CN103599788A - Cobalt-based catalyst for CO hydrogenation and preparation method and application thereof - Google Patents
Cobalt-based catalyst for CO hydrogenation and preparation method and application thereof Download PDFInfo
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Abstract
The Invention discloses a cobalt-based catalyst for CO hydrogenation, the catalyst comprises a composite metal oxide with a perovskite structure and a metal additive, the constitutional formula of the composite metal oxide with the perovskite structure is ABO3-y, wherein A is rare-earth metal, B is transition metals at least including cobalt, the mol ratio of the cobalt to other transition metals is not lower than 3:1, and preferably not lower than 4:1, y is the mol number of oxygen vacancies existing in the composite oxide; by weigh of the catalyst, the content of the additive metal elementary substance is 1 - 15%, and preferably 5%-10%. The catalyst can improve the ratio of diesel fraction in liquid hydrocarbon products, and reduce the selectivity of methane.
Description
Technical field
The present invention relates to a kind of cobalt-base catalyst for CO hydrogenation and its preparation method and application, relate in particular to and a kind ofly take synthesis gas as raw material, prepare CO hydrogenation Co based Fischer-Tropsch synthesis catalyst that carbon atom distributes concentrated and its preparation method and application.
Background technology
Liquid fuel is the blood that modern society relies and turns round, and it is mainly produced by crude refining, processing.In recent years, owing to the worry of crude supply prospect having been caused to liquid fuel price continuous rise, a large amount of uses of liquid fuel simultaneously have also brought serious problem of environmental pollution, and setting up continuable clean fuel liquid production method is the effective means that solves above-mentioned two problems.Fischer-tropsch synthesis process refers to coal, natural gas, living beings etc. is first converted into synthesis gas (CO and H containing carbon resource
2mixture), then synthesis gas is polymerized on catalyst to the process of gaseous state, liquid state and solid hydrocarbons, synthesis gas polymerization process is below called as Fischer-Tropsch synthesis (Fischer-Tropsch Synthesis).The liquid hydrocarbon of the synthetic preparation of Fischer-Tropsch, after hydrogenation upgrading, has the identical character of liquid fuel of producing with petroleum refining.Due to the known reserves of coal, the natural gas reserves of verifying much larger than oil, living beings are a kind of reproducible resources, therefore fischer-tropsch synthesis process can be within the longer time for society provides the sufficient liquid fuel that gasoline and diesel oil etc. are representative of take, be the technology of desirable production petroleum replacing fuel.
Fischer-tropsch reaction carries out on catalyst, and the catalyst (high activity, high selectivity, high stability) with excellent properties is the technical guarantee that realizes efficient fischer-tropsch synthesis process.Catalyst activity is high, can improve the specific productivity of reaction unit, and selective height can improve the utilization rate of reaction raw materials, high running at full capacity, the minimizing non-normal stop that is conducive to maintain reaction unit of stability.To the middle discovery of studying for a long period of time of fischer-tropsch reaction: nickel, ruthenium, iron and cobalt have fischer-tropsch reaction activity.Nickel-base catalyst, under fischer-tropsch reaction condition, can produce too many methane, and the while self is easy to generate volatile carbonyl nickel and runs off from reactor, is difficult to realize commercial Application.Ruthenium is the most active known fischer-tropsch reaction catalyst, but its high price and limited reserves have hindered its use on industrial Fischer-Tropsch device, and it is generally to add in iron-based and cobalt-base catalyst, improve their reactivity worth with auxiliary agent form.Only have iron-based and cobalt-base catalyst to be successfully used in Fischer-Tropsch compound probability.Ferrum-based catalyst and cobalt-base catalyst have bigger difference in reactivity worth.
Ferrum-based catalyst can have very high reactivity, but research [Fuel 76 (1997) 273.] finds that the CO reacting is converted into CO with higher ratio along with CO conversion ratio raises
2rather than hydrocarbon, generate hydrocarbon selectively along with CO conversion ratio raises and decline.In order to obtain higher hydrocarbon productive rate, it is suitable to lower CO conversion per pass work that ferrum-based catalyst is considered to, by reaction end gas, loop secondary response mode and reach high CO total conversion (synthesis gas utilization rate) and high hydrocarbon-selective, but this working method has increased the workloads such as tail gas separation, gas circulation compression and corresponding energy consumption, and the gross efficiency that has limited fischer-tropsch synthesis process improves.
Forming what contrast with ferrum-based catalyst reactivity worth is cobalt-base catalyst, and it is less that its performance is subject to generate in fischer-tropsch reaction the impact of water, and because its water-gas shift activity is very weak, the CO in synthesis gas is converted into hydrocarbon.So, use the fischer-tropsch synthesis process of cobalt-base catalyst to work in high conversion per pass mode, can save the operation to reaction end gas compression cycle, shortened technological process, be conducive to improve the gross efficiency of fischer-tropsch synthesis process.
US6765026B2 discloses a kind of Fischer-Tropsch synthesis method that special catalyst carries out catalysis of applying.The catalyst precursor that the method adopts is the soluble compounds of a kind of iron group (especially cobalt) metal or soluble compounds or the salt of salt and platinum.Presoma is contacted with the solution of hydroxyhy-drocarbyl amines or ammonium hydroxide, obtain a kind of special catalyst, make C
5 +hydrocarbon selective reaches 58% ~ 80%.
CN101224430A has reported a kind of hydrophobic organic modification of Co group Fischer-Tropsch synthesized catalyst, and noble metal and cobalt load on silica supports, then carries out organically-modified.Wherein when noble metal adopts Pt, catalyst system 15%Co0.8%Pt/SiO
2, organically-modified reagent adopts dimethyldiethoxysilane modification, and on pressurization static bed, reaction condition is 230 ℃, 1.0MPa, 1000h
-1(V/V), H
2/ CO=3/1, the conversion ratio of CO is 72.7%.
CN200810039490.0 discloses a kind of for the synthetic precipitated ferrum-cobalt catalyst of Fischer-Tropsch, the composition of this catalyst comprises: elemental iron, element cobalt 2～50g/100gFe, Element Potassium 1～10g/100gFe and in the siliceous oxygen species 5～100g/100gFe of silica weight.Preparation method is for adding precipitating reagent the mixed solution of iron-containing liquor and cobalt-carrying solution, after precipitating aging 24h, washing and filtering, obtain the co-precipitation filter cake of iron content cobalt, deionized water is added in filter cake, making beating makes it even, under constantly at the uniform velocity stirring, add SiO 2 powder and potassium carbonate powder, or add SiO 2 powder and potassium silicate colloid, mix, obtained catalyst pulp is dry, roasting, obtain described precipitated ferrum-cobalt catalyst, and its weight ratio consists of Fe: Co: K: SiO
2=100: 2～50: 1～10: 5～100.The sintering temperature of described catalyst pulp is that 400～500 ℃, roasting time are 2～6 hours.The method has higher gas conversion ratio equally.
In sum, Co based Fischer-Tropsch synthesis catalyst is compared ferrum-based catalyst and so, at the conversion ratio of synthesis gas and reduce in carbon dioxide selective and there is obvious advantage, but in high conversion, also existing liquid hydrocarbon product distribution relatively disperses, the long paraffinic components of carbochain is on the high side, the problems such as the selective height of methane; Be unfavorable for follow-up processing and utilization, the solution of these problems can further improve application and the popularization of Co based Fischer-Tropsch synthesis catalyst.
Summary of the invention
For the deficiencies in the prior art, the present invention discloses a kind of Co based Fischer-Tropsch synthesis catalyst for CO hydrogenation and its preparation method and application.This catalyst can improve diesel oil distillate in liquid hydrocarbon product ratio, reduce the selective of methane.
For a catalyst for CO hydrogenation, described catalyst is comprised of composite metal oxide and the metal promoter with perovskite structure, and the complex metal formula with perovskite structure is ABO
3-y, wherein, A is rare earth metal, and B, at least to comprise that the transition metal of cobalt, the mol ratio of cobalt and all the other transition metal are not less than 3:1, is preferably not less than 4:1, and y is the molal quantity in the oxygen room that exists in composite oxides; With the weighing scale of catalyst, metal promoter simple substance content is 1-15%, preferably 5%-10%.
The present invention is for the catalyst of CO hydrogenation, and described rare earth metal comprises one or more in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium.Described transition metal comprises one or more in iron, nickel, manganese, copper, zinc, chromium, vanadium, titanium, molybdenum, zirconium except cobalt.Described auxiliary agent is various auxiliary agents used in existing Fischer-Tropsch synthetic technology, as one or more in zirconium, potassium, ruthenium, platinum, nickel, manganese, copper, zinc, chromium, vanadium, titanium, molybdenum, zirconium.
The present invention is for the catalyst of CO hydrogenation, the composite metal oxide NdTi with perovskite structure that described catalyst is comprised of rare earth metal neodymium and transition metals Ti and iron
1-xco
xo
3-y, wherein 0.8<x< 0.95 and auxiliary agent zinc form.Composite metal oxide containing neodymium perovskite structure can produce diesel oil distillate in the further raising of synergy liquid hydrocarbon product with auxiliary agent zinc.
For a preparation method for the catalyst of CO hydrogenation, comprise preparation and the metal promoter loading process of the composite metal oxide with perovskite structure.
In the inventive method, the preparation of the described composite metal oxide with perovskite structure adopts complexometry, but is not limited to the method.Described complexometry comprises following process: first will measure the rare earth metal of ratio and the transition metal presoma of iron content with complexing agent mixing wiring solution-forming and stir, then carry out moisture evaporation, solution is transformed into the gel of thickness by transparent colloidal sol, final drying, roasting, make the composite metal oxide with perovskite structure after roasting.The composite metal oxide NdTi with preparation with perovskite structure
1-xco
xo
3-ywherein 0.8<x< 0.95 is example, specifically comprise following content: take neodymium nitrate, Titanium Nitrate, nickel nitrate is presoma, take citric acid or ethylene glycol as complexing agent, wiring solution-forming mixing and stirring, then carry out moisture evaporation, and solution is transformed into the gel of thickness by transparent colloidal sol, final drying, roasting, the sample after roasting is the catalyst for CO hydrogenation.
Above-mentioned complexometry preparation has in the composite metal oxide of perovskite structure, and complexing agent and metal ion mol ratio are 1:1～8:1, are preferably 1:1～4:1.Preparation and agitating solution, at 20～90 ℃, are preferably at 50～70 ℃ and carry out.Stir speed (S.S.) is 200～500rpm, is preferably 300～400rpm.Mixing time is 3～8 hours, is preferably 4～6 hours.Baking temperature is 60～200 ℃, is preferably 80～150 ℃.Be 1～36 hour drying time, is preferably 8～24 hours.Sintering temperature is 600～1000 ℃, and roasting time is roasting 2 ~ 15 hours, is preferably at 700～900 ℃ roasting 3～8 hours.
In the inventive method, described metal promoter loading process adopts infusion process, and incipient impregnation or excessively volume dipping all can.Can carry out single-steeping or repeatedly flood according to actual conditions.For example there is the composite metal oxide NdTi of perovskite structure
1-xco
xo
3-y(0.8<x< 0.95) upper equi-volume impregnating carried metal auxiliary agent Zn that adopts.
For a method of reducing for the catalyst of CO hydrogenation, reduction temperature is 400～1000 ℃, preferred 500-700 ℃, and the recovery time is 1-5h, reducing atmosphere is the low-carbon alkanes of hydrogen or C1-C3, preferably the latter.Adopt the CO hydrogenation catalyst of low-carbon alkanes reduction in reduction, to catalyst, to carry out suitable modification, reduce the selective of methane.
The present invention adopt B position containing the composite metal oxide with perovskite structure of cobalt as fischer-tropsch synthetic catalyst, when keeping high conversion, improved the content of diesel oil distillate in liquid hydrocarbon product, reduce the selective of methane, solved in prior art the ubiquitous liquid hydrocarbon product carbon number of Co based Fischer-Tropsch synthesis catalyst high and distribute wide, the higher problem of methane selectively.The present invention has in the preparation process of composite metal oxide of perovskite structure, and the variation of preparation condition can have a strong impact on generation and the purity of perovskite structure.In all conditions are controlled, choosing of sintering temperature is vital, although it is more close with the present invention that some catalyst of the prior art forms, because the crystalline structure of constituent content and inherence is obviously different, so do not there is the premium properties of catalyst of the present invention.
Accompanying drawing explanation
Fig. 1 is the complex metal compound LaCoO with perovskite structure of embodiment 1 preparation
3-yxRD figure.
The specific embodiment
Below in conjunction with embodiment, further illustrate process and the effect of the inventive method, but be not limited to following examples.
Embodiment 1
The mixed aqueous solution that preparation contains cobalt nitrate and lanthanum nitrate, is that 1.2:1 takes appropriate citric acid by metal ion total amount mol ratio in citric acid and mixed aqueous solution, in mixed aqueous solution, adds slowly citric acid, and stir on dropping limit, limit.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ to dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 4 hours at 800 ℃, obtain having the composite metal oxide LaCoO of perovskite structure
3-y, adopt infusion process at composite metal oxide LaCoO
3-ythe auxiliary agent potassium that upper load weight content is 5%, is dried 8 hours at 80 ℃, and in 350 ℃, roasting is 4 hours, makes catalyst and is designated as C-1, and evaluation result is in Table 1.
Embodiment 2
The mixed aqueous solution that preparation contains cobalt nitrate, cerous nitrate and Titanium Nitrate, is that 2:1 takes appropriate citric acid by metal ion total amount mol ratio in citric acid and mixed aqueous solution, in mixed aqueous solution, adds slowly citric acid, and stir on dropping limit, limit.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ to dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 6 hours at 700 ℃, obtain having the composite metal oxide CeCo of perovskite structure
0.9ti
0.1o
3-y, adopt infusion process at composite metal oxide CeCo
0.9ti
0.1o
3-ythe zinc that upper load weight content is 10%, makes catalyst and is designated as C-2, and evaluation result is in Table 1.
Embodiment 3
The mixed aqueous solution that preparation contains neodymium nitrate, cobalt nitrate and Titanium Nitrate, is that 2:1 takes appropriate citric acid by metal ion total amount mol ratio in citric acid and mixed aqueous solution, in mixed aqueous solution, adds slowly citric acid, and stir on dropping limit, limit.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ to dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 6 hours at 700 ℃, obtain having the composite metal oxide NdCo of perovskite structure
0.9ti
0.1o
3-y, adopt infusion process at composite metal oxide NdCo
0.9ti
0.1o
3-ythe zinc that upper load weight content is 10%, makes catalyst and is designated as C-3, and evaluation result is in Table 1.
Embodiment 4
The mixed aqueous solution that preparation contains neodymium nitrate, cobalt nitrate and Titanium Nitrate, is that 4:1 takes appropriate citric acid by metal ion total amount mol ratio in citric acid and mixed aqueous solution, in mixed aqueous solution, adds slowly citric acid, and stir on dropping limit, limit.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ to dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 8 hours at 600 ℃, obtain having the composite metal oxide NdTi of perovskite structure
0.15co
0.85o
3-y, adopt infusion process at composite metal oxide NdTi
0.15co
0.85o
3-ythe auxiliary agent zinc that upper load weight content is 5%, is dried 8 hours at 80 ℃, and in 350 ℃, roasting is 4 hours, makes catalyst C-4, and evaluation result is in Table 1.
Embodiment 5
The mixed aqueous solution that preparation contains cobalt nitrate, cerous nitrate, is that 3:1 takes appropriate citric acid by metal ion total amount mol ratio in citric acid and mixed aqueous solution, in mixed aqueous solution, adds slowly citric acid, and stir on dropping limit, limit.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ to dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 5 hours at 1000 ℃, obtain having the composite metal oxide CeCoO of perovskite structure
3-y, adopt infusion process at composite metal oxide CeCoO
3-ythe auxiliary agent manganese that upper load weight content is 8%, makes catalyst and is designated as C-5, and evaluation result is in Table 1.
Comparative example 1
Adopt conventional coprecipitation to make the cobalt of non-perovskite structure, lanthanum composite metal oxide, sintering temperature is 450 ℃, then floods auxiliary agent potassium, makes catalyst and is designated as B1, and in oxide, the weight content of lanthanum, cobalt, potassium is with embodiment 1, and evaluation result is in Table 1.
Catalyst prepared by above-described embodiment and comparative example carries out activity rating, and evaluation test is carried out in high pressure CSTR, usings paraffin as solvent.First catalyst is reduced 5 hours, reduction temperature is 650 ℃, and wherein embodiment 3 adopts methane gas reduction, and all the other adopt hydrogen reducing.After reduction, catalyst is put into reactor and carried out Fischer-Tropsch synthesis, reaction actual conditions is 200 ℃, 1000h
-1, 2.0MPa, H
2/ CO=2(mol ratio).The operation result of 200h is conversion per pass in Table the conversion ratio of 1, CO.
Table 1 embodiment and comparative example fischer-tropsch synthetic catalyst evaluation result
Claims (15)
1. for a catalyst for CO hydrogenation, it is characterized in that: described catalyst is comprised of composite metal oxide and the metal promoter with perovskite structure, the complex metal formula with perovskite structure is ABO
3-y, wherein, A is rare earth metal, and B is at least to comprise that the transition metal of cobalt, the mol ratio of cobalt and all the other transition metal are not less than 3:1, and y is the molal quantity in the oxygen room that exists in composite oxides; With the weighing scale of catalyst, metal promoter simple substance content is 1-15%.
2. method according to claim 1, is characterized in that: the mol ratio of cobalt and all the other transition metal is not less than 4:1; With the weighing scale of catalyst, metal promoter simple substance content is 5%-10%.
3. method according to claim 1, is characterized in that: described rare earth metal comprises one or more in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium.
4. method according to claim 1, is characterized in that: described transition metal comprises one or more in iron, nickel, manganese, copper, zinc, chromium, vanadium, titanium, molybdenum, zirconium except cobalt.
5. method according to claim 1, is characterized in that: described auxiliary agent comprises one or more in zirconium, potassium, ruthenium, platinum, nickel, manganese, copper, zinc, chromium, vanadium, titanium, molybdenum, zirconium.
6. method according to claim 1, is characterized in that: the composite metal oxide NdTi with perovskite structure that described catalyst is comprised of rare earth metal neodymium and transition metals Ti and cobalt
1-xco
xo
3-yform with auxiliary agent zinc, wherein composite metal oxide NdTi
1-xco
xo
3-ymiddle 0.8<x< 0.95.
7. the preparation method of the arbitrary described catalyst of claim 1 to 6, is characterized in that: the preparation and the metal promoter loading process that comprise the composite metal oxide with perovskite structure.
8. method according to claim 7, it is characterized in that: the preparation of the described composite metal oxide with perovskite structure adopts complexometry, comprise following process: first will measure the rare earth metal of ratio and the transition metal presoma of iron content with complexing agent mixing wiring solution-forming and stir, then carry out moisture evaporation, solution is transformed into the gel of thickness by transparent colloidal sol, final drying, roasting, make the composite metal oxide with perovskite structure after roasting.
9. method according to claim 8, it is characterized in that: take neodymium nitrate, cobalt nitrate, Titanium Nitrate is presoma, take citric acid or ethylene glycol as complexing agent, wiring solution-forming mixing and stirring, then carry out moisture evaporation, solution is transformed into the gel of thickness by transparent colloidal sol, final drying, roasting, and preparing after roasting has the composite metal oxide NdTi of perovskite structure
1-xco
xo
3-y, wherein 0.8<x< 0.95.
10. method according to claim 8, is characterized in that: complexing agent and metal ion mol ratio are 1:1～8:1; Preparation and agitating solution are at 20～90 ℃; Stir speed (S.S.) is 200～500rpm; Mixing time is 3～8 hours; Baking temperature is 60～200 ℃; Be 1～36 hour drying time; Sintering temperature is 600～1000 ℃, and roasting time is roasting 2 ~ 15 hours.
11. methods according to claim 10, is characterized in that: complexing agent and metal ion mol ratio are 1:1～4:1; Preparation and agitating solution carry out at 50～70 ℃; Stir speed (S.S.) is 300～400rpm; Mixing time is 4～6 hours; Baking temperature is 80～150 ℃; Be 8～24 hours drying time; Sintering temperature is 700～900 ℃, roasting time 3～8 hours.
12. methods according to claim 7, is characterized in that: described metal promoter loading process adopts infusion process, and incipient impregnation or excessively volume dipping all can.
13. methods according to claim 12, is characterized in that: have the composite metal oxide NdTi of perovskite structure
1-xco
xo
3-y(0.8<x< 0.95) upper equi-volume impregnating carried metal auxiliary agent Zn that adopts.
The method of reducing of the arbitrary described catalyst of 14. claim 1-6, is characterized in that: reduction temperature is 400～1000 ℃, and the recovery time is 1-5h, and reducing atmosphere is the low-carbon alkanes of hydrogen or C1-C3.
15. method of reducing according to claim 14, is characterized in that: reduction temperature is 500-700 ℃, the low-carbon alkanes that reducing atmosphere is C1-C3.
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| CN110876943A (en) * | 2019-11-19 | 2020-03-13 | 天津大学 | Oxide-modified Pt-Co bimetallic catalyst, preparation method and application thereof to CO oxidation |
| CN112121814A (en) * | 2020-10-19 | 2020-12-25 | 宁夏大学 | Preparation method and application of perovskite catalyst |
| CN112169817A (en) * | 2020-10-19 | 2021-01-05 | 宁夏大学 | Perovskite type composite oxygen carrier and application |
| CN112403491A (en) * | 2020-11-26 | 2021-02-26 | 厦门大学 | Catalyst for preparing liquid fuel by high-selectivity conversion of synthesis gas and preparation method and application thereof |
| CN114471589A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalyst, method for sulfur-tolerant shift catalytic reaction and method for preparing methane |
| CN114558586A (en) * | 2022-02-28 | 2022-05-31 | 中国科学技术大学 | KCoMnMoOxCatalyst, preparation method and application thereof |
| CN114700081A (en) * | 2022-03-18 | 2022-07-05 | 南京大学 | Preparation and application of perovskite type cerium metal salt with transition metal ion regulation and control performance |
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| CN109225234A (en) * | 2018-09-19 | 2019-01-18 | 石河子大学 | A kind of composition for carbon catalytic hydrogenation methane |
| CN109225234B (en) * | 2018-09-19 | 2021-07-20 | 石河子大学 | Composition for preparing methane by carbon catalytic hydrogenation |
| CN110876943A (en) * | 2019-11-19 | 2020-03-13 | 天津大学 | Oxide-modified Pt-Co bimetallic catalyst, preparation method and application thereof to CO oxidation |
| CN110876943B (en) * | 2019-11-19 | 2022-11-04 | 天津大学 | Oxide-modified Pt-Co bimetallic catalyst, preparation method and application thereof to CO oxidation |
| CN112121814A (en) * | 2020-10-19 | 2020-12-25 | 宁夏大学 | Preparation method and application of perovskite catalyst |
| CN112169817A (en) * | 2020-10-19 | 2021-01-05 | 宁夏大学 | Perovskite type composite oxygen carrier and application |
| CN112121814B (en) * | 2020-10-19 | 2021-10-29 | 宁夏大学 | Preparation method and application of perovskite catalyst |
| CN114471589A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalyst, method for sulfur-tolerant shift catalytic reaction and method for preparing methane |
| CN112403491A (en) * | 2020-11-26 | 2021-02-26 | 厦门大学 | Catalyst for preparing liquid fuel by high-selectivity conversion of synthesis gas and preparation method and application thereof |
| CN114558586A (en) * | 2022-02-28 | 2022-05-31 | 中国科学技术大学 | KCoMnMoOxCatalyst, preparation method and application thereof |
| CN114700081A (en) * | 2022-03-18 | 2022-07-05 | 南京大学 | Preparation and application of perovskite type cerium metal salt with transition metal ion regulation and control performance |
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