CN110813359A - Ruthenium-based ammonia synthesis catalyst with nitrogen-doped porous carbon material as carrier and preparation method thereof - Google Patents
Ruthenium-based ammonia synthesis catalyst with nitrogen-doped porous carbon material as carrier and preparation method thereof Download PDFInfo
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- CN110813359A CN110813359A CN201911159616.2A CN201911159616A CN110813359A CN 110813359 A CN110813359 A CN 110813359A CN 201911159616 A CN201911159616 A CN 201911159616A CN 110813359 A CN110813359 A CN 110813359A
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 92
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 49
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 39
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 38
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 100
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 36
- 239000011259 mixed solution Substances 0.000 claims abstract description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 14
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 12
- XTLNYNMNUCLWEZ-UHFFFAOYSA-N ethanol;propan-2-one Chemical compound CCO.CC(C)=O XTLNYNMNUCLWEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 72
- 229910052799 carbon Inorganic materials 0.000 claims description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000002243 precursor Substances 0.000 claims description 31
- 239000012265 solid product Substances 0.000 claims description 28
- 239000002131 composite material Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 17
- YLPJWCDYYXQCIP-UHFFFAOYSA-N nitroso nitrate;ruthenium Chemical compound [Ru].[O-][N+](=O)ON=O YLPJWCDYYXQCIP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 6
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 239000003337 fertilizer Substances 0.000 abstract description 2
- 150000003304 ruthenium compounds Chemical class 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 description 13
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000002604 ultrasonography Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- IDIFPUPZOAXKOV-UHFFFAOYSA-N azane ruthenium Chemical compound N.[Ru] IDIFPUPZOAXKOV-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 125000004355 nitrogen functional group Chemical group 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- OKZJGWWKRGIIRL-UHFFFAOYSA-N [N].NC1=NC(N)=NC(N)=N1 Chemical compound [N].NC1=NC(N)=NC(N)=N1 OKZJGWWKRGIIRL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/617—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention belongs to the technical field of fertilizer catalysts, and particularly relates to a ruthenium-based ammonia synthesis catalyst taking a nitrogen-doped porous carbon material as a carrier and a preparation method thereof. In the preparation process of the catalyst, zinc nitrate hexahydrate is dissolved in an alkaline aqueous solution, 2-methylimidazole is dissolved in N, N-dimethylformamide and then added into the alkaline aqueous solution, and the solution is uniformly mixed, subjected to hydrothermal reaction and carbonized to obtain the nitrogen-doped porous carbon material. Dissolving a chlorine-free ruthenium compound and polyvinylpyrrolidone into an ethylene glycol solution, heating, washing with an ethanol-acetone mixed solution, and adding an ethanol solution; the ruthenium-based ammonia synthesis catalyst with the nitrogen-doped porous carbon material as the carrier is obtained by adding the porous carbon material, stirring, standing, separating, drying and reducing, and the prepared catalyst not only has higher specific surface area, but also has higher nitrogen doping amount, so that the catalyst has higher ammonia synthesis activity and better application prospect.
Description
Technical Field
The invention belongs to the technical field of fertilizer catalysts, and particularly relates to a ruthenium-based ammonia synthesis catalyst taking a nitrogen-doped porous carbon material as a carrier and a preparation method thereof.
Background
The synthetic ammonia industry is the national economic industry of the prop, and the current Haber-Bosch method for industrial ammonia synthesis must produce ammonia under the harsh conditions of high temperature (400-. The key of energy saving and consumption reduction in the ammonia synthesis industry is the application of a high-performance catalyst, so the research and design of a high-efficiency ammonia synthesis catalyst are always the research hotspots in the field of catalysis, the active carbon supported ruthenium catalyst is the ammonia synthesis catalyst with the most application prospect in ammonia synthesis under mild conditions at present, the successful application of the active carbon supported ruthenium catalyst greatly reduces the energy consumption of the ammonia synthesis industry, but the carbon material supported ruthenium catalyst with higher performance needs to be further and deeply researched for realizing large-scale industrial application.
In recent years, with the rapid development of carbon materials, many novel carbon materials become carrier materials of metal catalysts, and the modification and modification of the carbon materials are expected to greatly improve the performance of the prepared metal catalysts, wherein nitrogen doping in the carbon materials can not only remove oxygen-containing groups on the surface, but also influence the electronic properties of the loaded metal and the adsorption properties of reaction gases, and the carbon materials are one of important means for modification and modification of the carbon materials. Patent CN106513030A reports that nitrogen-doped activated carbon is obtained by introducing melamine nitrogen-containing precursor into graphitized activated carbon, and performing mechanical stirring and mixing, constant-temperature water bath heating and calcining, but the nitrogen content obtained by this method is between 0.72 wt% and 7.61 wt%. Patent CN104785255A reports that nitrogen-containing precursor is introduced into commercial activated carbon, and after calcination and cooling, Soxhlet extraction is carried out to obtain nitrogen-doped activated carbon with high specific surface area, but the nitrogen content obtained by the method is between 1 and 10 weight percent, and the ammonia synthesis performance of the ruthenium catalyst prepared by taking the nitrogen-containing precursor as a carrier is still waited for furtherAnd (4) improving. Patent CN107694594A reports that a carbon material and metal ion ammonia are mixed and subjected to microwave reaction in a carbon bath under inert atmosphere to obtain a metal-supported nitrogen-doped carbon material, but the nitrogen content obtained by the method is between 1 and 4 weight percent, and the specific surface area of the prepared material is only 380 to 450m2(ii) in terms of/g. Obviously, the nitrogen-doped carbon material prepared by the prior art is difficult to simultaneously maintain high specific surface area and higher nitrogen content, and is not suitable to be used as an ideal carrier material of ruthenium-based ammonia synthesis catalyst.
Disclosure of Invention
The invention aims to provide a nitrogen-doped porous carbon composite material, wherein a nitrogen functional group is introduced in the preparation process of the composite material, so that the prepared nitrogen-doped porous carbon composite material carrier has higher specific surface area and higher nitrogen doping amount, and becomes an ideal carrier material of a ruthenium-based ammonia synthesis catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
the ruthenium-based ammonia synthesis catalyst with the nitrogen-doped porous carbon material as the carrier has the nitrogen mass fraction of 12-18% and the BET specific surface area of 700-900 m2/g。
The preparation method of the ruthenium-based ammonia synthesis catalyst with the nitrogen-doped porous carbon material as the carrier takes the nitrogen-doped porous carbon composite material as the carrier and ruthenium as an active component, wherein the addition amount of the ruthenium is 1-10wt% calculated by the mass of the nitrogen-doped porous carbon composite material.
The method specifically comprises the following steps:
1) dissolving zinc nitrate hexahydrate in an alkaline aqueous solution;
2) dissolving dimethyl imidazole in N, N-dimethylformamide solution, and then adding alkaline aqueous solution;
3) after the solutions obtained in the steps 1) and 2) are mixed and stirred uniformly, and subjected to hydrothermal reaction for a certain time, centrifuging, washing and drying the obtained suspension to obtain a solid product;
4) carbonizing the solid product obtained in the step 3) at high temperature to obtain a nitrogen-doped porous carbon composite material;
5) dissolving ruthenium nitrosyl nitrate and polyvinylpyrrolidone into an ethylene glycol solution, heating the obtained mixed solution to form a thick liquid, and washing the thick liquid in an ethanol-acetone mixed solution to obtain a solid ruthenium precursor;
6) and (3) dispersing the ruthenium precursor in an absolute ethyl alcohol solution, adding the solution into the nitrogen-doped porous carbon composite material obtained in the step (4), uniformly stirring, standing for a certain time, separating to remove liquid, drying and reducing to obtain the ruthenium-based catalyst taking the nitrogen-doped porous carbon as a carrier.
The molar ratio of the zinc nitrate in the step 1) to the solute in the alkaline aqueous solution in the step 1) is (1:7) - (1: 68);
the alkaline solution in the steps 1) and 2) is a sodium hydroxide or potassium hydroxide aqueous solution, and the concentration is 1-8 mol/L; the mass ratio of the zinc nitrate hexahydrate to the 2-methylimidazole is (1:0.6) - (1: 1); the molar ratio of the dimethyl imidazole to the solute in the alkaline solution in the step 2) is (1:0.2) - (1: 1.4). Based on the mass of the 2-methylimidazole, 3-6 mL of N, N-dimethylformamide solution is needed for each gram of the 2-methylimidazole.
The hydrothermal reaction temperature in the step 3) is 100-150 ℃, and the reaction time is 2-20 hours.
The washing step in the step 3) takes a methanol water solution as a washing liquid, wherein the volume fraction content of methanol is not lower than 80%; the drying is carried out in vacuum or inert gas, and the drying temperature is 50-80 ℃.
The high-temperature carbonization treatment temperature in the step 4) is 400-900 ℃; the treatment time is 1-5 hours; the carbonization process is carried out in a hydrogen-containing mixed gas, wherein the content of hydrogen is 3-100% (volume fraction), and other gas components of the mixed gas are gases formed by mixing one or more of nitrogen or a zero-group inert gas.
And 5) the molar ratio of the ruthenium nitrosyl nitrate to the polyvinylpyrrolidone is (1:1) - (1:2), the heating temperature is 160-240 ℃, and the heating time is 3-9 hours.
The volume ratio of the ethanol to the acetone in the ethanol-acetone mixed solution used in the washing in the step 5) is (1:1) - (1: 3).
Step 6), standing for 1-20 hours; the drying is carried out in vacuum or inert gas, the drying temperature is 50-120 ℃, the reduction is carried out in hydrogen-containing mixed gas at the temperature of 300-600 ℃, the volume fraction of hydrogen in the mixed gas is 3-100%, and the reduction time is 0.3-36 hours.
The invention has the following remarkable advantages:
compared with the prior art, the catalyst prepared by the invention has higher specific surface area and strength and higher ammonia synthesis activity compared with the existing nitrogen-doped carbon and commercial active carbon-loaded ruthenium-based ammonia synthesis catalyst, so the catalyst has better application prospect.
Compared with a carbon material carrier, the preparation method of the ruthenium-based ammonia synthesis catalyst taking the nitrogen-doped porous carbon material as the carrier disclosed by the invention has great advantages, the ammonia synthesis ruthenium-based catalyst taking ruthenium as an active component integrates the characteristics of other preparation methods, nitrogen functional groups are introduced in the preparation process of the carbon material, and the specific surface area of the prepared nitrogen-doped porous carbon composite material carrier is higher.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1:
1) 1.93 g of zinc nitrate hexahydrate are dissolved in 48 ml of sodium hydroxide solution (6 mol/L);
2) 2.104 g of 2-methylimidazole were dissolved in 9.6ml of N, N-dimethylformamide (purity 99.5%), and then 6.4ml of sodium hydroxide (6 mol/L) solution was added;
3) uniformly mixing and stirring the solutions obtained in the steps (1) and (2), heating and reacting for 4 hours at a constant temperature of 120 ℃ in a hydrothermal kettle to obtain a milk-white solution, washing and centrifuging by using a methanol solution to obtain a solid product, and drying for 12 hours at a constant temperature in a vacuum drying oven at 80 ℃ to obtain a solid product;
4) putting the solid product obtained in the step (3) into a tube furnace, and adding the solid product into the tube furnace at 10% (volume fraction) of H2Maintaining the temperature at the rate of 2 ℃/min to 800 ℃ for 4 hours under the-Ar atmosphere for high-temperature carbonization to obtain a nitrogen-doped porous carbon material;
5) dissolving 12.52 ml of ruthenium nitrosyl nitrate solution and 1.91 g of polyvinylpyrrolidone into 120 ml of ethylene glycol solution under the conditions of ultrasound and stirring, heating the obtained mixed solution at 200 ℃ for 3 hours in an air atmosphere until a thick liquid is formed, collecting the mixed solution, and washing the mixed solution for 5 times by using an ethanol-acetone mixed solution (volume ratio of 1:3) to obtain a solid ruthenium precursor;
6) dispersing the ruthenium precursor in 40 ml of absolute ethanol solution, adding the solution into 1.5 g of nitrogen-doped porous carbon material obtained in the step (4), mixing and stirring for 12 hours, standing for 2 hours, separating to remove liquid, carrying out vacuum drying at 60 ℃ for 10 hours, and then carrying out drying at 500 ℃ for 10% (volume fraction) H2And reducing for 2 h under an-Ar atmosphere to obtain the ruthenium-based catalyst with the nitrogen-doped porous carbon as the carrier, wherein the addition amount of ruthenium is 1.5wt% calculated by the mass of the nitrogen-doped porous carbon composite material.
Example 2:
1) 1.26 g of zinc nitrate hexahydrate is dissolved in 30 ml of sodium hydroxide solution (6 mol/L);
2) 2.104 g of 2-methylimidazole was dissolved in 15 ml of N, N-dimethylformamide (purity: 99.5%), and then 6ml of sodium hydroxide (6 mol/L) solution was added;
3) uniformly mixing and stirring the solutions obtained in the steps (1) and (2), heating and reacting for 4 hours at the constant temperature of 130 ℃ in a hydrothermal kettle to obtain a milk white solution, washing and centrifuging by using a methanol solution to obtain a solid product, and drying for 12 hours at the constant temperature in a vacuum drying oven at the temperature of 70 ℃ to obtain the solid product;
4) subjecting the product obtained in the step (3) toThe solid product was placed in a tube furnace at 10% (volume fraction) H2Maintaining the temperature at the temperature rising rate of 2 ℃/min to 700 ℃ for 5 hours under the-Ar atmosphere to carry out high-temperature carbonization, thus obtaining the nitrogen-doped porous carbon material;
5) dissolving 12.52 ml of ruthenium nitrosyl nitrate solution (ruthenium 1.5% w/v) and 2.1 g of polyvinylpyrrolidone into 130 ml of ethylene glycol solution under the conditions of ultrasound and stirring, heating the obtained mixed solution at 210 ℃ for 3.5 hours in an air atmosphere until thick liquid is formed, collecting the mixed solution, and washing the mixed solution for 5 times by using ethanol-acetone mixed solution (volume ratio is 1:3) to obtain a solid ruthenium precursor;
6) dispersing the ruthenium precursor in 50 ml of absolute ethanol solution, adding the solution into 1.5 g of nitrogen-doped porous carbon material obtained in the step (4), mixing and stirring for 8 hours, standing for 3 hours, separating to remove liquid, carrying out vacuum drying at the drying temperature of 80 ℃ for 10 hours, and then carrying out drying at the temperature of 450 ℃ for 10% (volume fraction) H2And reducing for 3 h under an-Ar atmosphere to obtain the ruthenium-based catalyst with the nitrogen-doped porous carbon as the carrier, wherein the addition amount of ruthenium is 1.3wt% calculated by the mass of the nitrogen-doped porous carbon composite carrier.
Example 3:
1) 1.93 g of zinc nitrate hexahydrate are dissolved in 48 ml of sodium hydroxide solution (6 mol/L);
2) 2.104 g of 2-methylimidazole were dissolved in 9.6ml of N, N-dimethylformamide (purity 99.5%), and then 6.4ml of sodium hydroxide (6 mol/L) solution was added;
3) uniformly mixing and stirring the solutions obtained in the steps (1) and (2), heating and reacting for 4 hours at the constant temperature of 140 ℃ in a hydrothermal kettle to obtain a milk white solution, washing and centrifuging by using a methanol solution to obtain a solid product, and drying for 10 hours at the constant temperature in a vacuum drying oven at the temperature of 80 ℃ to obtain the solid product;
4) putting the solid product obtained in the step (3) into a tube furnace, and reacting in pure H2Maintaining the temperature at the rate of 2 ℃/min to 900 ℃ for 3 hours under the atmosphere to carry out high-temperature carbonization, thus obtaining the nitrogen-doped porous carbon material;
5) dissolving 12.52 ml of ruthenium nitrosyl nitrate solution (ruthenium 1.5% w/v) and 1.91 g of polyvinylpyrrolidone into 150 ml of ethylene glycol solution under the conditions of ultrasound and stirring, heating the obtained mixed solution at 200 ℃ for 3 hours in an air atmosphere until a thick liquid is formed, collecting the mixed solution, and washing the collected mixed solution for 5 times by using an ethanol-acetone mixed solution (volume ratio of 1:3) to obtain a solid ruthenium precursor;
6) dispersing the ruthenium precursor in 40 ml of absolute ethanol solution, adding the solution into 1.5 g of nitrogen-doped porous carbon material obtained in the step (4), mixing and stirring for 10 hours, standing for 2 hours, separating to remove liquid, carrying out vacuum drying at 60 ℃ for 10 hours, and then drying at 500 ℃ for 30% (volume fraction) H2And reducing for 2 h under an-Ar atmosphere to obtain the ruthenium-based catalyst with the nitrogen-doped porous carbon as the carrier, wherein the addition amount of ruthenium is 1.5wt% calculated by the mass of the nitrogen-doped porous carbon composite carrier.
Example 4:
1) 1.93 g of zinc nitrate hexahydrate is dissolved in 48 ml of potassium hydroxide solution (4 mol/L);
2) 2.104 g of 2-methylimidazole was dissolved in 9.6ml of N, N-dimethylformamide (purity: 99.5%), and then 6.4ml of a potassium hydroxide (4 mol/L) solution was added;
3) uniformly mixing and stirring the solutions obtained in the steps (1) and (2), heating and reacting for 4 hours at the constant temperature of 150 ℃ in a hydrothermal kettle to obtain a milk white solution, washing for 7 times by using a methanol solution, centrifuging to obtain a solid product, and drying for 12 hours at the constant temperature in a vacuum drying oven at the temperature of 60 ℃ to obtain the solid product;
4) putting the solid product obtained in the step (3) into a tube furnace, and reacting in pure H2Maintaining the temperature at the rate of 5 ℃/min to 700 ℃ for 5 hours under the atmosphere to carry out high-temperature carbonization, thus obtaining the nitrogen-doped porous carbon material;
5) dissolving 12.52 ml of ruthenium nitrosyl nitrate solution (ruthenium 1.5% w/v) and 2.1 g of polyvinylpyrrolidone into 140 ml of ethylene glycol solution under the conditions of ultrasound and stirring, heating the obtained mixed solution at 200 ℃ for 4 hours in an air atmosphere until thick liquid is formed, collecting the mixed solution, and washing the collected mixed solution for 6 times by using ethanol-acetone mixed solution (volume ratio is 1:2) to obtain a solid ruthenium precursor;
6) dispersing the ruthenium precursor in 50 ml of absolute ethanol solution, adding the solution into 1.5 g of nitrogen-doped porous carbon material obtained in the step (4), mixing and stirring for 10 hours, standing for 2 hours, separating to remove liquid, carrying out vacuum drying at the drying temperature of 80 ℃ for 10 hours, and then drying at the temperature of 500 ℃ for 70% (volume fraction) H2And under an-Ar atmosphere, obtaining the ruthenium-based catalyst with the nitrogen-doped porous carbon as the carrier after 3 h, wherein the addition amount of ruthenium is 1.4wt% calculated by the mass of the nitrogen-doped porous carbon composite carrier.
Example 5:
1) 3.86 g of zinc nitrate hexahydrate are dissolved in 48 ml of potassium hydroxide solution (3 mol/L);
2) 3.86 g of 2-methylimidazole were dissolved in 19.2ml of N, N-dimethylformamide (purity 99.5%), and then 19.2ml of a potassium hydroxide solution (3 mol/L) was added;
3) uniformly mixing and stirring the solutions obtained in the steps (1) and (2), heating and reacting for 5 hours at the constant temperature of 120 ℃ in a hydrothermal kettle to obtain a milk white solution, washing and centrifuging by using a methanol solution to obtain a solid product, and drying for 12 hours at the constant temperature in a vacuum drying oven at the temperature of 80 ℃ to obtain the solid product;
4) putting the solid product obtained in the step (3) into a tube furnace, and adding the solid product into the tube furnace at 10% (volume fraction) of H2Carrying out high-temperature carbonization at the temperature rising rate of 5 ℃/min to 750 ℃ for 5 hours under the-Ar atmosphere to obtain a nitrogen-doped porous carbon material;
5) dissolving 25 ml of ruthenium nitrosyl nitrate solution (ruthenium 1.5% w/v) and 3.82 g of polyvinylpyrrolidone into 200 ml of ethylene glycol solution under the conditions of ultrasound and stirring, heating the obtained mixed solution at 200 ℃ for 4 hours in an air atmosphere until thick liquid is formed, collecting the mixed solution, and washing the mixed solution for 6 times by using ethanol-acetone mixed solution (volume ratio is 1:1) to obtain a solid ruthenium precursor;
6) dispersing the ruthenium precursor in 50 ml of absolute ethanol solution, and then adding the solution to the step(4) Mixing and stirring the obtained 1.5 g of nitrogen-doped porous carbon material for 12 hours, standing for 2 hours, separating to remove liquid, performing vacuum drying at 90 ℃ for 10 hours, and performing 50% (volume fraction) H drying at 450 ℃ for 50%2-34% (volume fraction) N2And (3) reducing for 15 h under an Ar atmosphere with the volume fraction of-16% to obtain the ruthenium-based catalyst with the nitrogen-doped porous carbon as the carrier, wherein the addition amount of ruthenium is 3.1wt% calculated by the mass of the nitrogen-doped porous carbon composite carrier.
Example 6:
1) 1.93 g of zinc nitrate hexahydrate are dissolved in 48 ml of sodium hydroxide solution (3 mol/L);
2) 2.104 g of 2-methylimidazole were dissolved in 9.6ml of N, N-dimethylformamide (purity 99.5%), and then 9.6ml of sodium hydroxide solution (3 mol/L) was added;
3) uniformly mixing and stirring the solutions obtained in the steps (1) and (2), heating and reacting for 4 hours at a constant temperature of 120 ℃ in a hydrothermal kettle to obtain a milk-white solution, washing and centrifuging by using a methanol solution to obtain a solid product, and drying for 12 hours at a constant temperature in a vacuum drying oven at 80 ℃ to obtain a solid product;
4) putting the solid product obtained in the step (3) into a tube furnace, and adding the solid product into the tube furnace at 10% (volume fraction) of H2Maintaining the temperature at the rate of 5 ℃/min to 800 ℃ for 3 hours under the-Ar atmosphere to carry out high-temperature carbonization, thus obtaining the nitrogen-doped porous carbon material;
5) dissolving 12.52 ml of ruthenium nitrosyl nitrate solution (ruthenium 1.5% w/v) and 1.91 g of polyvinylpyrrolidone into 120 ml of ethylene glycol solution under the conditions of ultrasound and stirring, heating the obtained mixed solution at 200 ℃ for 3 hours in an air atmosphere until a thick liquid is formed, collecting the mixed solution, and washing the collected mixed solution for 5 times by using an ethanol-acetone mixed solution (volume ratio is 1:3) to obtain a solid ruthenium precursor;
6) dispersing the ruthenium precursor in 50 ml of absolute ethanol solution, adding the solution into 1.5 g of nitrogen-doped porous carbon material obtained in the step (4), mixing and stirring for 12 hours, standing for 2 hours, separating to remove liquid, and drying in vacuum at the drying temperature of 90 DEG CThe drying time was 10 hours, then 10% (volume fraction) H at 300 ℃2And reducing for 30 hours in an-Ar atmosphere to obtain the ruthenium-based catalyst with the nitrogen-doped porous carbon as the carrier, wherein the addition amount of ruthenium is 1.6wt% calculated by the mass of the nitrogen-doped porous carbon composite carrier.
Example 7:
1) 3.86 g of zinc nitrate hexahydrate are dissolved in 48 ml of sodium hydroxide solution (4 mol/L);
2) 4.208 g of 2-methylimidazole are dissolved in 19.2ml of N, N-dimethylformamide (purity 99.5%), and then 12.8 ml of sodium hydroxide solution (4 mol/L) are added;
3) uniformly mixing and stirring the solutions obtained in the steps (1) and (2), heating and reacting for 5 hours at a constant temperature of 120 ℃ in a hydrothermal kettle to obtain a milk-white solution, washing with a methanol solution, centrifuging to obtain a solid product, and drying for 12 hours at a constant temperature in a vacuum drying oven at a temperature of 80 ℃ at a heating rate of 5 ℃/min to obtain a solid product;
4) putting the solid product obtained in the step (3) into a tube furnace, and reacting in pure H2Maintaining at 800 ℃ for 3 hours at the heating rate of 2 ℃/min under the atmosphere for high-temperature carbonization to obtain the nitrogen-doped porous carbon material;
5) dissolving 25.04 ml of ruthenium nitrosyl nitrate solution (ruthenium 1.5% w/v) and 3.82 g of polyvinylpyrrolidone into 160 ml of ethylene glycol solution under the conditions of ultrasound and stirring, heating the obtained mixed solution at 210 ℃ for 5 hours in an air atmosphere until a thick liquid is formed, collecting the mixed solution, and washing the collected mixed solution for 6 times by using an ethanol-acetone mixed solution (volume ratio is 1:3) to obtain a solid ruthenium precursor;
6) dispersing the ruthenium precursor in 60 ml of absolute ethanol solution, adding the solution into 1.5 g of nitrogen-doped porous carbon material obtained in the step (4), mixing and stirring for 12 h, standing for 2 h, separating to remove liquid, carrying out vacuum drying at 90 ℃ for 10 h, reducing at 500 ℃ for 3 h under a pure hydrogen atmosphere to obtain the ruthenium-based catalyst with nitrogen-doped porous carbon as a carrier, wherein the addition amount of ruthenium is 3wt% calculated by the mass of the nitrogen-doped porous carbon composite carrier.
Comparative example 1:
1) pretreatment of commercial activated carbon: weighing 4.0 g of commercial activated carbon C1And drying and washing the mixture for later use without doping nitrogen elements.
2) 6.67 ml of ruthenium nitrosyl nitrate solution (ruthenium 1.5% w/v) is dried at 70 ℃ for 6 h and then dissolved in 6ml of methanol solution with volume concentration of 50% to obtain ruthenium precursor alcohol solution;
3) dipping the ruthenium precursor alcohol solution obtained in the step 2) into the commercial activated carbon carrier treated in the step 1) at 30 ℃ for 1.5 hours;
4) drying the prepared sample at 100 ℃ for 1 h, and then reducing the dried sample with pure hydrogen at 500 ℃ for 3 h to obtain the Ru/C of the ruthenium ammonia synthesis catalyst taking common active carbon as a carrier1The addition amount of ruthenium was 5wt% based on the mass of the nitrogen-doped porous carbon composite carrier.
Comparative example 2:
1) pretreatment of commercial activated carbon: weighing 4.0 g of commercial activated carbon C4And drying and washing the mixture for later use without doping nitrogen elements.
2) Drying 4ml of ruthenium nitrosyl nitrate solution (ruthenium 1.5% w/v) at 70 ℃ for 5 h, and dissolving the dried solution into 6ml of 50% methanol solution with volume concentration to obtain ruthenium precursor alcohol solution;
3) dipping the ruthenium precursor alcohol solution obtained in the step 2) into 2 g of commercial activated carbon carrier treated in the step 1) at 30 ℃ for 1.5 hours;
4) the prepared samples were dried at 100 ℃ for 1H and then purified H2Reducing the mixture for 3 hours at 500 ℃ to obtain Ru/C of ruthenium ammonia synthesis catalyst taking common active carbon as carrier1The addition amount of ruthenium was 3wt% based on the mass of the nitrogen-doped porous carbon composite carrier.
Comparative example 3:
1) pretreatment of commercial activated carbon: weighing 4.0 g of commercial activated carbon C4And drying and washing the mixture for later use without doping nitrogen elements.
2) 6.67 ml of ruthenium nitrosyl nitrate solution (ruthenium 1.5% w/v) is dried at 70 ℃ for 6 h and then dissolved in 6ml of methanol solution with volume concentration of 50% to obtain ruthenium precursor alcohol solution;
3) dipping the ruthenium precursor alcohol solution obtained in the step 2) into the commercial activated carbon carrier treated in the step 1) at 30 ℃ for 1.5 hours;
4) the prepared samples were dried at 100 ℃ for 1H and then purified H2Reducing the mixture for 3 hours at 500 ℃ to obtain Ru/C of ruthenium ammonia synthesis catalyst taking common active carbon as carrier1The addition amount of ruthenium was 5wt% based on the mass of the nitrogen-doped porous carbon composite carrier.
Comparative example 4:
1) preparing a nitrogen-doped carbon carrier: 10.0 g of melamine was weighed into a ceramic crucible with a lid and placed in a tube furnace in N2And (3) carrying out high-temperature polymerization in the atmosphere, and heating the polymerization temperature to 500 ℃ at the speed of 5 ℃/min and maintaining for 3 h to obtain the common nitrogen-doped carbon carrier.
2) Drying 6.67 ml of ruthenium nitrosyl nitrate solution at 70 ℃ for 6 h, and dissolving the dried solution into 6ml of methanol solution with volume concentration of 50% to obtain ruthenium precursor alcohol solution;
3) dipping the ruthenium precursor alcohol solution obtained in the step 2) into 2 g of the common nitrogen-doped carbon carrier treated in the step 1) at 30 ℃ for 1 hour;
4) the prepared samples were dried at 100 ℃ for 1H and then purified H2Reducing the mixture for 3 hours at 500 ℃ to obtain Ru/C of ruthenium ammonia synthesis catalyst taking common active carbon as carrier3N4The addition amount of ruthenium was 5wt% based on the mass of the nitrogen-doped porous carbon composite carrier.
Comparative example 5:
1) preparing a nitrogen-doped carbon carrier: 10.0 g of melamine was weighed into a ceramic crucible with a lid and placed in a tube furnace in N2And (3) carrying out high-temperature polymerization in the atmosphere, and heating the polymerization temperature to 500 ℃ at the speed of 5 ℃/min and maintaining for 3 h to obtain the common nitrogen-doped carbon carrier.
2) Drying 2ml of ruthenium nitrosyl nitrate solution (ruthenium 1.5% w/v) at 70 ℃ for 4h, and dissolving the solution into 6ml of 50% methanol solution with volume concentration to obtain ruthenium precursor alcohol solution;
3) dipping the ruthenium precursor alcohol solution obtained in the step 2) into 2 g of the common nitrogen-doped carbon carrier treated in the step 1) at 30 ℃ for 1 hour;
4) the prepared samples were dried at 100 ℃ for 1H and then purified H2Reducing the mixture for 3 hours at 500 ℃ to obtain Ru/C of ruthenium ammonia synthesis catalyst taking common active carbon as carrier3N4The addition amount of ruthenium was 1.5wt% based on the mass of the nitrogen-doped porous carbon composite carrier.
The ruthenium catalysts obtained in examples 1 to 5 and the ruthenium-based ammonia synthesis catalysts obtained in comparative examples 1 to 3 were evaluated for their catalytic activity in a high-pressure activity test apparatus. The reactor is a fixed bed with an inner diameter of 12 mm. During the test, 0.2 g of catalyst was mixed with quartz sand of larger particle size and packed in the isothermal zone of the reactor. The reaction gas is a nitrogen-hydrogen mixed gas obtained by ammonia high-temperature catalytic cracking, and the ratio of hydrogen to nitrogen is 3: 1; the reaction conditions are as follows: the pressure is 1 MPa, the reaction temperature is 400 ℃, and the reaction space velocity is 3.6 multiplied by 104h-1The results are shown in Table 1.
TABLE 1 specific surface area of catalyst and Ammonia Synthesis reaction Rate
As can be seen from Table 1, the catalyst prepared by the present invention has not only higher specific surface area but also higher ammonia synthesis activity under the same conditions.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (10)
1. A ruthenium-based ammonia synthesis catalyst taking a nitrogen-doped porous carbon material as a carrier is characterized in that: the catalyst takes a nitrogen-doped porous carbon material as a carrier, takes ruthenium as an active component, the mass fraction of nitrogen in the nitrogen-doped porous carbon material is 12-18%, and the addition amount of ruthenium is 1-10wt% calculated by the mass of the nitrogen-doped porous carbon material.
2. A method for preparing a ruthenium-based ammonia synthesis catalyst supported on a nitrogen-doped porous carbon material according to claim 1, characterized in that: the method specifically comprises the following steps:
1) dissolving zinc nitrate hexahydrate in an alkaline aqueous solution;
2) dissolving dimethyl imidazole in N, N-dimethylformamide solution, and then adding alkaline aqueous solution;
3) after the solutions obtained in the steps (1) and (2) are mixed and stirred uniformly, after hydrothermal reaction is carried out for a certain time, the obtained suspension is centrifuged, washed and dried to obtain a solid product;
4) carbonizing the solid product obtained in the step (3) at high temperature to obtain a nitrogen-doped porous carbon composite material;
5) dissolving ruthenium nitrosyl nitrate and polyvinylpyrrolidone into an ethylene glycol solution, heating the obtained mixed solution to form a thick liquid, and washing the thick liquid in an ethanol-acetone mixed solution to obtain a solid ruthenium precursor;
6) and (3) dispersing the ruthenium precursor in an absolute ethyl alcohol solution, adding the solution into the nitrogen-doped porous carbon composite material obtained in the step (4), uniformly stirring, standing for a certain time, separating to remove liquid, drying and reducing to obtain the ruthenium-based catalyst taking the nitrogen-doped porous carbon as a carrier.
3. The ruthenium-based ammonia synthesis catalyst taking nitrogen-doped porous carbon material as a carrier according to claim 2, wherein the molar ratio of zinc nitrate in the step 1) to solute in the alkaline aqueous solution in the step 1) is 1:7 to 1: 68.
4. The ruthenium-based ammonia synthesis catalyst taking nitrogen-doped porous carbon material as a carrier according to claim 2, wherein the alkaline solution in the step 1) and the step 2 is an aqueous solution of sodium hydroxide or potassium hydroxide, and the concentration is 1-8 mol/L; the mass ratio of zinc nitrate hexahydrate to 2-methylimidazole in the steps 1) and 2) is 1: 0.6-1: 1; the molar ratio of the dimethyl imidazole to the solute in the alkaline solution in the step 2) is 1: 0.2-1: 1.4, and each gram of 2-methyl imidazole needs 3-6 mL of N, N-dimethyl formamide solution based on the mass of the 2-methyl imidazole.
5. The ruthenium-based ammonia synthesis catalyst based on nitrogen-doped porous carbon material as carrier according to claim 2, wherein the hydrothermal reaction temperature in step 3) is 100-150 ℃ and the reaction time is 2-20 hours.
6. The ruthenium-based ammonia synthesis catalyst based on nitrogen-doped porous carbon material as carrier according to claim 2, wherein the washing step of step 3) uses methanol aqueous solution as washing liquid, wherein the volume fraction content of methanol is not less than 80%; the drying is carried out in vacuum or inert gas, and the drying temperature is 50-80 ℃.
7. The ruthenium-based ammonia synthesis catalyst based on nitrogen-doped porous carbon material as carrier according to claim 2, wherein the high temperature carbonization temperature in step 4) is 400-900 ℃; the treatment time is 1-5 hours; the carbonization process is carried out in a hydrogen-containing mixed gas, wherein the content of hydrogen is 3-100 vol%, and other gas components of the mixed gas are gases formed by mixing one or more of nitrogen or a zero-group inert gas.
8. The ruthenium-based ammonia synthesis catalyst taking the nitrogen-doped porous carbon material as the carrier according to claim 2, wherein the molar ratio of the ruthenium nitrosyl nitrate to the polyvinylpyrrolidone in the step 5) is 1: 1-1: 2, the heating temperature is 160-240 ℃, and the heating time is 3-9 hours.
9. The ruthenium-based ammonia synthesis catalyst based on nitrogen-doped porous carbon material as carrier according to claim 2, wherein the volume ratio of ethanol to acetone in the ethanol-acetone mixed solution used in the washing in the step 5) is 1: 1-1: 3.
10. The ruthenium-based ammonia synthesis catalyst based on nitrogen-doped porous carbon material as carrier according to claim 2, wherein the standing time in step 6) is 1-20 hours; the drying is carried out in vacuum or inert gas, the drying temperature is 50-120 ℃, the reduction is carried out in hydrogen-containing mixed gas at the temperature of 300-600 ℃, the volume fraction of hydrogen in the mixed gas is 3-100%, and the reduction time is 0.3-36 hours.
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