CN115779901B - Ruthenium-loaded metal oxide catalyst, preparation method and application thereof - Google Patents
Ruthenium-loaded metal oxide catalyst, preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 78
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims description 23
- 229910052707 ruthenium Inorganic materials 0.000 title claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 5
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- 238000001035 drying Methods 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 37
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- 239000000725 suspension Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 239000002244 precipitate Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 15
- 238000011068 loading method Methods 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 11
- 230000001105 regulatory effect Effects 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 229910052788 barium Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 3
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 abstract description 29
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000011148 porous material Substances 0.000 abstract description 6
- 150000003384 small molecules Chemical class 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
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- 230000002349 favourable effect Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 23
- 239000000203 mixture Substances 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 17
- 239000002245 particle Substances 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 16
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 16
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000005303 weighing Methods 0.000 description 10
- 230000001276 controlling effect Effects 0.000 description 9
- -1 ruthenium acetate ethanol Chemical compound 0.000 description 9
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 8
- 229910001960 metal nitrate Inorganic materials 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000004445 quantitative analysis Methods 0.000 description 8
- 239000012495 reaction gas Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 5
- 238000007036 catalytic synthesis reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009620 Haber process Methods 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 238000012216 screening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention provides a ruthenium-supported metal oxide catalyst, a preparation method and application thereof. The active component of the metal oxide catalyst is Ru, the carrier is metal oxide, and the metal oxide is selected from CeO, mgO, baO and La 2 O 3 Wherein the mass ratio of Ce, mg, ba and La is (1-3): (0-5): (2-5): (0-2). The invention utilizes the small molecule regulation technology to make the pore canal structure of the catalyst more suitable for N 2 And H 2 The adsorption of the catalyst is favorable for the reaction of synthesizing ammonia, so that the reaction temperature can be reduced on the basis of the prior art, the energy conservation and consumption reduction in the production process are facilitated, and the catalyst is efficient and environment-friendly.
Description
Technical Field
The invention relates to the field of preparation of catalyst materials for catalytic synthesis of ammonia reaction, in particular to a ruthenium-supported metal oxide catalyst, a preparation method and application thereof.
Background
Ammonia (NH) 3 ) As an indispensable product in industrial production, plays a vital role in the production of human agricultural products. With the increasing global population, the demand of agricultural products is continuously increased, and the consumption of ammonia is also continuously increased, so that the yield of ammonia plays a vital role in the survival and development of human beings. At the same time NH 3 As hydrogen (H) 2 ) Up to 17.6wt% H, is also considered to be an important hydrogen carrier, with gaseous H 2 It is easier to store and transport than it is. In particular, NH as a carbon-free energy storage intermediate 3 Generates nitrogen (N) 2 ) And water, thereby not facingThe atmosphere emits harmful gases such as carbon monoxide (CO) and carbon dioxide.
Currently, ammonia is produced industrially mainly by the Haber-Bosch process, which for the first time achieves the aim of converting nitrogen (N) in air 2 ) Reduction to NH 3 . With the outstanding contribution of this process, haber obtained the 1918 nobel chemical prize. However, the process is carried out at high temperature and high pressure (400-600 ℃ and 150-300 atm), the annual global ammonia production is about 1.5 hundred million tons, and the demand is still increasing, which results in the production of NH 3 The process requires the consumption of large amounts of fossil energy. Therefore, the research on the catalyst capable of synthesizing ammonia at lower temperature and pressure is beneficial to saving energy and reducing consumption, and carbon neutralization is realized early.
CN114182293a discloses a preparation method of Ru-based catalyst and application in 'renewable energy source electrolytic hydrogen production synthesis ammonia', the method specifically comprises the following steps: (1) Uniformly dispersing nitrogen-containing organic matters and magnesium oxide in a solvent to prepare slurry; (2) Heating and roasting the slurry in the step (1) to obtain a roasting product; (3) Treating the roasting product in an acid solution to remove magnesium oxide, thereby obtaining the Ru-based catalyst; the ruthenium precursor can be dispersed with a nitrogen-containing organic matter in a solvent in the step (1), or can be added after roasting is finished to prepare the Ru-based catalyst. In the Ru-based catalyst, ru exists in different scale forms, and the performance of the Ru-based catalyst for synthesizing ammonia at low temperature can be adjusted by adjusting the particle size of Ru, so that high-efficiency ammonia synthesis under mild conditions is realized. However, as a carbon supported catalyst, the mass production difficulty is high, which causes the cost rise, and the problems of high molding difficulty, difficult filling and the like are also present.
Therefore, the development of a supported metal oxide catalyst having a pore internal structure suitable for catalyzing the ammonia synthesis reaction and having high catalytic activity and stability is a problem to be solved.
Disclosure of Invention
In order to solve the problems, the invention provides a ruthenium-supported metal oxide catalyst, the active component of the metal oxide catalyst is Ru, the carrier is metal oxide, and the catalyst is prepared fromThe metal oxide is selected from CeO, mgO, baO and La 2 O 3 Wherein the mass ratio of Ce, mg, ba and La is (1-3): 0-5): 2-5): 0-2.
Further, the loading amount of Ru is 0.005-0.05, preferably 0.005-0.03, based on the mass of the support.
Further, the loading amount of Ru is preferably 0.005 to 0.03, particularly preferably 0.01, based on the mass of the support.
The invention also provides a preparation method of the metal oxide catalyst, which comprises the following steps:
step S1: preparing a metal salt solution: two or more nitrates of cerium, magnesium, barium and lanthanum are fully dissolved in water at 60-70 ℃ to prepare a metal salt solution, and then the metal salt solution is transferred into a stirring kettle to be continuously stirred;
step S2: coprecipitation reaction: slowly adding ammonia water with the mass concentration of 10-15% into the stirring kettle, and regulating the pH value of the suspension in the adding process until the pH value is 8.5-9.5, and stopping dropwise adding the ammonia water;
step S3: aging: precipitating and aging the suspension at 60-80 ℃ for 0.5-5h;
step S4: washing, drying and roasting the aged mixed precipitate;
step S5: according to the loading amount of ruthenium, adding ethanol solution of ruthenium acetate and deionized water into the baked solid, and carrying out reduced pressure distillation, drying, baking and reduction on the mixed reaction liquid to obtain the metal oxide catalyst.
Further, in the step S1, the mass ratio of Ce, mg, ba and La is (1-3): (0-5): (2-5): (0-2).
Further, in step S1, the nitrate is preferably dissolved and mixed at a temperature of 65 ℃.
Further, in step S1, the prepared metal salt solution is transferred to a stirring kettle, and stirring is continuously performed at a speed of 300r/min or more.
Further, in the step S2, the adding time of the ammonia water is controlled to be 1-1.5 hours.
Further, in step S2, the temperature of the reaction vessel is controlled to 60 to 70 ℃, preferably 65 ℃ by a water bath.
Further, in step S2, the pH value of the suspension is continuously detected in the adding process, the dropping of ammonia water is stopped until the pH value is 8.5-9.5, and then the suspension is continuously stirred for 1h.
Further, in step S3, during the aging process, 30 to 45% H is introduced into the suspension 2 H of (2) 2 And N 2 Is a mixed gas of (a) and (b).
In the preparation method of the invention, a small molecule regulation technology is adopted to prepare the catalyst. For example during the ageing of step S3 by adding small molecules of a gas such as H 2 And N 2 The pore canal structure of the finally prepared catalyst is more similar to the reactant N in the subsequent catalytic reaction 2 And H 2 Is a size of (c) a. The gas micromolecules are equivalent to templates, occupy sites in the aging process, promote the surface control synthesis of the catalyst through specific strong adsorption, regulate and control the formation of a catalyst chemisorption layer, thereby influencing the internal structure of the catalyst, being beneficial to the adsorption of reactants and the removal of products in the subsequent catalytic reaction, and further increasing the catalytic activity.
Further, in step S3, the aging is preferably performed at 65 ℃ for 2 hours.
Further, in step S4, the mixed precipitate is washed with water and suction filtered several times until the pH after washing is between 6.5 and 7.8, preferably between 7 and 7.3.
Further, in step S4, the mixed precipitate is stirred for more than 40 minutes for the first washing, and more than 20 minutes for the remaining several times, and is washed three to five times.
Further, in step S4, the filtrate is dried overnight, preferably for 12 hours, in a constant temperature oven at a temperature of 100 ℃.
Further, in step S4, the filtrate is put into a muffle furnace to be baked at a temperature of 400-600 ℃ for 3-7 hours, preferably at a temperature of 450 ℃ for 6 hours, or at a temperature of 550 ℃ for 4 hours.
Further, in step S5, according to the load of ruthenium, adding ruthenium acetate ethanol solution and deionized water into the baked solid, stirring and mixing for 12 hours at 60 ℃, then distilling under reduced pressure, putting the obtained solid into a constant temperature drying oven at 100 ℃ for drying for 8 hours, finally putting the sample into a muffle furnace for baking for 6 hours at 400-450 ℃, and finally using H 2 And reducing to obtain the metal oxide catalyst.
The invention also provides an application of the metal oxide catalyst for catalyzing ammonia synthesis reaction, which comprises the following steps:
filling the metal oxide catalyst into a fixed bed reactor, setting the air pressure to be 5Mpa, controlling the reaction temperature to be 300-400 ℃, adopting a temperature programming controller to control, detecting data once at 10 ℃, and mixing the hydrogen and nitrogen gas at the volume airspeed of 20000-25000 h -1 Introducing into a reaction tube, wherein the molar ratio of the mixed gas is as follows: nitrogen= (3-5): 1.
further, the reaction temperature is preferably 375 to 400 ℃.
Further, the mass ratio of the metal oxide catalyst to the raw material mixture is (0.33-0.5): 1, the particular amount depends on the scale of the catalytic device.
The invention also provides the application of the metal oxide catalyst in catalyzing synthesis of ammonia.
The beneficial effects of the invention are as follows:
(1) Compared with the prior art, the catalyst for synthesizing ammonia under mild conditions provided by the invention has the advantages that in the aging process of preparing the catalyst, the small molecule regulation technology is utilized, so that the pore channel structure of the catalyst is more suitable for N 2 And H 2 From fig. 5, it can be seen that the catalyst regulated by small molecules has smaller pore diameter, which is favorable for the synthesis of ammonia, so that the reaction temperature can be reduced on the basis of the prior art, and the catalyst is favorable for energy conservation, consumption reduction, high efficiency and environmental protection in the production process.
(2) The cost of the catalyst is effectively reduced on the basis of keeping the original catalytic activity by screening the proportion of the carrier and the active components, and meanwhile, the physical property is increased, so that the cost of the complete equipment can be effectively reduced;
(3) The catalyst has low activation temperature and high conversion rate, and can greatly improve the production efficiency and reduce the related cost when being applied to industrial production.
Drawings
FIG. 1 is a graph showing the reaction rates of catalytic synthesis of ammonia for catalyst A of example 1 and catalyst I of the comparative example.
FIG. 2 is a graph of the reaction rates of catalytic synthesis of ammonia for catalyst B and catalyst C of examples 2 and 3 (varying the pH of the wash).
FIG. 3 is a graph showing the reaction rates of the catalytic synthesis of ammonia by catalysts D and E of example 4 and example 5 (composition of the support was changed).
FIG. 4 is a graph of the reaction rates of catalytic synthesis of ammonia for catalysts G and H (varying ruthenium loading) of example 6 and example 7.
Fig. 5 is a comparative graph of catalyst pore diameters of example 1 and comparative example.
Detailed Description
The invention will be described in detail with reference to examples.
Examples
Example 1
The metal oxide catalyst loaded with ruthenium comprises Ru as an active ingredient, a carrier is metal oxide, the metal oxide is selected from CeO, mgO and BaO, wherein the mass ratio of Ce, mg and Ba is 2:3:5,
wherein the loading of Ru is 1%, based on the mass of the support.
The preparation method comprises the following steps:
weighing 35mL of deionized water, pouring the deionized water into a 100mL beaker, adding a magnetic stirring rod, stirring and heating in a constant-temperature magnetic stirrer, and setting the temperature to be 65 ℃; adding 2.52g of cerium nitrate hexahydrate, 5.56g of magnesium nitrate and 4.26g of barium nitrate into a beaker, stirring and dissolving uniformly, and then adding into a dynamic reaction kettle;
under the condition of heating and stirring at 65 ℃, the rotating speed of a stirring paddle is 300r/min, 15% ammonia water is dropwise added into the metal nitrate solution, the mixing time is controlled to be 30min, the dropwise addition is stopped after the pH value of the suspension is regulated to be about 9, and the mixed solution is continuously stirred for 1h;
after stirring has ceased, the precipitate is aged for 2h at a constant temperature of 65℃and during this process a suspension containing 10% H is introduced 2 H of (2) 2 And N 2 Is a mixed gas of (a) and (b);
repeatedly washing the mixed precipitate with deionized water for four times, wherein the water consumption is 300ml each time, the stirring time of the first washing is one hour, and then the washing time is half an hour each time; washing to a pH of between 7 and 7.3, and drying the filtrate in a constant temperature drying oven at 100 ℃ overnight; placing the sample into a muffle furnace for roasting for 4 hours at 550 ℃ to obtain a metal oxide carrier;
then placing the carrier into a 100mL beaker, adding 5mL ruthenium acetate ethanol solution with the mass fraction of ruthenium of 1% and 50mL deionized water, and stirring and mixing for 12h at 65 ℃ and 300 r/min; then the liquid is distilled under reduced pressure, and the obtained solid is put into a constant temperature drying oven at 100 ℃ for drying for 8 hours; then placing the mixture into a muffle furnace for roasting for 6h at 450 ℃, and finally reducing the mixture in the tubular furnace for 5h under the condition of 400 ℃ and normal pressure to obtain the supported metal oxide catalyst A.
Catalytic activity evaluation experiment:
the prepared metal oxide powder is pressed into tablets and ground, particles with 40-60 meshes are sieved out, 0.1g of catalyst particles are weighed and put into a fixed bed stainless steel tube reactor for activity evaluation test of simulated synthetic ammonia reaction gas, the air pressure is normal pressure, and the molar ratio is hydrogen: nitrogen=3: 1, with a volume space velocity of 20000h -1 Introducing the mixture into a reaction tube, raising the pressure to 5Mpa, controlling the reaction temperature to 300-400 ℃, and detecting data once at 10 ℃ by adopting a temperature programming controller. And (3) carrying out online quantitative analysis on the gas by adopting a gas chromatograph using a TCD detector, thereby obtaining the generation speed of the ammonia gas. The results of the experiment are shown in FIG. 1.
Example 2
The metal oxide catalyst loaded with ruthenium comprises Ru as an active ingredient, a carrier is metal oxide, the metal oxide is selected from CeO, mgO and BaO, wherein the mass ratio of Ce, mg and Ba is 2:3:5,
wherein the loading of Ru is 1%, based on the mass of the support.
The preparation method comprises the following steps:
weighing 35mL of deionized water, pouring the deionized water into a 100mL beaker, adding a magnetic stirring rod, stirring and heating in a constant-temperature magnetic stirrer, and setting the temperature to be 65 ℃; adding 2.52g of cerium nitrate hexahydrate, 5.56g of magnesium nitrate and 4.26g of barium nitrate into a beaker, stirring and dissolving uniformly, and then adding into a dynamic reaction kettle;
under the condition of heating and stirring at 65 ℃, the rotating speed of a stirring paddle is 300r/min, 15% ammonia water is dropwise added into the metal nitrate solution, the mixing time is controlled to be 30min, the dropwise addition is stopped after the pH value of the suspension is regulated to be about 9, and the mixed solution is continuously stirred for 1h;
after stirring has ceased, the precipitate is aged for 2h at a constant temperature of 65℃and during this process a suspension containing 10% H is introduced 2 H of (2) 2 And N 2 Is a mixed gas of (a) and (b);
repeatedly washing the mixed precipitate with deionized water for four times, wherein the water consumption is 300ml each time, the stirring time of the first washing is one hour, and then the washing time is half an hour each time; washing to a pH of between 7.5 and 7.8, and drying the filtrate in a constant temperature drying oven at 100 ℃ overnight; placing the sample into a muffle furnace for roasting for 4 hours at 550 ℃ to obtain a metal oxide carrier;
then placing the carrier into a 100mL beaker, adding 5mL ruthenium acetate ethanol solution with the mass fraction of ruthenium of 1% and 50mL deionized water, and stirring and mixing for 12h at 65 ℃ and 300 r/min; then the liquid is distilled under reduced pressure, and the obtained solid is put into a constant temperature drying oven at 100 ℃ for drying for 8 hours; then placing the mixture into a muffle furnace for roasting for 6h at 450 ℃, and finally reducing the mixture in a tubular furnace for 5h under the condition of 400 ℃ and normal pressure to obtain the supported metal oxide catalyst B.
Catalytic activity evaluation experiment:
tabletting and grinding the prepared metal oxide powder, sieving out 40-60 mesh particles, weighing 0.1g of catalyst particles, and placing into a fixed bedThe activity evaluation test of the simulated synthetic ammonia reaction gas is carried out in the stainless steel tube reactor, the air pressure is normal pressure, and the molar ratio is hydrogen: nitrogen=3: 1, with a volume space velocity of 20000h -1 Introducing the mixture into a reaction tube, raising the pressure to 5Mpa, controlling the reaction temperature to 300-400 ℃, and detecting data once at 10 ℃ by adopting a temperature programming controller. And (3) carrying out online quantitative analysis on the gas by adopting a gas chromatograph using a TCD detector, thereby obtaining the generation speed of the ammonia gas. The results of the experiment are shown in FIG. 2.
Example 3
The metal oxide catalyst loaded with ruthenium has Ru as active component, carrier of metal oxide selected from CeO, mgO and BaO, ce, mg and Ba in the weight ratio of 2 to 3 to 5,
wherein the loading of Ru is (specific value) 1%, based on the mass of the support.
The preparation method comprises the following steps:
weighing 35mL of deionized water, pouring the deionized water into a 100mL beaker, adding a magnetic stirring rod, stirring and heating in a constant-temperature magnetic stirrer, and setting the temperature to be 65 ℃; adding 2.52g of cerium nitrate hexahydrate, 5.56g of magnesium nitrate and 4.26g of barium nitrate into a beaker, stirring and dissolving uniformly, and then adding into a dynamic reaction kettle;
under the condition of heating and stirring at 65 ℃, the rotating speed of a stirring paddle is 300r/min, 15% ammonia water is dropwise added into the metal nitrate solution, the mixing time is controlled to be 30min, the dropwise addition is stopped after the pH value of the suspension is regulated to be about 9, and the mixed solution is continuously stirred for 1h;
after stirring has ceased, the precipitate is aged for 2h at a constant temperature of 65℃and during this process a suspension containing 10% H is introduced 2 H of (2) 2 And N 2 Is a mixed gas of (a) and (b);
repeatedly washing the mixed precipitate with deionized water for four times, wherein the water consumption is 300ml each time, the stirring time of the first washing is one hour, and then the washing time is half an hour each time; washing to a pH of between 6.5 and 7, and drying the filtrate in a constant temperature drying oven at 100 ℃ overnight; placing the sample into a muffle furnace for roasting for 4 hours at 550 ℃ to obtain a metal oxide carrier;
then placing the carrier into a 100mL beaker, adding 5mL ruthenium acetate ethanol solution with the mass fraction of ruthenium of 1% and 50mL deionized water, and stirring and mixing for 12h at 65 ℃ and 300 r/min; then the liquid is distilled under reduced pressure, and the obtained solid is put into a constant temperature drying oven at 100 ℃ for drying for 8 hours; then placing the mixture into a muffle furnace for roasting for 6h at 450 ℃, and finally reducing the mixture in a tubular furnace for 5h under the condition of 400 ℃ and normal pressure to obtain the supported metal oxide catalyst C.
Catalytic activity evaluation experiment:
the prepared metal oxide powder is pressed into tablets and ground, particles with 40-60 meshes are sieved out, 0.1g of catalyst particles are weighed and put into a fixed bed stainless steel tube reactor for activity evaluation test of simulated synthetic ammonia reaction gas, the air pressure is normal pressure, and the molar ratio is hydrogen: nitrogen=3: 1, with a volume space velocity of 20000h -1 Introducing the mixture into a reaction tube, raising the pressure to 5Mpa, controlling the reaction temperature to 300-400 ℃, and detecting data once at 10 ℃ by adopting a temperature programming controller. And (3) carrying out online quantitative analysis on the gas by adopting a gas chromatograph using a TCD detector, thereby obtaining the generation speed of the ammonia gas. The results of the experiment are shown in FIG. 2.
Example 4
The metal oxide catalyst loaded with ruthenium comprises Ru as an active ingredient, a carrier is metal oxide, the metal oxide is selected from CeO, mgO and BaO, wherein the mass ratio of Ce, mg and Ba is 3:4:3,
wherein the loading of Ru is 1%, based on the mass of the support.
The preparation method comprises the following steps:
weighing 35mL of deionized water, pouring the deionized water into a 100mL beaker, adding a magnetic stirring rod, stirring and heating in a constant-temperature magnetic stirrer, and setting the temperature to be 65 ℃; adding 3.78g of cerium nitrate hexahydrate, 7.41g of magnesium nitrate and 2.56g of barium nitrate into a beaker, stirring and dissolving uniformly, and then adding into a dynamic reaction kettle;
under the condition of heating and stirring at 65 ℃, the rotating speed of a stirring paddle is 300r/min, 15% ammonia water is dropwise added into the metal nitrate solution, the mixing time is controlled to be 30min, the dropwise addition is stopped after the pH value of the suspension is regulated to be about 9, and the mixed solution is continuously stirred for 1h;
after stirring has ceased, the precipitate is aged for 2h at a constant temperature of 65℃and during this process a suspension containing 10% H is introduced 2 H of (2) 2 And N 2 Is a mixed gas of (a) and (b);
repeatedly washing the mixed precipitate with deionized water for four times, wherein the water consumption is 300ml each time, the stirring time of the first washing is one hour, and then the washing time is half an hour each time; washing to a pH of between 7 and 7.3, and drying the filtrate in a constant temperature drying oven at 100 ℃ overnight; placing the sample into a muffle furnace for roasting for 4 hours at 550 ℃ to obtain a metal oxide carrier;
then placing the carrier into a 100mL beaker, adding 5mL ruthenium acetate ethanol solution with the mass fraction of ruthenium of 1% and 50mL deionized water, and stirring and mixing for 12h at 65 ℃ and 300 r/min; then the liquid is distilled under reduced pressure, and the obtained solid is put into a constant temperature drying oven at 100 ℃ for drying for 8 hours; then placing the mixture into a muffle furnace for roasting for 6h at 450 ℃, and finally reducing the mixture in a tubular furnace for 5h under the condition of 400 ℃ and normal pressure to obtain the supported metal oxide catalyst D.
Catalytic activity evaluation experiment:
the prepared metal oxide powder is pressed into tablets and ground, particles with 40-60 meshes are sieved out, 0.1g of catalyst particles are weighed and put into a fixed bed stainless steel tube reactor for activity evaluation test of simulated synthetic ammonia reaction gas, the air pressure is normal pressure, and the molar ratio is hydrogen: nitrogen=3: 1, with a volume space velocity of 20000h -1 Introducing the mixture into a reaction tube, raising the pressure to 5Mpa, controlling the reaction temperature to 300-400 ℃, and detecting data once at 10 ℃ by adopting a temperature programming controller. And (3) carrying out online quantitative analysis on the gas by adopting a gas chromatograph using a TCD detector, thereby obtaining the generation speed of the ammonia gas. The results of the obtained experiment are shown in FIG. 3.
Example 5:
the metal oxide catalyst loaded with ruthenium comprises Ru as an active ingredient, a carrier is metal oxide, the metal oxide is selected from CeO, mgO and BaO, wherein the mass ratio of Ce, mg and Ba is 2:1:2,
wherein the loading of Ru is 1%, based on the mass of the support.
The preparation method comprises the following steps:
weighing 35mL of deionized water, pouring the deionized water into a 100mL beaker, adding a magnetic stirring rod, stirring and heating in a constant-temperature magnetic stirrer, and setting the temperature to be 65 ℃; adding 5.05g of cerium nitrate hexahydrate, 3.71g of magnesium nitrate and 3.41g of barium nitrate into a beaker, and stirring and dissolving uniformly;
under the condition of heating and stirring in a water bath at 65 ℃, the rotating speed of a stirring paddle is 400r/min, 15% ammonia water of a precipitator is dropwise added into a metal nitrate solution, the mixing time is controlled to be 30min, meanwhile, the dropwise addition is stopped after the pH value of a suspension is regulated to be about 9 through the water bath in a reaction kettle, and the mixed solution is continuously stirred for 1h;
after stirring has ceased, the precipitate is aged for 2h at a constant temperature of 65℃and during this process a suspension containing 10% H is introduced 2 H of (2) 2 And N 2 Is a mixed gas of (a) and (b);
repeatedly washing the mixed precipitate with tap water for four times, wherein the water consumption is 300ml each time, the stirring time of the first washing is one hour, then the washing time is half an hour each time, the washing is carried out until the pH value is between 7 and 7.3, and the filtrate is placed into a constant-temperature drying oven at 100 ℃ for drying overnight; placing the sample into a muffle furnace for roasting for 4 hours at 550 ℃ to obtain a metal oxide carrier;
adding 5mL of ruthenium acetate ethanol solution with the ruthenium mass fraction of 1% and 50mL of deionized water, placing into a reaction kettle, stirring and mixing for 12H at 65 ℃ and 300r/min, and introducing 10% H into the suspension in the process 2 H of (2) 2 And N 2 Is a mixed gas of (a) and (b); then placing the filtrate into a constant temperature drying oven at 100 ℃ for drying overnight; placing the sample into a muffle furnace, roasting for 4H at 550 ℃, and then placing the sample into a tubular furnace at 400 ℃ under normal pressure, H 2 And reducing for 5h to obtain the supported metal oxide catalyst E.
Catalytic activity evaluation experiment:
tabletting and grinding the prepared metal oxide powder, sieving out 40-60 mesh particles, weighing 0.1gThe catalyst particles are put into a fixed bed stainless steel tube reactor for activity evaluation test of simulated synthetic ammonia reaction gas, the air pressure is normal pressure, and the molar ratio is hydrogen: nitrogen=3: 1, with a volume space velocity of 20000h -1 Introducing the mixture into a reaction tube, raising the pressure to 5Mpa, controlling the reaction temperature to 300-400 ℃, and detecting data once at 10 ℃ by adopting a temperature programming controller. And (3) carrying out online quantitative analysis on the gas by adopting a gas chromatograph using a TCD detector, thereby obtaining the generation speed of the ammonia gas. The results of the obtained experiment are shown in FIG. 3.
Example 6:
the metal oxide catalyst loaded with ruthenium has Ru as active component, metal oxide as carrier and CeO, mgO and La as metal oxide 2 O 3 Wherein the mass ratio of Ce, mg and La is 4:2:1,
wherein the loading of Ru is 1%, based on the mass of the support.
The preparation method comprises the following steps:
weighing 35mL of deionized water, pouring the deionized water into a 100mL beaker, adding a magnetic stirring rod, stirring and heating in a constant-temperature magnetic stirrer, and setting the temperature to be 65 ℃; adding 5.1g of cerium nitrate hexahydrate, 3.41g of magnesium nitrate and 1.33g of lanthanum nitrate hexahydrate into a beaker, and stirring and dissolving uniformly;
under the condition of heating and stirring in a water bath at 65 ℃, the rotating speed of a stirring paddle is 400r/min, 15% ammonia water of a precipitator is dropwise added into a metal nitrate solution, the mixing time is controlled to be 30min, meanwhile, the dropwise addition is stopped after the pH value of a suspension is regulated to be about 9 through the water bath in a reaction kettle, and the mixed solution is continuously stirred for 1h;
after stirring has ceased, the precipitate is aged for 2h at a constant temperature of 65℃and during this process a suspension containing 10% H is introduced 2 H of (2) 2 And N 2 Is a mixed gas of (a) and (b);
repeatedly washing the mixed precipitate with tap water for four times, wherein the water consumption is 300ml each time, the stirring time of the first washing is one hour, and then the washing time is half an hour each time; washing to a pH of between 7 and 7.3, and drying the filtrate in a constant temperature drying oven at 100 ℃ overnight; placing the sample into a muffle furnace for roasting for 4 hours at 550 ℃ to obtain a metal oxide carrier;
adding 5mL of ruthenium acetate ethanol solution with the ruthenium mass fraction of 1% and 50mL of deionized water, placing into a reaction kettle, stirring and mixing for 12h at 65 ℃ and 300r/min, and introducing 10% H into the suspension in the process 2 H of (2) 2 And N 2 Is a mixed gas of (a) and (b); then placing the filtrate into a constant temperature drying oven at 100 ℃ for drying overnight; and (3) placing the sample into a muffle furnace for roasting for 4 hours at 550 ℃, and then reducing H2 in the tubular furnace for 5 hours under the condition of 400 ℃ and normal pressure to obtain the supported metal oxide catalyst G.
Catalytic activity evaluation experiment:
the prepared metal oxide powder is pressed into tablets and ground, particles with 40-60 meshes are sieved out, 0.1g of catalyst particles are weighed and put into a fixed bed stainless steel tube reactor for activity evaluation test of simulated synthetic ammonia reaction gas, the air pressure is normal pressure, and the molar ratio is hydrogen: nitrogen=3: 1, with a volume space velocity of 20000h -1 Introducing the mixture into a reaction tube, raising the pressure to 5Mpa, controlling the reaction temperature to 300-400 ℃, and detecting data once at 10 ℃ by adopting a temperature programming controller. And (3) carrying out online quantitative analysis on the gas by adopting a gas chromatograph using a TCD detector, thereby obtaining the generation speed of the ammonia gas. The results of the obtained experiment are shown in FIG. 4.
Example 7
The metal oxide catalyst loaded with ruthenium comprises Ru as an active ingredient, a carrier is metal oxide, the metal oxide is selected from CeO, mgO and BaO, wherein the mass ratio of Ce, mg and Ba is 2:3:5,
wherein the loading of Ru is 2% based on the mass of the support.
The preparation method comprises the following steps:
weighing 35mL of deionized water, pouring the deionized water into a 100mL beaker, adding a magnetic stirring rod, stirring and heating in a constant-temperature magnetic stirrer, and setting the temperature to be 65 ℃; 2.52g of cerium nitrate hexahydrate, 5.56g of magnesium nitrate and 4.26g of barium nitrate are added into a beaker, and stirred and dissolved uniformly;
under the condition of heating and stirring in a water bath at 65 ℃, the rotating speed of a stirring paddle is 400r/min, 15% ammonia water of a precipitant is dropwise added into a metal nitrate solution, the mixing time is controlled to be 30min, meanwhile, the dropwise addition is stopped after the pH value of a suspension is regulated to be about 9 through the water bath in a reaction kettle, and the mixed solution is continuously stirred for 1h;
after stirring has ceased, the precipitate is aged for 2h at a constant temperature of 65℃and during this process a suspension containing 10% H is introduced 2 H of (2) 2 And N 2 Is a mixed gas of (a) and (b);
the mixed precipitate was repeatedly washed with tap water four times with 300ml of water each time, the stirring time for the first washing was one hour, and then the washing time was half an hour. Washing to a pH of between 7 and 7.3, and drying the filtrate in a constant temperature drying oven at 100 ℃ overnight; placing the sample into a muffle furnace for roasting for 4 hours at 550 ℃ to obtain a metal oxide carrier;
adding 10mL of ruthenium acetate ethanol solution with the ruthenium mass fraction of 1% and 50mL of deionized water, placing into a reaction kettle, stirring and mixing for 12H at 65 ℃ and 300r/min, and introducing 10% H into the suspension in the process 2 H of (2) 2 And N 2 Is a mixed gas of (a) and (b); then placing the filtrate into a constant temperature drying oven at 100 ℃ for drying overnight; placing the sample into a muffle furnace, roasting for 4H at 550 ℃, and then placing the sample into a tubular furnace at 400 ℃ under normal pressure, H 2 And reducing for 5H to obtain the supported metal oxide catalyst H.
Catalytic activity evaluation experiment:
the prepared metal oxide powder is pressed into tablets and ground, particles with 40-60 meshes are sieved out, 0.1g of catalyst particles are weighed and put into a fixed bed stainless steel tube reactor for activity evaluation test of simulated synthetic ammonia reaction gas, the air pressure is normal pressure, and the molar ratio is hydrogen: nitrogen=3: 1, with a volume space velocity of 20000h -1 Introducing the mixture into a reaction tube, raising the pressure to 5Mpa, controlling the reaction temperature to 300-400 ℃, and detecting data once at 10 ℃ by adopting a temperature programming controller. And (3) carrying out online quantitative analysis on the gas by adopting a gas chromatograph using a TCD detector, thereby obtaining the generation speed of the ammonia gas. The results of the obtained experiment are shown in FIG. 5.
Comparative example
Weighing 35mL of deionized water, pouring the deionized water into a 100mL beaker, adding a magnetic stirring rod, stirring and heating in a constant-temperature magnetic stirrer, and setting the temperature to be 65 ℃;
adding 2.52g of cerium nitrate hexahydrate, 5.56g of magnesium nitrate and 4.26g of barium nitrate into a beaker, stirring and dissolving uniformly, and then adding into a dynamic reaction kettle; under the condition of heating and stirring at 65 ℃, the rotating speed of a stirring paddle is 300r/min, 15% ammonia water is dropwise added into the metal nitrate solution, the mixing time is controlled to be 30min, the dropwise addition is stopped after the pH value of the suspension is regulated to be about 9, and the mixed solution is continuously stirred for 1h;
after stirring is stopped, ageing the precipitate for 2 hours at a constant temperature of 65 ℃, repeatedly washing and filtering the mixed precipitate liquid with deionized water for four times, wherein the water consumption is 300ml each time, the stirring time of the first washing is one hour, and the washing time is half an hour later; washing to a pH of between 7 and 7.3, and drying the filtrate in a constant temperature drying oven at 100 ℃ overnight; placing the sample into a muffle furnace for roasting for 4 hours at 550 ℃ to obtain a metal oxide carrier;
then placing the carrier into a 100mL beaker, adding 5mL ruthenium acetate ethanol solution with the mass fraction of ruthenium of 1% and 50mL deionized water, and stirring and mixing for 12h at 65 ℃ and 300 r/min; then the liquid is distilled under reduced pressure, and the obtained solid is put into a constant temperature drying oven at 100 ℃ for drying for 8 hours; then placing the mixture into a muffle furnace for roasting for 6h at 450 ℃, and finally reducing the mixture in a tubular furnace for 5h under the condition of 400 ℃ and normal pressure to obtain the supported metal oxide catalyst I.
Catalytic activity evaluation experiment:
the prepared metal oxide powder is pressed into tablets and ground, particles with 40-60 meshes are sieved out, 0.1g of catalyst particles are weighed and put into a fixed bed stainless steel tube reactor for activity evaluation test of simulated synthetic ammonia reaction gas, the air pressure is normal pressure, and the molar ratio is hydrogen: nitrogen=3: 1, with a volume space velocity of 20000h -1 Introducing the mixture into a reaction tube, raising the pressure to 5Mpa, controlling the reaction temperature to 300-400 ℃, and detecting data once at 10 ℃ by adopting a temperature programming controller. Performing online quantitative analysis of gas by using gas chromatograph using TCD detector to obtainTo the rate of ammonia production. The results of the experiment are shown in FIG. 1.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any other way, but is intended to cover any modifications or equivalent variations according to the technical spirit of the present invention, which fall within the scope of the present invention as defined by the appended claims.
Claims (10)
1. A ruthenium-supported metal oxide catalyst is characterized in that the active component of the metal oxide catalyst is Ru, the carrier is metal oxide, and the metal oxide is selected from CeO, mgO, baO and La 2 O 3 Wherein the mass ratio of Ce, mg, ba and La is (1-3): 0-5): 2-5): 0-2;
the preparation method of the metal oxide catalyst comprises the following steps:
step S1: preparing a metal salt solution: two or more nitrates of cerium, magnesium, barium and lanthanum are fully dissolved in water at 60-70 ℃ to prepare a metal salt solution, and then the metal salt solution is transferred into a stirring kettle to be continuously stirred;
step S2: coprecipitation reaction: slowly adding ammonia water with the mass concentration of 10-15% into the stirring kettle, and regulating the pH value of the suspension in the adding process until the pH value is 8.5-9.5, and stopping dropwise adding the ammonia water;
step S3: aging: precipitating and aging the suspension at 60-80 ℃ for 0.5-5h; during the aging process, 10% H was introduced into the suspension 2 H of (2) 2 And N 2 Is a mixed gas of (a) and (b);
step S4: washing, drying and roasting the aged mixed precipitate;
step S5: according to the loading amount of ruthenium, adding ethanol solution of ruthenium acetate and deionized water into the baked solid, and carrying out reduced pressure distillation, drying, baking and reduction on the mixed reaction liquid to obtain the metal oxide catalyst.
2. The metal oxide catalyst according to claim 1, characterized in that the loading of Ru is 0.005-0.05 based on the mass of the support.
3. The metal oxide catalyst according to claim 1 or 2, wherein in step S2, the addition time of the aqueous ammonia is controlled to be 1 to 1.5 hours.
4. A metal oxide catalyst according to claim 3, characterized in that in step S2 the temperature of the stirred tank is controlled to 60-70 ℃ by means of a water bath.
5. The metal oxide catalyst according to claim 4, wherein in step S2, the pH value of the suspension is continuously detected during the addition until the pH value is 8.5 to 9.5, and then the dropwise addition of ammonia water is stopped, and the suspension is stirred for 1 hour.
6. The metal oxide catalyst according to claim 1 or 2, characterized in that in step S4, the mixed precipitate is washed with water and suction filtered several times until the pH after washing is between 6.5 and 7.8.
7. The metal oxide catalyst according to claim 6, wherein in step S4, the mixed precipitate is washed with water and suction filtered a plurality of times until the pH after washing is 7 to 7.3.
8. The metal oxide catalyst according to claim 7, wherein in step S4, the filtrate is calcined in a muffle furnace at a temperature of 400-600 ℃ for 3-7 h.
9. The metal oxide catalyst according to claim 8, characterized in that in step S4 the filtrate is placed in a muffle furnace for 6 hours at a temperature of 450 ℃ or for 4 hours at a temperature of 550 ℃.
10. According to claim 1 or 2In the step S5, according to the load of ruthenium, adding ethanol solution of ruthenium acetate and deionized water into the roasted solid, stirring and mixing for 12 hours at 60 ℃, then carrying out reduced pressure distillation, putting the obtained solid into a constant temperature drying oven at 100 ℃ for drying for 8 hours, finally putting the sample into a muffle furnace for roasting for 6 hours at 400-450 ℃, and finally using H 2 And reducing to obtain the metal oxide catalyst.
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