary agents - Google Patents

Preparation and application of reverse water gas shift catalyst with sodium and potassium as auxiliary agents Download PDF

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CN116351428A
CN116351428A CN202310173190.6A CN202310173190A CN116351428A CN 116351428 A CN116351428 A CN 116351428A CN 202310173190 A CN202310173190 A CN 202310173190A CN 116351428 A CN116351428 A CN 116351428A
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catalyst
precursor
nitrate
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mixture
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郭振峰
陈洪胜
黎锦兴
臧云浩
高峰
曲江英
顾建峰
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Dongguan Zhenliang Precision Technology Co ltd
Dongguan University of Technology
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Dongguan University of Technology
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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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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
    • B01J23/78—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 alkali- or alkaline earth metals
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention provides a supported catalyst A/MO for reverse water gas shift reaction 2 -X, and its use, the composition of the catalyst comprising: active component A, auxiliary agent X and oxide carrier MO 2 The active component A is nickel, cobalt or platinum, the auxiliary agent X is potassium or sodium, and the carrier MO 2 Is cerium oxide, titanium oxide or zirconium oxide. Catalyst A/M prepared according to the invention 2 O x X is used for reverse water gas shift reaction, shows excellent catalytic activity, has carbon monoxide (CO) selectivity close to 100%, and has application prospect.

Description

Preparation and application of reverse water gas shift catalyst with sodium and potassium as auxiliary agents
Technical Field
The invention relates to a preparation and application of a catalyst for reverse water gas shift reaction, in particular to a catalyst which takes nickel, cobalt or platinum as an active component A, sodium or potassium as an auxiliary agent X, titanium oxide, zirconium oxide or cerium oxide MO 2 Catalyst A/MO as support 2 -synthesis of X and its use in a high selectivity reverse water gas shift reaction.
Background
As the consumption of global fossil energy continues to increase, CO 2 Emissions are also increasing, and as a typical greenhouse gas, too high a concentration in the atmosphere can cause a series of environmental problems. But from the viewpoint of resource utilization, CO 2 Is a large and cheap 'carbon source'. CO 2 Is currently reducing CO in the atmosphere 2 One of the most potential technological routes for concentration development. CO is an excellent platform compound in C1 chemistry by means of reverse water gas shift reaction (RWGS, CO 2 +H 2 →CO+H 2 OΔH 298K ＝41.3KJ·mol -1 ) CO is firstly processed 2 Reducing into more active CO, and then further hydrogenating and converting the CO into high-added value chemicals such as olefin, aromatic hydrocarbon, gasoline and the like. Thus, the RWGS reaction is an important step in achieving carbon recycling.
CO at normal pressure 2 Hydrogenation for preparing CO and CH 4 The RWGS reaction can be considered an intermediate step in the methanation process as competing reactions, because the CO produced can continue to be deeply hydrogenated to methane. Nickel-based catalysts and cobalt-based catalysts are typically methanation catalysts that are less prone to sintering at high temperatures than copper-based catalysts commonly used in RWGS reactions, and have received extensive attention from researchers (Journal of energy chemistry,2016,25 (4): 553-565;International journal of hydrogen energy,2013,38 (24): 10012-10018). In addition, RWGS reactions are endothermic and often require high temperature conditions, platinum-based catalystsAlthough there is a high CO selectivity at low temperatures, the CO selectivity gradually decreases as the reaction temperature increases (Applied Catalysis B: environmental,2021,291: 120101). The selective regulation and control of the nickel, cobalt or platinum catalyst for RWGS reaction at high temperature has good application prospect.
For CO 2 Hydrogenation reactions, currently generally considered to follow CO intermediate mechanisms, CO 2 The hydrogenation product depends on the adsorption strength of the CO intermediate: CO 2 Hydrogenation firstly generates intermediate product CO, and weak adsorption state CO (CO) is beneficial to CO rapid desorption, so that higher CO selectivity is shown; and stronger CO adsorption is beneficial to further deep hydrogenation reduction to obtain CH 4 Exhibit a higher CH 4 Selectivity. Thus regulating CO 2 The essence of hydrogenation product selectivity is to regulate the adsorption strength of CO as an intermediate product.
To facilitate forward progression of RWGS reactions, researchers have proposed 3 means of selective regulation: reducing the metal particle size (ACS catalyst.2013, 3, 2449-2455), utilizing metal-support interactions (MSI) (Journal of Catalysis,2019, 374:60-71), and preparing bimetallic catalysts (CN 109499577B, iScience,2019,17,315-324). However, the disadvantage of the above regulation means is that: catalyst CO prepared by the first two methods 2 The conversion rate is lower (500 ℃ to 10%), and the preparation method of the bimetallic catalyst is complex and has no universality.
Research shows that adding sodium and potassium metal salts as assistants to the catalyst is favorable to adsorbing and activating carbon dioxide and thus raised catalytic performance. Existing studies have two conclusions: 1) The addition of sodium and potassium metal salts can promote the activity of the catalyst on the reverse water gas reaction and properly improve the selectivity of CO (< 50%) (CN 108144637A); 2) Sodium, potassium metal salts can promote methanation reactions by increasing carrier basicity and introducing oxygen vacancies (CN 101773833a; catalysts,2020,10 (7): 812). However, in the current research, the addition of sodium and potassium metal salts is only aimed at CO 2 Hydrogenation catalysts increase their own catalytic performance and fail to achieve near 100% CO selectivity control.
By combining the research background, the work breaks through the traditional selective regulation framework by adding sodium hydroxide or potassium hydroxide into a low-load nickel, cobalt or platinum-based catalyst, and synthesizes the RWGS catalyst with higher reactivity, high CO selectivity and good stability.
Disclosure of Invention
The invention aims to solve the prior technical problems and provides a catalyst A/MO for reverse water gas shift reaction 2 -X preparation and application method. The catalyst has high reaction activity in reverse water gas shift reaction, CO selectivity close to 100% and good stability.
In order to achieve the above object of the present invention, the following technical scheme is adopted:
a catalyst is prepared from Ni, co or Pt as active component A, na or K as assistant X, and titanium oxide, zirconium oxide or cerium oxide MO 2 Catalyst A/MO as support 2 -a method of synthesis of X comprising the steps of:
1.MO 2 is synthesized by the following steps:
1) Taking an M precursor and ammonia water in deionized water, adjusting the pH value to be 8-11, and stirring for 0.5-10h;
2) Transferring the solution into a centrifuge tube, and washing with deionized water for 1-10 times;
3) Drying the obtained precipitate in an oven at 30-150 ℃;
4) Calcining the dried solid in air atmosphere at 400-900 ℃ for 1-10h to obtain MO 2 A carrier.
2. A method for preparing a catalyst comprising the steps of:
1) Dissolving an active component precursor, an auxiliary agent precursor and a carrier MO2 in ionized water, and magnetically stirring for 0.5-10h;
2) Drying the mixed solution in an oven at 30-150 ℃ to obtain a solid catalyst precursor;
3) Calcining the catalyst precursor in air atmosphere at 400-900 deg.c for 1-10 hr to obtain AO y /MO 2 -X(AO y An oxide of A
4) To the AO y /MO 2 -X is placed inReducing for 1-5h in hydrogen atmosphere at 400-900 ℃ to obtain A/MO 2 -X catalyst
3. Application of catalyst
The catalyst obtained in the step 4) is used for the reverse water gas shift reaction, and the evaluation conditions are as follows: crushing the catalyst to 40-80 meshes, filling 0.05-1g into a quartz tube, placing the quartz tube into a fixed bed reactor for reaction evaluation, and taking carbon dioxide and hydrogen as reaction raw materials, wherein the molar ratio of the carbon dioxide is as follows: hydrogen = 1:4, nitrogen as diluent gas; the gas space velocity GHSV is 1000-50000 mL.h -1 ·g -1 The reaction pressure is normal pressure or nearly normal pressure (0.1 Mpa-1 Mpa), and the reaction temperature is 300 ℃ -800 ℃; the selectivity of carbon monoxide (CO) in the product obtained by the reaction is close to 100 percent.
Drawings
Fig. 1 is XRD patterns of inventive example 1 and comparative example 1.
Fig. 2 is a TEM image of example 1 of the present invention.
Fig. 3 is an XPS diagram of K element of inventive example 1 and comparative example 1.
FIG. 4 is a graph of catalytic performance for example 1 (right panel) and comparative example 1 (left panel) of the present invention.
Fig. 5 is a graph of catalytic stability test of example 1 (right panel) and comparative example 1 (left panel) of the present invention.
FIG. 6 is a graph of catalytic performance for example 2 (right panel) and comparative example 2 (left panel) of the present invention.
FIG. 7 is a graph of catalytic performance for example 3 (right panel) and comparative example 3 (left panel) of the present invention.
Detailed Description
Example 1:
1) Synthesis of cerium oxide:
2.5g cerium nitrate was weighed into 100mL deionized water, 2mL ammonia was slowly added with stirring, and ph=8 was adjusted. Stirring was continued for 2h. The resulting mixed solution was placed in a centrifuge tube and washed 3 times by centrifugation at 9000 r/min. The obtained precipitate was transferred to a petri dish, dried at 60 ℃, and the obtained solid was placed in a muffle furnace (air atmosphere), and the muffle furnace temperature was raised from room temperature to 500 ℃ at a heating rate of 5 ℃/min and calcined for 2 hours to obtain a cerium oxide carrier.
2) Catalyst Ni/CeO 2 -preparation of K:
weighing 0.5g of cerium oxide, 0.0195g of nickel nitrate hexahydrate and 0.035g of potassium hydroxide, mixing into 20mL of deionized water, stirring for 30min to dissolve completely; drying the mixed solution in an oven at 60 ℃ for 12 hours to obtain a solid catalyst precursor; the obtained catalyst precursor was placed in a muffle furnace (air atmosphere), the muffle furnace temperature was raised from room temperature to 500℃at a heating rate of 5℃per minute and calcined for 2 hours, and the obtained sample was named NiO/CeO 2 -K. NiO/CeO 2 K is reduced for 2 hours in a hydrogen atmosphere (the volume ratio of hydrogen to nitrogen is 10%) at 500 ℃, and the final catalyst is named Ni/CeO 2 -K. FIG. 1 is Ni/CeO 2 XRD pattern of K catalyst, it can be seen that CeO was successfully synthesized 2 But no peak occurs due to too small Ni loading. FIG. 2 is Ni/CeO 2 TEM image of K catalyst.
3) Catalyst application:
the prepared Ni/CeO 2 K is applied to the reverse water gas shift reaction. Tabletting and crushing the catalyst into 40-80 mesh size, and filling 0.2g into a quartz tube reactor; introducing reaction gas under the condition of near normal pressure (0.1 Mpa), wherein the molar ratio of the gas is hydrogen: carbon dioxide: nitrogen = 4:1:5, a step of; the reaction temperature is 300-500 ℃ and the airspeed is 15000 mL.h -1 ·g -1 . CO at a reaction temperature of 500 DEG C 2 The conversion of (2) was 48.6% and the CO selectivity was 93.8%. After 20 hours of stability testing at 500 ℃, CO 2 The conversion of (2) was 40.1% and the CO selectivity was 99.9%. The right graph of FIG. 4 shows Ni/CeO 2 -K catalytic Performance graph (300 ℃ C. -500 ℃ C.; 15000 mL.multidot.h) -1 ·g -1 ). The right graph of FIG. 5 shows Ni/CeO 2 Catalytic stability test chart of-K (500 ℃ C.; 15000 mL.h) -1 ·g -1 )。
Example 2:
1) Synthesis of cerium oxide as in example 1
2) Catalyst Pt/CeO 2 Preparation of-K
Weighing 0.5g of cerium oxide and 0.0088g of chlorineDissolving platinum and 0.035g potassium hydroxide in 20mL deionized water, stirring for 30min to dissolve completely; drying the mixed solution in an oven at 60 ℃ for 12 hours to obtain a solid catalyst precursor; the obtained catalyst precursor was placed in a muffle furnace (air atmosphere), the muffle furnace temperature was raised from room temperature to 500℃at a heating rate of 5℃per minute and calcined for 2 hours, and the obtained sample was named PtO/CeO 2 -K. PtO/CeO 2 K is reduced for 2 hours in a hydrogen atmosphere (the volume ratio of hydrogen to nitrogen is 10 percent) at 500 ℃, and the final catalyst is named Pt/CeO 2 -K。
3) The catalyst was used in the same manner as in example 1. CO at a reaction temperature of 500 DEG C 2 The conversion of (2) was 48.5% and the CO selectivity was 99.8%. The right graph of FIG. 6 shows Pt/CeO 2 -K catalytic Performance graph (300 ℃ C. -500 ℃ C.; 15000 mL.multidot.h) -1 ·g -1 )。
Example 3:
1) Synthesis of titanium oxide:
1.09g of titanium tetrachloride was weighed into 100mL of deionized water, 2mL of ammonia was slowly added with stirring, and pH=8 was adjusted. Stirring was continued for 2h. The resulting mixed solution was placed in a centrifuge tube and washed 3 times by centrifugation at 9000 r/min. The obtained precipitate was transferred to a petri dish, dried at 60 ℃, and the obtained solid was placed in a muffle furnace (air atmosphere), and the muffle furnace temperature was raised from room temperature to 500 ℃ at a heating rate of 5 ℃/min and calcined for 2 hours to obtain a titanium oxide carrier.
2) Catalyst Ni/TiO 2 Preparation of Na:
weighing 0.5g of titanium oxide, 0.0195g of nickel nitrate hexahydrate and 0.025g of sodium hydroxide, dissolving in 20mL of deionized water, and stirring for 30min to completely dissolve; drying the mixed solution in an oven at 60 ℃ for 12 hours to obtain a solid catalyst precursor; the obtained catalyst precursor was placed in a muffle furnace (air atmosphere), the muffle furnace temperature was raised from room temperature to 500℃at a heating rate of 5℃per minute and calcined for 2 hours, and the obtained sample was named NiO/TiO 2 Na. NiO/TiO 2 Na is placed in a hydrogen atmosphere (mixture of hydrogen and nitrogen, volume of hydrogen in mixture) at 500 DEG CThe ratio is 10 percent) for 2 hours, and the final catalyst is named as Ni/TiO 2 -Na。
3) The catalyst was used in the same manner as in example 1. CO at a reaction temperature of 500 DEG C 2 The conversion of (2) was 36.2% and the CO selectivity was 95.7%. The right graph of FIG. 7 shows Ni/TiO 2 Catalytic performance diagram of Na (300 ℃ C. -500 ℃ C.; 15000 mL. H) -1 ·g -1 )。
Comparative example 1:
as a comparative experimental group, a synthesis method similar to that of example 1 above was employed, except that potassium hydroxide was not added.
1) Synthesis of cerium oxide as in example 1
2) Catalyst Ni/CeO 2 Is prepared from
Weighing 0.5g of cerium oxide and 0.0195g of nickel nitrate hexahydrate, dissolving in 20mL of deionized water, and stirring for 30min to completely dissolve; drying the mixed solution in an oven at 60 ℃ for 12 hours to obtain a solid catalyst precursor; the obtained catalyst precursor was placed in a muffle furnace (air atmosphere), the muffle furnace temperature was raised from room temperature to 500℃at a heating rate of 5℃per minute and calcined for 2 hours, and the obtained sample was named NiO/CeO 2 . NiO/CeO 2 Reducing for 2h in 500 ℃ hydrogen atmosphere (the volume ratio of hydrogen to nitrogen is 10 percent in the mixed gas), and obtaining the final catalyst named Ni/CeO 2 。
3) The catalyst was used in the same manner as in example 1. CO at a reaction temperature of 500 DEG C 2 The conversion of (2) was 55.0% and the CO selectivity was 24.5%. After 20 hours of stability testing at 500 ℃, CO 2 The conversion of (2) was 49.8% and the CO selectivity was 18.7%. The left graph of FIG. 4 shows Ni/CeO 2 The catalytic performance of (300-500 ℃ C.; 15000 mL.h) -1 ·g -1 ). The left graph of FIG. 5 shows Ni/CeO 2 Catalytic stability test chart (500 ℃ C.; 15000 mL.h) -1 ·g -1 )。
Comparative example 2:
as a comparative experimental group, a synthesis method similar to that of example 2 above was employed, except that potassium hydroxide was not added.
1) Synthesis of cerium oxide as in example 1
2) Catalyst Pt/CeO 2 Is prepared from
Weighing 0.5g of cerium oxide and 0.0088g of platinum chloride, dissolving in 20mL of deionized water, and stirring for 30min to completely dissolve; drying the mixed solution in an oven at 60 ℃ for 12 hours to obtain a solid catalyst precursor; the obtained catalyst precursor was placed in a muffle furnace (air atmosphere), the muffle furnace temperature was raised from room temperature to 500℃at a heating rate of 5℃per minute and calcined for 2 hours, and the obtained sample was designated PtO 2 /CeO 2 . PtO is to 2 /CeO 2 Reducing for 2h in 500 ℃ hydrogen atmosphere (the volume ratio of hydrogen to nitrogen is 10 percent in the mixed gas), and obtaining the final catalyst named Pt/CeO 2 。
3) The catalyst was used in the same manner as in example 1. CO at a reaction temperature of 500 DEG C 2 The conversion of (2) was 49.3% and the CO selectivity was 50.2%. The left graph of FIG. 6 shows Pt/CeO 2 The catalytic performance of (300-500 ℃ C.; 15000 mL.h) -1 ·g -1 )。
Comparative example 3:
as a comparative experimental group, a synthesis method similar to that of example 3 above was employed, except that sodium hydroxide was not added.
1) The synthesis of titanium oxide was the same as in example 3
2) Catalyst Ni/TiO 2 Is prepared from the following steps:
weighing 0.5g of titanium oxide and 0.0195g of nickel nitrate hexahydrate, dissolving in 20mL of deionized water, and stirring for 30min to completely dissolve; drying the mixed solution in an oven at 60 ℃ for 12 hours to obtain a solid catalyst precursor; the obtained catalyst precursor was placed in a muffle furnace (air atmosphere), the muffle furnace temperature was raised from room temperature to 500℃at a heating rate of 5℃per minute and calcined for 2 hours, and the obtained sample was named NiO/TiO 2 . NiO/TiO 2 Reducing for 2h in 500 ℃ hydrogen atmosphere (the volume ratio of hydrogen to nitrogen is 10 percent in the mixed gas), and obtaining the final catalyst which is named as Ni/TiO 2 。
3) The catalyst was used in the same manner as in example 1. CO at a reaction temperature of 500 DEG C 2 The conversion of (2) was 20.7% and the CO selectivity was 48.8%. The left graph of FIG. 7 shows Ni/TiO 2 The catalytic performance of (300-500 ℃ C.; 15000 mL.h) -1 ·g -1 )。
It should be apparent that the above experimental examples are given for clarity of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.

Claims (9)

1. Catalyst A/MO for reverse water gas shift reaction 2 X, consisting of an active ingredient A, an auxiliary X and a carrier MO 2 The composition is characterized in that the active component A is nickel, cobalt or platinum, the auxiliary agent X is potassium or sodium, and the carrier MO 2 The catalyst comprises, by mass, 0.5-5% of an active component A and 0.5-5% of an auxiliary agent X, wherein the active component A is titanium oxide, zirconium oxide or cerium oxide.
2. The catalyst A/MO according to claim 1 2 -X, characterized in that when the active component a is nickel, the precursor is one or a mixture of several of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, nickel acetylacetonate; when the active component A is cobalt, the precursor is one or a mixture of a plurality of cobalt nitrate, cobalt chloride, cobalt sulfate and cobalt carbonate; when the active component A is platinum, the precursor is one or a mixture of a plurality of platinum chloride, chloroplatinic acid, platinum nitrate, tetramine platinum nitrate and dinitroso diammine platinum.
3. The catalyst A/MO according to claim 1 2 -X, characterized in that, when the auxiliary X is potassium, the precursor is potassium hydroxide; when the auxiliary agent X is sodium, the precursor is sodium hydroxide.
4. The catalyst A/MO according to claim 1 2 -X, characterized in that the support MO 2 Is one or a mixture of a plurality of titanium oxide, zirconium oxide or cerium oxide; the titanium oxide precursor is one or a mixture of a plurality of titanium tetrachloride, butyl titanate and titanyl nitrate; the zirconia precursor is one or a mixture of more of zirconyl nitrate, zirconium nitrate and zirconium chloride; the cerium oxide precursor is one or a mixture of more of cerium nitrate, cerium chloride, cerium sulfate and cerium ammonium nitrate.
5. The catalyst A/MO according to claim 1 2 -X, characterized in that the support MO 2 The synthesis steps of (a) comprise:
1) MO is taken 2 The precursor and ammonia water are put into deionized water, the pH value is regulated to be 8-11, and the mixture is stirred for 0.5-10h;
2) Transferring the solution into a centrifuge tube, and washing with deionized water for 1-10 times;
3) Drying the obtained precipitate in an oven at 30-150 ℃;
4) Calcining the dried solid in air atmosphere at 400-900 ℃ for 1-10h to obtain MO 2 A carrier.
6. The catalyst A/MO as claimed in claim 1 to 5 2 -X, characterized in that it comprises the following steps:
1) Taking active component precursor, auxiliary agent precursor and carrier MO 2 Dissolving in ionized water, and magnetically stirring for 0.5-10h;
2) Drying the mixed solution in an oven at 30-150 ℃ to obtain a solid catalyst precursor;
3) The solid catalyst precursor is put into an air atmosphere with the temperature of 400 ℃ to 900 ℃ to be roasted for 1 to 10 hours, thus obtaining AO y /MO 2 -X(AO y An oxide of a);
4) To the AO y /MO 2 X is reduced for 1 to 5 hours in a hydrogen atmosphere at 400 to 900 ℃ to obtain A/MO 2 -an X catalyst.
7. The method of manufacturing according to claim 6, wherein: in the step 3), the heating rate of the roasting process is 5 ℃/min-20 ℃/min.
8. The method of manufacturing according to claim 6, wherein: in the step 4), the hydrogen atmosphere is a mixed gas of hydrogen and inert gas, the inert gas is nitrogen or argon, and the volume ratio of the hydrogen in the mixed gas is 1% -30%.
9. The catalyst A/MO as claimed in claim 1 to 5 2 -X application, characterized in that: for the reverse water gas shift reaction: crushing the catalyst to 40-80 meshes, filling 0.05-1g into a quartz tube, placing the quartz tube into a fixed bed reactor for reaction evaluation, and taking carbon dioxide and hydrogen as reaction raw materials, wherein the molar ratio of the carbon dioxide is as follows: hydrogen = 1:4, nitrogen as diluent gas; the gas space velocity GHSV is 1000-50000 mL.h -1 ·g -1 The reaction pressure is normal pressure or near normal pressure, and the reaction temperature is 300-800 ℃;
the selectivity of carbon monoxide in the product obtained by the reaction is close to 100 percent.
CN202310173190.6A 2023-02-27 2023-02-27 Preparation and application of reverse water gas shift catalyst with sodium and potassium as auxiliary agents Pending CN116351428A (en)

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