CN105772024A - Iron and ruthenium compounded ammonia synthesis catalyst and preparation method thereof - Google Patents
Iron and ruthenium compounded ammonia synthesis catalyst and preparation method thereof Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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Abstract
The invention discloses an iron and ruthenium compounded ammonia synthesis catalyst formed by an iron catalyst loaded with metal ruthenium and a preparation of the iron and ruthenium compounded ammonia synthesis catalyst.According to the catalyst, the metal ruthenium serves as an active component, the iron-based catalyst serves as a carrier, and/or one or more of alkali metal, alkaline-earth metal and transition elements form auxiliary catalysts.An adding method of the active component metal ruthenium comprises the steps of mechanically mixing a ruthenium precursor according to a certain proportion, conducting gas phase precipitation and liquid phase immersion, and conducting pyrolysis treatment in air, nitrogen and vacuum, wherein the auxiliary catalysts can be melted to iron oxide before ruthenium is loaded or loaded with the ruthenium precursor at the same time.The iron and ruthenium compounded ammonia synthesis catalyst has the advantages of being simple in equipment procedure, short in preparation cycle and low in energy consumption and having high activity of a ruthenium catalyst and high stability of an iron catalyst and the like.
Description
Technical field
The invention belongs to catalyst technical field, be specifically related to a kind of ferrum ruthenium compound ammonia synthesis catalyst and preparation method thereof.
Background technology
The existing century-old developing history of ammonia synthesis catalyst, the Continual Improvement of catalyst is always up one of ammonia synthesizing industry critical path reducing energy consumption.
Traditional industrial ammonia synthesis catalyst is with Fe3O4The fused iron catalyst that (magnetic iron ore) is parent.Experienced by the development in a nearly century, highly developed, activity to improve again 0.5 percentage point also very difficult.1986, patent CN1091997A disclosed a kind of with Fe1-xO(wustite) for the new system catalyst of parent.Fe1-xO ammonia synthesis catalyst has extra high activity, especially easy reduction, active temperature low especially, high mechanical strength and applicable H2/N2The features such as wide ranges and service life (up to more than 10 years), are current a new generation the highest, state-of-the-art of activity in the world fused iron catalysts.
1972, activity higher [JournalofCatalysis, 1972,27 (3): 424 431] when the ruthenium catalyst that Japanese scholars Ozaki etc. finds is with activated carbon for carrier.1992, BP company of Britain cooperated with Kellogg company of the U.S., succeed in developing with the activated carbon of graphitization high-specific surface area be carrier, with Ru3(CO)12Ruthenium catalyst for parent.This catalyst has high activity, can operate under low temperature, low-pressure.But, Carbon supports in activated carbon for the ruthenium catalyst of carrier is easy and hydrogen reaction generation methane under ammonia synthesis reaction (facing hydrogen) condition, under the catalytic action of ruthenium, cause its carrier unstable, and constantly run off along with the carrying out of methanation reaction, thus having a strong impact on its service life, and ruthenium natural resources shortage, expensive.These all have a strong impact on the use of ruthenium catalyst, and cause that its commercial Application is very limited [AppliedCatalysisA:General.208 (2001) 271].
For this, patent CN102744060A adopts BaTiO3, patent CN1390637A adopts Al2O3And patent CN101053835A to adopt oxide to substitute activated carbon be the methanation problem that carrier carrys out resolved vector, but catalyst activity is well below the catalyst being carrier with activated carbon.Patent CN1382527A and US4600571 finds activated carbon is performed for more than 1900oThe noble gas high-temperature process of C can form graphitization activated carbon and improve vector stabilisation to a certain extent.But, after high-temperature process, activated carbon surface is long-pending sharply declines, thus need to by aoxidizing reaming raising surface area.This destroys graphite-structure again and causes carrier easily by methanation to a certain extent.
Accordingly, because active component ruthenium inherently carbon hydrogenation generates the excellent catalyst of methane, so the methanation of ruthenium catalyst is difficult to avoid that.This is a fatal weakness of ruthenium catalyst, is the difficult problem that must pull against.
Obviously, iron catalyst is stable and activity lower than ruthenium catalyst, and ruthenium catalyst activity is high and stability not as iron catalyst.Ferrum ruthenium double activated component compound ammonia synthesis catalyst that it is an object of the invention to provide a kind of high activity and high stability and preparation method thereof.
Summary of the invention
The present invention utilizes ferrum and the respective advantage of ruthenium catalyst, unstable high-area carbon is substituted as carrier using the iron catalyst that stability is high, highly active active component ruthenium is carried on iron catalyst, prepares the double activated component compound ammonia synthesis catalyst of high activity and high stability.Catalyst of the present invention is with metal Ru for active component, and with iron based ammonia synthesis catalyst for carrier, with alkali metal, alkaline-earth metal and one or more in transition elements are promoter.Catalyst preparation process process of the present invention is simple, has the high stability of iron catalyst and the high activity of ruthenium catalyst concurrently, has prospects for commercial application widely at ammonia synthesizing industry and preparing hydrogen by ammonia decomposition industrial circle.
Described a kind of ferrum ruthenium compound ammonia synthesis catalyst, it is characterised in that being obtained on iron catalyst carrier by metal Ru load, described metal Ru load capacity is 0.1-5wt%, it is preferable that 0.1-3wt%.
Described a kind of ferrum ruthenium compound ammonia synthesis catalyst, it is characterised in that described iron catalyst carrier includes the molten mixture of ferroso-ferric oxide base ammonia synthetic catalyst, ferrous oxide catalyst for amino synthesis and iron oxides, wherein:
(1) Fe3O4Base ammonia synthetic catalyst is by major constituent Fe3O4With promoter Al2O3、K2O, CaO, MgO etc. form, and the present invention adopts the dead catalyst or freshly prepd catalyst that commercial product (such as A110 catalyst series) or industrial application cross；
(2) Fe1-xO base ammonia synthetic catalyst is by major constituent Fe1-xO and promoter Al2O3、K2O、CaO、MgO、V2O5Deng composition, the present invention adopts the dead catalyst or freshly prepd catalyst that commercial product (such as A301, ZA-5, AmoMX-10 type catalyst) or industrial application cross；
(3) molten mixture of iron oxides is by Fe2O3With or Fe3O4With or FeO and mixture composition, adopt fusion method prepare.
Described a kind of ferrum ruthenium compound ammonia synthesis catalyst, it is characterised in that the lead compound of described metal Ru is Ru3(CO)12、Ru(C5H7O2)3Or K2RuO4, it is preferable that Ru3(CO)12Or Ru (C5H7O2)3。
Described a kind of ferrum ruthenium compound ammonia synthesis catalyst, characterized by further comprising promoter, the mol ratio of described promoter and metal Ru is 0～16:1, it is preferably 0.2～5:1, described promoter is one or more in alkali metal, alkaline-earth metal and transition metal, and the lead compound of described promoter is the oxide of each metal, hydroxide, nitrate or carbonate.
Described a kind of ferrum ruthenium compound ammonia synthesis catalyst, it is characterised in that described alkali metal includes sodium, potassium, rubidium and caesium；Alkaline-earth metal includes calcium, magnesium and barium；Transition metal includes vanadium, titanium and zirconium.
The preparation method of described a kind of ferrum ruthenium compound ammonia synthesis catalyst, it is characterised in that specifically include following steps:
1) load of active component ruthenium precursor compound is on iron catalyst carrier, the product ferrum ruthenium compound ammonia synthesis catalyst presoma obtained；
2) the active component ruthenium precursor compound in ferrum ruthenium compound ammonia synthesis catalyst presoma is decomposed into metal Ru, and load is on iron catalyst carrier, prepare the ferrum ruthenium compound ammonia synthesis catalyst of ruthenium dispersion height, good stability.
The preparation method of described a kind of ferrum ruthenium compound ammonia synthesis catalyst, it is characterized in that interpolation promoter in step 1), the mol ratio of described promoter and metal Ru is 0～16:1, it is preferably 0.2～5:1, described promoter is one or more in alkali metal, alkaline-earth metal and transition metal, the lead compound of described promoter is the oxide of each metal, hydroxide, nitrate or carbonate, it is preferred to described alkali metal includes sodium, potassium, rubidium and caesium；Alkaline-earth metal includes calcium, magnesium and barium；Transition metal includes vanadium, titanium and zirconium.
The preparation method of described a kind of ferrum ruthenium compound ammonia synthesis catalyst, it is characterized in that in described step 1), the precursor compound load of active component ruthenium adopts mechanical mixing, vapour deposition process or liquid-phase impregnation process on iron catalyst carrier, it is preferred to use mechanical mixing and vapour deposition process.
The preparation method of described a kind of ferrum ruthenium compound ammonia synthesis catalyst, it is characterised in that described mechanical mixing includes the mechanical mixer mixing of ball milling, grinding, stirring, pneumatic stirring or industrial advanced person；Described vapour deposition process includes chemical vapour deposition (CVD), physical vapour deposition (PVD) or plasma gas phase deposition；Described liquid-phase impregnation process includes equi-volume impregnating, excessive infusion process, multiple maceration, dipper precipitation method, or in liquid-phase system, utilizes reducing agent reduction ruthenium ion preparation nanometer ruthenium granule, impregnated on iron catalyst carrier again through above-mentioned dipping method.
The preparation method of described a kind of ferrum ruthenium compound ammonia synthesis catalyst, it is characterized in that described step 2) in adopt heat treating process the active component ruthenium precursor compound in ferrum ruthenium compound ammonia synthesis catalyst presoma is decomposed into metal Ru, and load is on iron catalyst carrier, described pyrolysis processing is specially active component ruthenium precursor compound in vacuum, air, pyrolysis is carried out under nitrogen or hydrogen atmosphere, it is made to be decomposed into zero-valent metal ruthenium, and load is on carrier, reaction condition is temperature 100～500 DEG C, pressure 0.01～5MPa, 0.5～24 hour response time, it is preferably temperature 100～200 DEG C, pressure 0.01～1MPa.
The catalyst of the present invention can apply in fields such as ammonia synthesizing industry and preparing hydrogen by ammonia decomposition industry, and the preparation technology of the present invention is simple, and equipment requirements is low, and the time is shorter, it does not have waste liquid produces, and more meets environmental requirement, has good prospects for commercial application.
Accompanying drawing explanation
Fig. 1 be before ruthenium load (left side) afterwards (in) and reaction after (right side) catalyst SEM image.
Detailed description of the invention
Below in conjunction with being embodied as example, the present invention is described further, but protection scope of the present invention is not limited except as.
Embodiment 1
KNO is weighed respectively with analytical balance313.1g, BaCO32.6g, Al2O318.1g, CaCO332.0g, MgO7.5g, iron powder 232g, selected magnetite powder 704g, these materials are put in mortar be fully ground, mix homogeneously, be subsequently placed in electric smelter melted, after the cooled solidification of fused mass, namely obtain Fe1-xO is catalyst based, through Fe broken, that screening obtains 14-18 order granularity1-xO based catalyst carrier.Weigh this ferrum-based catalyst carrier 8.0g, Ru respectively3(CO)12The load capacity of 0.0337g(ruthenium is 0.2wt), then load in blender together, after mix homogeneously, be loaded in sublimation apparatus, pressure is maintained at-0.1MPa by evacuation, then heats up, and distil 5h at 140 DEG C, is namely able to Fe1-xThe catalyst based composite catalyst for carrier of O.Then catalyst is at 150 DEG C of air atmospheres, and 0.05MPa processes 4h, obtains ferrum ruthenium composite catalyst.
Before and after this catalyst load and reacted scanning electron microscope (SEM) photograph, as shown in Figure 1.
Embodiment 2
Repeat embodiment 1 process, the load capacity of original ruthenium is become 1.0%.Weigh this with Fe1-xThe catalyst based composite catalyst presoma 8.0g for carrier of O, is then loaded in sublimation apparatus, and sublimation apparatus pressure is maintained at-0.1MPa by evacuation, then heats up, and distil 5h at 140 DEG C, is namely able to Fe1-xThe catalyst based composite catalyst for carrier of O.Then catalyst is at 200 DEG C of nitrogen atmospheres, and 0.1MPa processes 4h, obtains ferrum ruthenium composite catalyst.
Embodiment 3
KNO is weighed respectively with analytical balance313.1g, BaCO32.6g, Al2O318.1g, CaCO332.0g, MgO7.5g, iron powder 23g, selected magnetite powder 940g.Then these materials are put in mortar be fully ground, mix homogeneously, place in electric smelter and melt together, after the cooled solidification of fused mass, namely obtain Fe3O4Catalyst based, through carrier broken, that screening obtains 14-18 order granularity, weigh this carrier 8.0g, Ru3(CO)12The load capacity of 0.1281g(ruthenium is 0.76wt), then load in blender together, obtain with Fe after mix homogeneously3O4The catalyst based composite catalyst presoma for carrier.Then catalyst is at 400 DEG C of air atmospheres, and 0.06MPa processes 8h, obtains ferrum ruthenium composite catalyst.
Embodiment 4
Iron powder 78.3g, selected magnetite powder 921.7g is weighed respectively with analytical balance.Then these materials are put in mortar be fully ground, mix homogeneously, place in electric smelter and melt together, namely obtain by 47.3%Fe after the cooled solidification of fused mass2O3, 46.4%FeO composition molten mixture, through carrier broken, that screening obtains 14-18 order granularity, weigh this carrier 8.0g, Ru3(CO)12The load capacity of 0.2696g(ruthenium is 1.6wt), then load in blender together, after mix homogeneously, obtain the composite catalyst being carrier with the molten mixture of iron oxides.Then catalyst processes 6h at 250 DEG C of vacuum atmospheres, obtains ferrum ruthenium composite catalyst.
Embodiment 5
Business Fe is weighed with analytical balance1-xO base ammonia synthetic catalyst (A301 or ZA-5 or AmoMX-10 type) 8.0g, Ru3(CO)12The load capacity of 0.4381g(ruthenium is 2.6wt), load evacuation in sublimation apparatus after mix homogeneously so that it is pressure is maintained at-0.1MPa, then heat to constant temperature distillation 5h at 140 DEG C, be namely able to business Fe1-xO base ammonia synthetic catalyst is the composite catalyst of carrier.
Embodiment 6
Repeat embodiment 1, prepare Fe1-xO is catalyst based.Weigh Fe respectively1-xO based catalyst carrier 8.0g, Ru3(CO)12The load capacity of 0.2022g(ruthenium is 1.2wt), KNO30.056g or CsNO30.066g, then loads in blender together, obtains with Fe after mix homogeneously1-xO is catalyst based for carrier, the composite catalyst presoma adding promoter K or Cs.Then, again under 120 DEG C of nitrogen atmospheres, 1MPa processes 4h, obtains ferrum ruthenium composite catalyst.
Embodiment 7
Repeat embodiment 1, prepare Fe1-xO is catalyst based.Weigh Fe respectively1-xO based catalyst carrier 8.0g, Ru (C5H7O2)3The load capacity of 0.0630g(ruthenium is 0.2wt), Ba (NO3)20.024g, then loads in blender together, obtains with Fe after mix homogeneously1-xO is catalyst based for carrier, the composite catalyst presoma adding cocatalyst B a.Then 120 DEG C of nitrogen atmospheres again, process 1h, obtain ferrum ruthenium composite catalyst under 0.1MPa.
Embodiment 8
Repeat embodiment 1, prepare Fe1-xO is catalyst based.Weigh Fe respectively1-xO based catalyst carrier 8.0g, Ru (C5H7O2)3The load capacity of 0.0630g(ruthenium is 0.2wt), Ba (NO3)20.024g、KNO30.056g, then loads in blender together, obtains with Fe after mix homogeneously1-xO is catalyst based for carrier, the composite catalyst presoma adding promoter K and Ba.Then 120 DEG C of nitrogen atmospheres again, process 0.5h, obtain ferrum ruthenium composite catalyst under 0.1MPa.
Embodiment 9
Repeat embodiment 1, prepare Fe1-xO is catalyst based.Weigh Fe respectively1-xO based catalyst carrier 8.0g, Ba (NO3)20.024g and KNO30.056g.Then the material weighed up is loaded in agitating device.The iron catalyst after adding promoter is obtained after mix homogeneously.Then Ru is weighed again3(CO)12The load capacity of 0.1687g(ruthenium is 1).Then the iron catalyst after the ruthenium weighed and interpolation auxiliary agent is loaded in sublimation apparatus.Evacuation, is maintained at-0.1MPa by sublimation apparatus pressure.Then heating up, at 140 DEG C, distil under-0.1MPa 5h, obtains catalyst.
Embodiment 10
Repeat embodiment 1, prepare Fe1-xO is catalyst based.Measure 100mL ethylene glycol solution to add in there-necked flask, then weigh sodium acetate 0.3g, ruthenium trichloride 0.1581g respectively, add together in there-necked flask after having claimed, then start to warm up, 150 DEG C of isothermal reactions 30 minutes in whipping process.After reaction, solution centrifugal 15min when 8000r/min obtains Ru-NPs, after centrifugal by its ultrasonic dissolution in dehydrated alcohol, is subsequently adding 0.05gBa (NO3)2, after stirring, add 2mL ammonia.Then ultrasonic disperse, adds 8gFe1-xO based catalyst carrier.Use dehydrated alcohol quick wash after dipping 3h, then dry 3h in an oven at 100 DEG C, obtain composite catalyst after drying.
Embodiment 11
Catalyst activity evaluation carries out in high pressure activating test device.Reactor is the fixing bed of internal diameter 14mm.Catalyst granules is 1.0-1.4mm, and stacking volume is 2ml, and Catalyst packing is in the isothermal region of reactor.Reaction gas is the hydrogen nitrogen mixed gas that H-N ratio is 3:1 that ammonia pyrolytic obtains.Before reaction, catalyst is at 5MPa, 30000h-1,H2/N2In the gaseous mixture of=3, temperature is 400 DEG C, 425 DEG C, reduces 4h, 8h, 8h and 4h at 450 DEG C and 475 DEG C respectively.After reduction terminates, at 10MPa, 10000h-1And 375 DEG C, 400 DEG C and respectively assaying reaction device outlet ammonia density under 425 DEG C of conditions.The measurement result of the various embodiments described above is as shown in table 1.
The ammonia synthesis reaction activity of table 1 embodiment
As shown in Table 1, the catalyst of the present invention has high ammonia synthesis reaction activity.Finding with the Patent Reference that other iron oxides are carrier, in patent CN102921413A and CN102744060A, catalyst contrasts under the same conditions, and during their catalyst 425 DEG C, the active best result of catalyst is not 15.8% and 7.42%.Significantly improved by the activity of catalyst of the present invention.
Claims (10)
1. a ferrum ruthenium compound ammonia synthesis catalyst, it is characterised in that being obtained on iron catalyst carrier by metal Ru load, described metal Ru load capacity is 0.1-5wt%, it is preferable that 0.1-3wt%.
2. a kind of ferrum ruthenium compound ammonia synthesis catalyst as claimed in claim 1, it is characterised in that described iron catalyst carrier includes the molten mixture of ferroso-ferric oxide base ammonia synthetic catalyst, ferrous oxide catalyst for amino synthesis and iron oxides.
3. a kind of ferrum ruthenium compound ammonia synthesis catalyst as claimed in claim 1, it is characterised in that the lead compound of described metal Ru is Ru3(CO)12、Ru(C5H7O2)3Or K2RuO4, it is preferable that Ru3(CO)12Or Ru (C5H7O2)3。
4. a kind of ferrum ruthenium compound ammonia synthesis catalyst as claimed in claim 1, characterized by further comprising promoter, the mol ratio of described promoter and metal Ru is 0～16:1, it is preferably 0.2～5:1, described promoter is one or more in alkali metal, alkaline-earth metal and transition metal, and the lead compound of described promoter is the oxide of each metal, hydroxide, nitrate or carbonate.
5. a kind of ferrum ruthenium compound ammonia synthesis catalyst as claimed in claim 4, it is characterised in that described alkali metal includes sodium, potassium, rubidium and caesium；Alkaline-earth metal includes calcium, magnesium and barium；Transition metal includes vanadium, titanium and zirconium.
6. the preparation method of a kind of ferrum ruthenium compound ammonia synthesis catalyst as described in claim 1,2 or 3, it is characterised in that specifically include following steps:
1) load of active component ruthenium precursor compound is on iron catalyst carrier, the product ferrum ruthenium compound ammonia synthesis catalyst presoma obtained；
2) the active component ruthenium precursor compound in ferrum ruthenium compound ammonia synthesis catalyst presoma is decomposed into metal Ru, and load is on iron catalyst carrier, prepare the ferrum ruthenium compound ammonia synthesis catalyst of ruthenium dispersion height, good stability.
7. the preparation method of a kind of ferrum ruthenium compound ammonia synthesis catalyst as claimed in claim 6, it is characterized in that interpolation promoter in described step 1), the mol ratio of described promoter and metal Ru is 0～16:1, it is preferably 0.2～5:1, described promoter is one or more in alkali metal, alkaline-earth metal and transition metal, the lead compound of described promoter is the oxide of each metal, hydroxide, nitrate or carbonate, it is preferred to described alkali metal includes sodium, potassium, rubidium and caesium；Alkaline-earth metal includes calcium, magnesium and barium；Transition metal includes vanadium, titanium and zirconium.
8. the preparation method of a kind of ferrum ruthenium compound ammonia synthesis catalyst as claimed in claim 6, it is characterized in that in described step 1), the precursor compound load of active component ruthenium adopts mechanical mixing, vapour deposition process or liquid-phase impregnation process on iron catalyst carrier, it is preferred to use mechanical mixing and vapour deposition process.
9. the preparation method of a kind of ferrum ruthenium compound ammonia synthesis catalyst as claimed in claim 8, it is characterised in that described mechanical mixing includes the mechanical mixer mixing of ball milling, grinding, stirring, pneumatic stirring or industrial advanced person；Described vapour deposition process includes chemical vapour deposition (CVD), physical vapour deposition (PVD) or plasma gas phase deposition；Described liquid-phase impregnation process includes equi-volume impregnating, excessive infusion process, multiple maceration, dipper precipitation method, or in liquid-phase system, utilizes reducing agent reduction ruthenium ion preparation nanometer ruthenium granule, impregnated on iron catalyst carrier again through above-mentioned dipping method.
10. the preparation method of a kind of ferrum ruthenium compound ammonia synthesis catalyst as claimed in claim 6, it is characterized in that described step 2) in adopt heat treating process the active component ruthenium precursor compound in ferrum ruthenium compound ammonia synthesis catalyst presoma is decomposed into metal Ru, and load is on iron catalyst carrier, described pyrolysis processing is specially active component ruthenium precursor compound in vacuum, air, pyrolysis is carried out under nitrogen or hydrogen atmosphere, it is made to be decomposed into zero-valent metal ruthenium, and load is on carrier, reaction condition is temperature 100～500 DEG C, pressure 0.01～5MPa, 0.5～24 hour response time, it is preferably temperature 100～200 DEG C, pressure 0.01～1MPa.
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| CN106799232A (en) * | 2016-12-15 | 2017-06-06 | 浙江工业大学 | Iron based ammonia synthesis catalyst of Nanoscale Iron modification prepared by a kind of solid state chemical reaction and its preparation method and application |
| CN108435179A (en) * | 2018-05-04 | 2018-08-24 | 山东师范大学 | A kind of preparation method of the monatomic ammonia synthesis catalyst of double activated |
| CN110280268A (en) * | 2019-07-03 | 2019-09-27 | 北京氦舶科技有限责任公司 | A kind of synthetic ammonia catalyst and preparation method thereof |
| CN112007641A (en) * | 2020-07-20 | 2020-12-01 | 浙江工业大学 | High-dispersion Ru/ABOxSupported catalyst and preparation method and application thereof |
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| CN106799232A (en) * | 2016-12-15 | 2017-06-06 | 浙江工业大学 | Iron based ammonia synthesis catalyst of Nanoscale Iron modification prepared by a kind of solid state chemical reaction and its preparation method and application |
| CN106799232B (en) * | 2016-12-15 | 2019-08-06 | 浙江工业大学 | A kind of iron based ammonia synthesis catalyst and its preparation method and application of the Nanoscale Iron modification of solid state chemical reaction preparation |
| CN108435179A (en) * | 2018-05-04 | 2018-08-24 | 山东师范大学 | A kind of preparation method of the monatomic ammonia synthesis catalyst of double activated |
| CN108435179B (en) * | 2018-05-04 | 2020-11-20 | 山东师范大学 | Preparation method of double-activity monatomic ammonia synthesis catalyst |
| CN110280268A (en) * | 2019-07-03 | 2019-09-27 | 北京氦舶科技有限责任公司 | A kind of synthetic ammonia catalyst and preparation method thereof |
| CN112007641A (en) * | 2020-07-20 | 2020-12-01 | 浙江工业大学 | High-dispersion Ru/ABOxSupported catalyst and preparation method and application thereof |
| CN112007641B (en) * | 2020-07-20 | 2023-05-16 | 浙江工业大学 | Highly dispersed Ru/ABO x Supported catalyst and preparation method and application thereof |
| CN115999550A (en) * | 2023-01-06 | 2023-04-25 | 浙江大学 | Porous ammonia synthesis catalyst and preparation method and application thereof |
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