CN102133526A - Method for preparing ruthenium carbon catalyst - Google Patents
Method for preparing ruthenium carbon catalyst Download PDFInfo
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- CN102133526A CN102133526A CN2010106138924A CN201010613892A CN102133526A CN 102133526 A CN102133526 A CN 102133526A CN 2010106138924 A CN2010106138924 A CN 2010106138924A CN 201010613892 A CN201010613892 A CN 201010613892A CN 102133526 A CN102133526 A CN 102133526A
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Abstract
The invention discloses a method for preparing a ruthenium carbon catalyst, which comprises the following steps of: mixing soluble ruthenium salt solution and urea uniformly, then adding dry active carbon pretreated by nitric acid to perform impregnation, performing uniform precipitation treatment with heating so that the ruthenium forms a hydroxide and the hydroxide is loaded on the surface of the active carbon, finally adding a reducing agent, performing filtration after thorough reduction, washing the filtrate till no Cl<-> is produced, transferring the filter cakes to a drying oven, and drying the filter cakes to obtain the ruthenium carbon catalyst. By the method for preparing the ruthenium carbon catalyst, the supported nano noble metal ruthenium carbon catalyst with high dispersion can be obtained, the active metal particle size of the catalyst belongs to nano scale, the particle diameter is controllable, the operation is simple, and the method is convenient for industrialization.
Description
Technical field
The invention belongs to catalyst preparation technical field, especially a kind of preparation method of ruthenium Pd/carbon catalyst.
Background technology
The ruthenium Pd/carbon catalyst has good hydrogenation performance; Can activate N2 and H2 molecule at normal temperatures and pressures, be applicable to low-temp low-pressure synthetic ammonia.Simultaneously in aliphatic carbonyl compound and aromatic hydrocarbon ring, hydrogenation under situation more leniently shows high activity and does not have side reaction, and when having water in the reaction system, ruthenium catalyst presents higher activity.Ruthenium catalyst is stablized in acid and basic solvent and can be used in the strong acid reaction.
The technology of preparing of ruthenium Pd/carbon catalyst mainly adopts infusion process, the precipitation method etc.U.S. Pat 6495730B1 has reported that solubility ruthenium trichloride impregnated carrier has prepared the hydrogenation reaction that ruthenium base charcoal carried catalyst is used for carboxylic acid.Chinese patent CN1970143A disclose a kind of solubility ruthenium salt and surfactant are mixed after, be reduced to ruthenium colloidal solution with reducing agent, add carrier then and obtain nano hydrogenation ruthenium Pd/carbon catalyst by the infusion process load.Liu Shouchang etc. have studied the ruthenium Pd/carbon catalyst of immersion process for preparing benzene partial hydrogenation cyclohexene.After Xu Sankui etc. adopt solubility ruthenium trichloride and carrier active carbon mixing stirring and refluxing, regulate PH with NaOH the Ru post precipitation is reduced with formaldehyde, obtain the Ru/C catalyst.All there are certain defective in above-mentioned ruthenium Pd/carbon catalyst preparation method or technology.The basic principle of immersion process for preparing technology, on the one hand be because the hole of solid when contacting with liquid owing to capillary effect produces capillary pressure, make liquid be penetrated into capillary inside; Be the absorption of active component on the other hand at carrier surface.But the final decentralization that is deposited on the metal of catalyst carrier depends on the interaction of many factors, these factors comprise the intensity of dipping method, absorption, the metallic compound that exists with occlusion solute form is than the degree that is adsorbed on the species on the hole wall, and the chemical change of heating generation when dry etc.Therefore, difficult to the control ratio of above-mentioned influence factor, thus cause Metal Distribution difficult by default distribution control, the load capacity of metal is on the low side etc.The precipitation method are a kind of method for preparing catalyst of classical extensive use, and its basic principle is, in containing the solution of metallic salt, add precipitating reagent by metathesis reaction, generate the salt of indissoluble or hydrous metal oxides or gel and are precipitated out from solution.The influence factor of the precipitation method is a lot, mainly contain solution concentration, PH, temperature, feed way, stirring intensity etc., precipitation process is very complicated, the precipitation crystal that generates is reunited easily, thereby cause the size distribution of final metallic inhomogeneous, the precipitation method are contained impurity easily simultaneously, introduce other impurity.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of preparation method of ruthenium Pd/carbon catalyst is provided, this method utilizes a certain chemical reaction to make configurational ion in the solution by slowly discharging equably in the solution, by precipitating reagent concentration in the control solution, guarantee that the precipitation in the solution is in a kind of poised state, thereby separate out uniformly.The present invention can obtain the loaded nano noble ruthenium Pd/carbon catalyst of high degree of dispersion, and not only the preparation method operates easily, controls simply, and cost is low, and industrialization easily realizes.
The objective of the invention is to solve by the following technical programs:
The preparation method of ruthenium Pd/carbon catalyst of the present invention is: earlier solubility ruthenium salting liquid and urea are mixed, add then with the good dry state active carbon of nitric acid pretreatment and flood, again through being heated evenly precipitation process, make ruthenium form hydroxide and load to activated carbon surface, add reducing agent at last, after the reduction thoroughly, filter, washing is not to there being Cl-, filter cake is transferred to oven drying after, obtain described ruthenium Pd/carbon catalyst.
Specifically may further comprise the steps of above method:
1) is to add urea in 0.1～5mol/L solubility ruthenium salting liquid at first, constantly stirs and make its dissolving mixing formation mixed solution to dissolving good concentration in advance; The addition of described urea is 1～10 times of quality of noble ruthenium;
2) select the active carbon of wooden, shell or coconut husk class high-specific surface area for use, adopting concentration is that 15% salpeter solution refluxed 4 hours with 80 ℃, wash then to PH to equal 7,120 ℃ down the oven dry back form described dry state active carbon;
3) above-mentioned dry state active carbon is added in the mixed solution of step 1), and continue to stir dipping 0.1～5 hour,, make ruthenium form hydroxide and load to activated carbon surface afterwards through the homogeneous precipitation of being heated;
4) according to mass ratio, with reducing agent: Ru=1～10: 1 adding reducing agents, the recovery time is 0.5～15 hour, after the reduction thoroughly, filters, and washing leaching cake is to there not being Cl
-, filter cake is transferred to oven drying, baking temperature is 80 ℃.
Above-mentioned solubility ruthenium salt is a kind of or its combination in ruthenium trichloride, nitric acid ruthenium, the acetic acid ruthenium.
More than in preparation process the mode by electrical heating, infrared heating or heating using microwave heat.
Above-mentioned reducing agent is one or more the mixture in formaldehyde, hydrazine hydrate, potassium borohydride, sodium borohydride or the lithium aluminium hydride reduction.
The present invention has following beneficial effect:
Ruthenium Pd/carbon catalyst preparation method provided by the invention can obtain the high loaded nano noble ruthenium Pd/carbon catalyst of decentralization, this activity of such catalysts metal particle size belongs to nanoscale, particle diameter is controlled, and preparation method of the present invention is simple to operate, is convenient to industrialization.
Description of drawings
Fig. 1 is the sem photograph of loaded nano noble ruthenium Pd/carbon catalyst of the present invention.
The specific embodiment
The preparation method of ruthenium Pd/carbon catalyst of the present invention is: earlier solubility ruthenium salting liquid and urea are mixed, add then with the good dry state active carbon of nitric acid pretreatment and flood, again through being heated evenly precipitation process, make ruthenium form hydroxide and load to activated carbon surface, add reducing agent at last, after the reduction thoroughly, filter, washing is to there not being Cl
-, filter cake is transferred to oven drying after, obtain described ruthenium Pd/carbon catalyst.The preliminary treatment of dry state active carbon of the present invention is: it is 15%HNO that the absorbent charcoal carrier of high-specific surface area (wooden, shell or coconut husk class) is joined concentration
380 ℃ of solution refluxed 4 hours, washed then to PH to equal standby after 7,120 ℃ of oven dry.
Specifically describe preparation method of the present invention by the following examples.
Embodiment 1
Is ruthenium with 0.1mol/L ruthenium trichloride solution and urea according to mass ratio: urea=after 1: 6 even mixing, the wood activated charcoal carrier of the high-specific surface area that preliminary treatment is good adds wherein, stirred dipping 0.5 hour, then through 90 ℃ of electrical heating 3 hours, the urea decomposes, form precipitation with ruthenium, be carried on activated carbon surface.Add 10% solution of potassium borohydride then and reduce that (ruthenium: potassium borohydride=1: 5), last filtration washing was to there not being Cl in 1.5 hours
-, filter cake is transferred to 80 ℃ of oven dryings, obtains loaded nano noble ruthenium Pd/carbon catalyst, and the average grain diameter of ruthenium particle is 22.8nm.
Embodiment 2
0.1mol/L ruthenium trichloride solution and urea are evenly mixed (by quality ratio, ruthenium: urea=1: 6), the active fruit shell carbon carrier of the high-specific surface area that preliminary treatment is good adds wherein, stirred dipping 0.5 hour, then through 90 ℃ of electrical heating 3 hours, the urea decomposes forms precipitation with ruthenium, is carried on activated carbon surface.Add 10% sodium borohydride solution then and reduce that (ruthenium by quality ratio: sodium borohydride=1: 8), last filtration washing was to there not being Cl in 1.5 hours
-, filter cake is transferred to 80 ℃ of oven dryings, obtains loaded nano noble ruthenium Pd/carbon catalyst, and the average grain diameter of ruthenium particle is 22.3nm.
Embodiment 3
0.1mol/L ruthenium trichloride solution and urea are evenly mixed (by quality ratio, ruthenium: urea=1: 6), the cocoanut active charcoal carrier of the high-specific surface area that preliminary treatment is good adds wherein, stirred dipping 0.5 hour, then through 90 ℃ of electrical heating 3 hours, the urea decomposes forms precipitation with ruthenium, is carried on activated carbon surface.Add 10% solution of potassium borohydride then and reduce that (ruthenium by quality ratio: potassium borohydride=1: 5), last filtration washing was to there not being Cl in 1.5 hours
-, filter cake is transferred to 80 ℃ of oven dryings, obtains loaded nano noble ruthenium Pd/carbon catalyst, and the average grain diameter of ruthenium particle is 18.8nm.
Embodiment 4
0.5mol/L ruthenium trichloride solution and urea are evenly mixed (by quality ratio, ruthenium: urea=1: 6), the cocoanut active charcoal carrier of the high-specific surface area that preliminary treatment is good adds wherein, stirred dipping 3 hours, heated by microwave is 0.5 hour then, the urea decomposes forms precipitation with ruthenium, is carried on activated carbon surface.Add 10% solution of potassium borohydride then and reduce that (ruthenium by quality ratio: potassium borohydride=1: 5), last filtration washing was to there not being Cl in 1.5 hours
-, filter cake is transferred to 80 ℃ of oven dryings, obtains loaded nano noble ruthenium Pd/carbon catalyst, and the average grain diameter of ruthenium particle is 11.4nm.
Embodiment 5
1.0mol/L ruthenium trichloride solution and urea are evenly mixed (by quality ratio, ruthenium: urea=1: 6), the active fruit shell carbon carrier of the high-specific surface area that preliminary treatment is good adds wherein, stirred dipping 0.5 hour, then by infrared heating 1.5 hours, the urea decomposes forms precipitation with ruthenium, is carried on activated carbon surface.Add 10% solution of potassium borohydride then and reduce that (ruthenium by quality ratio: potassium borohydride=1: 5), last filtration washing was to there not being Cl in 1.5 hours
-, filter cake is transferred to 80 ℃ of oven dryings, obtains loaded nano noble ruthenium Pd/carbon catalyst, and the average grain diameter of ruthenium particle is 32.2nm.
Embodiment 6
0.1mol/L nitric acid ruthenium solution and urea are evenly mixed (by quality ratio, ruthenium: urea=1: 6), the active fruit shell carbon carrier of the high-specific surface area that preliminary treatment is good adds wherein, stirred dipping 0.5 hour, then by heating using microwave 0.5 hour, the urea decomposes forms precipitation with ruthenium, is carried on activated carbon surface.Add 10% solution of potassium borohydride then and reduce that (ruthenium by quality ratio: potassium borohydride=1: 5), last filtration washing was to there not being Cl in 1.5 hours
-, filter cake is transferred to 80 ℃ of oven dryings, obtains loaded nano noble ruthenium Pd/carbon catalyst, and the average grain diameter of ruthenium particle is 13.2nm.
Embodiment 7
0.1mol/L acetic acid ruthenium solution and urea are evenly mixed (by quality ratio, ruthenium: urea=1: 6), the active fruit shell carbon carrier of the high-specific surface area that preliminary treatment is good adds wherein, stirred dipping 0.5 hour, then by heating using microwave 0.5 hour, the urea decomposes forms precipitation with ruthenium, is carried on activated carbon surface.Add 10% solution of potassium borohydride then and reduce that (ruthenium by quality ratio: potassium borohydride=1: 5), last filtration washing was to there not being Cl in 1.5 hours
-, filter cake is transferred to 80 ℃ of oven dryings, obtains loaded nano noble ruthenium Pd/carbon catalyst, and the average grain diameter of ruthenium particle is 9.9nm.
Embodiment 8
0.1mol/L ruthenium trichloride solution and urea are evenly mixed (by quality ratio, ruthenium: urea=1: 9), the active fruit shell carbon carrier of the high-specific surface area that preliminary treatment is good adds wherein, stirred dipping 0.5 hour, then by infrared heating 1.5 hours, the urea decomposes forms precipitation with ruthenium, is carried on activated carbon surface.Add formalin then and reduce that (ruthenium by quality ratio: formaldehyde=1: 5), last filtration washing was to there not being Cl in 5.5 hours
-, filter cake is transferred to 80 ℃ of oven dryings, obtains loaded nano noble ruthenium Pd/carbon catalyst, and the average grain diameter of ruthenium particle is 20.2nm.
Embodiment 9
0.1mol/L ruthenium trichloride solution and urea are evenly mixed (by quality ratio, ruthenium: urea=1: 7), the active fruit shell carbon carrier of the high-specific surface area that preliminary treatment is good adds wherein, stirred dipping 0.5 hour, then by infrared heating 1.5 hours, the urea decomposes forms precipitation with ruthenium, is carried on activated carbon surface.Add hydrazine hydrate solution then and reduce that (ruthenium by quality ratio: hydrazine hydrate=1: 5), last filtration washing was to there not being Cl in 4.5 hours
-, filter cake is transferred to 80 ℃ of oven dryings, obtains loaded nano noble ruthenium Pd/carbon catalyst, and the average grain diameter of ruthenium particle is 17.2nm.
Embodiment 10
1.0mol/L ruthenium trichloride solution and urea are evenly mixed (by quality ratio, ruthenium: urea=1: 8), the active fruit shell carbon carrier of the high-specific surface area that preliminary treatment is good adds wherein, stirred dipping 0.5 hour, then by infrared heating 1.5 hours, the urea decomposes forms precipitation with ruthenium, is carried on activated carbon surface.Adding lithium aluminium hydride reduction then carries out reductase 12 .5 hour (ruthenium by quality ratio: lithium aluminium hydride reduction=1: 4), last filtration washing is to there not being Cl
-, filter cake is transferred to 80 ℃ of oven dryings, obtains loaded nano noble ruthenium Pd/carbon catalyst, and the average grain diameter of ruthenium particle is 32.2nm.
Embodiment 11
Present embodiment carries out according to following steps:
1) at first in dissolving the ruthenium trichloride solution that good concentration is 5mol/L in advance, adds urea, constantly stir and make its dissolving mixing formation mixed solution; The addition of described urea is that 10 times of quality of noble ruthenium (are urea: ruthenium=1～10);
2) select the active carbon of coconut husk class high-specific surface area for use, adopting concentration is that 15% salpeter solution refluxed 4 hours with 80 ℃, washs then to PH to equal 7, at 120 ℃ of dry state active carbons of forming of oven dry back down;
3) above-mentioned dry state active carbon is added in the mixed solution of step 1), and continue to stir dipping 5 hours,, make ruthenium form hydroxide and load to activated carbon surface afterwards through the homogeneous precipitation of being heated;
4) according to mass ratio, add reducing agent with reducing agent: Ru=1～10: 1, reducing agent is selected hydrazine hydrate for use, the recovery time is 0.5～15 hour, make its reduction thoroughly after, filter, washing leaching cake is to there not being Cl
-, filter cake is transferred to oven drying, baking temperature is 80 ℃.
Embodiment 12
Present embodiment carries out according to following steps:
1) is to add urea in the 1mol/L solubility ruthenium salting liquid at first, constantly stirs and make its dissolving mixing formation mixed solution to dissolving good concentration in advance; The addition of described urea is that 8 times of quality of noble ruthenium (are urea: ruthenium=1～8); Wherein solubility ruthenium salt is selected ruthenium trichloride.
2) select the active carbon of wooden class high-specific surface area for use, adopting concentration is that 15% salpeter solution refluxed 4 hours with 80 ℃, wash then to PH to equal 7,120 ℃ down the oven dry back form described dry state active carbon;
3) above-mentioned dry state active carbon is added in the mixed solution of step 1), and continue to stir dipping 0.1～5 hour,, make ruthenium form hydroxide and load to activated carbon surface afterwards through the homogeneous precipitation of being heated;
4) according to mass ratio, add reducing agent with reducing agent: Ru=1～1, the recovery time is 10 hours, after the reduction thoroughly, filters, washing leaching cake is to there not being Cl
-, filter cake is transferred to oven drying, baking temperature is 80 ℃.Described reducing agent select formaldehyde and hydrazine hydrate arbitrarily than mixture.
Embodiment 12
Present embodiment carries out according to following steps:
1) is to add urea in the 3mol/L solubility ruthenium salting liquid at first, constantly stirs and make its dissolving mixing formation mixed solution to dissolving good concentration in advance; The addition of described urea is that 3 times of quality of noble ruthenium (are urea: ruthenium=1～3); Wherein solubility ruthenium salt is selected the acetic acid ruthenium.
2) select the active carbon of wooden, shell or coconut husk class high-specific surface area for use, adopting concentration is that 15% salpeter solution refluxed 4 hours with 80 ℃, wash then to PH to equal 7,120 ℃ down the oven dry back form described dry state active carbon;
3) above-mentioned dry state active carbon is added in the mixed solution of step 1), and continue to stir dipping 5 hours,, make ruthenium form hydroxide and load to activated carbon surface afterwards through the homogeneous precipitation of being heated;
4) according to mass ratio, with reducing agent: Ru=9: 1 adds reducing agent, and the recovery time is 3 hours, after the reduction thoroughly, filters, and washing leaching cake is to there not being Cl
-, filter cake is transferred to oven drying, baking temperature is 80 ℃.Described reducing agent is a lithium aluminium hydride reduction.
Embodiment 13
Present embodiment carries out according to following steps:
1) is to add urea in the 0.1mol/L solubility ruthenium salting liquid at first, constantly stirs and make its dissolving mixing formation mixed solution to dissolving good concentration in advance; The addition of described urea is that 4 times of quality of noble ruthenium (are urea: ruthenium=1～4); Wherein solubility ruthenium salt is any than combination of ruthenium trichloride and acetic acid ruthenium.
2) select the active carbon of shell class high-specific surface area for use, adopting concentration is that 15% salpeter solution refluxed 4 hours with 80 ℃, wash then to PH to equal 7,120 ℃ down the oven dry back form described dry state active carbon;
3) above-mentioned dry state active carbon is added in the mixed solution of step 1), and continue to stir dipping 2 hours,, make ruthenium form hydroxide and load to activated carbon surface afterwards through the homogeneous precipitation of being heated;
4) according to mass ratio, with reducing agent: Ru=2: 1 adds reducing agent, and the recovery time is 2 hours, after the reduction thoroughly, filters, and washing leaching cake is to there not being Cl
-, filter cake is transferred to oven drying, baking temperature is 80 ℃.Wherein reducing agent is selected sodium borohydride for use.
The sem photograph of the loaded nano noble ruthenium Pd/carbon catalyst that the present invention is prepared as shown in Figure 1, this activity of such catalysts metal particle size belongs to nanoscale as can be seen, and the active metal particles size is even.
Claims (5)
1. the preparation method of a ruthenium Pd/carbon catalyst, it is characterized in that, earlier solubility ruthenium salting liquid and urea are mixed, add then with the good dry state active carbon of nitric acid pretreatment and flood, again through being heated evenly precipitation process, make ruthenium form hydroxide and load to activated carbon surface, add reducing agent at last, after the reduction thoroughly, filter, washing is not to there being Cl-, filter cake is transferred to oven drying after, obtain described ruthenium Pd/carbon catalyst.
2. the preparation method of ruthenium Pd/carbon catalyst according to claim 1 is characterized in that, specifically may further comprise the steps:
1) is to add urea in 0.1～5mol/L solubility ruthenium salting liquid at first, constantly stirs and make its dissolving mixing formation mixed solution to dissolving good concentration in advance; The addition of described urea is 1～10 times of quality of noble ruthenium;
2) select the active carbon of wooden, shell or coconut husk class high-specific surface area for use, adopting concentration is that 15% salpeter solution refluxed 4 hours with 80 ℃, wash then to PH to equal 7,120 ℃ down the oven dry back form described dry state active carbon;
3) above-mentioned dry state active carbon is added in the mixed solution of step 1), and continue to stir dipping 0.1～5 hour,, make ruthenium form hydroxide and load to activated carbon surface afterwards through the homogeneous precipitation of being heated;
4) according to mass ratio, with reducing agent: Ru=1～10: 1 adding reducing agents, the recovery time is 0.5～15 hour, after the reduction thoroughly, filters, and washing leaching cake is to there not being Cl
-, filter cake is transferred to oven drying, baking temperature is 80 ℃.
3. the preparation method of ruthenium Pd/carbon catalyst as claimed in claim 1 or 2 is characterized in that described solubility ruthenium salt is a kind of or its combination in ruthenium trichloride, nitric acid ruthenium, the acetic acid ruthenium.
4. the preparation method of ruthenium Pd/carbon catalyst as claimed in claim 1 or 2 is characterized in that the mode by electrical heating, infrared heating or heating using microwave in the preparation process heats.
5. the preparation method of ruthenium Pd/carbon catalyst as claimed in claim 1 or 2 is characterized in that, described reducing agent is one or more the mixture in formaldehyde, hydrazine hydrate, potassium borohydride, sodium borohydride or the lithium aluminium hydride reduction.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103447083A (en) * | 2012-05-31 | 2013-12-18 | 冯良荣 | Catalyst for acetylene-method synthesis of vinyl acetate and preparation method thereof |
| CN108160072A (en) * | 2016-12-07 | 2018-06-15 | 中国科学院大连化学物理研究所 | A kind of magnesia for preparing hydrogen by ammonia decomposition carries ruthenium catalyst and its preparation and application |
| CN108405881A (en) * | 2018-02-02 | 2018-08-17 | 贵研铂业股份有限公司 | A kind of preparation method of high pure spherical ruthenium powder |
| CN112371192A (en) * | 2021-01-14 | 2021-02-19 | 江苏欣诺科催化剂有限公司 | Composite ruthenium catalyst and preparation method and application thereof |
| CN112678939A (en) * | 2019-10-17 | 2021-04-20 | 中国科学院大连化学物理研究所 | Method for removing hydrazine nitrate and hydroxylamine nitrate in nitric acid |
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| CN101502798A (en) * | 2008-12-30 | 2009-08-12 | 西安凯立化工有限公司 | Nano ruthenium carbon-supported metal hydrogenating catalyst and method for producing the same |
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| CN101502798A (en) * | 2008-12-30 | 2009-08-12 | 西安凯立化工有限公司 | Nano ruthenium carbon-supported metal hydrogenating catalyst and method for producing the same |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103447083A (en) * | 2012-05-31 | 2013-12-18 | 冯良荣 | Catalyst for acetylene-method synthesis of vinyl acetate and preparation method thereof |
| CN108160072A (en) * | 2016-12-07 | 2018-06-15 | 中国科学院大连化学物理研究所 | A kind of magnesia for preparing hydrogen by ammonia decomposition carries ruthenium catalyst and its preparation and application |
| CN108405881A (en) * | 2018-02-02 | 2018-08-17 | 贵研铂业股份有限公司 | A kind of preparation method of high pure spherical ruthenium powder |
| CN112678939A (en) * | 2019-10-17 | 2021-04-20 | 中国科学院大连化学物理研究所 | Method for removing hydrazine nitrate and hydroxylamine nitrate in nitric acid |
| CN112678939B (en) * | 2019-10-17 | 2021-12-14 | 中国科学院大连化学物理研究所 | Method for removing hydrazine nitrate and hydroxylamine nitrate in nitric acid |
| CN112371192A (en) * | 2021-01-14 | 2021-02-19 | 江苏欣诺科催化剂有限公司 | Composite ruthenium catalyst and preparation method and application thereof |
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Application publication date: 20110727 |