CN102580778A - Ruthenium-based ammonia synthesis catalyst with polyhydroxy ruthenium complex as precursor - Google Patents
Ruthenium-based ammonia synthesis catalyst with polyhydroxy ruthenium complex as precursor Download PDFInfo
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- CN102580778A CN102580778A CN2012100247880A CN201210024788A CN102580778A CN 102580778 A CN102580778 A CN 102580778A CN 2012100247880 A CN2012100247880 A CN 2012100247880A CN 201210024788 A CN201210024788 A CN 201210024788A CN 102580778 A CN102580778 A CN 102580778A
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a ruthenium-based ammonia synthesis catalyst with a polyhydroxy ruthenium complex as a precursor and a preparation method of the ruthenium-based ammonia synthesis catalyst. The catalyst comprises one of the following components: RuL+M1+M2/AC, M1-(RuL+M1+M2)/AC, (RuL+M1+M2)-M1/AC, and (RuL+M1+M2)-M2-M1/AC, wherein RuL is a water-soluble ruthenium complex which is generated by the reaction of ruthenium with polyhydroxy ether, polyhydroxy aldehyde or polyhydroxy ketone, M1 is one or more than one of barium nitrate, barium acetate, magnesium nitrate, ammonium nitrate, aluminium nitrate and zirconium nitrate, M2 is one or more than one of nitrate, acetate or hydroxide of rare-earth metal and alkali metal such as sodium, potassium, rubidium, and caesium, and AC is a carrier, namely activated carbon or graphitized activated carbon. According to the method, the graphitized activated carbon is taken as the carrier, and the ammonia synthesis catalyst is prepared by steps of potassium ruthenate preparation, precursor preparation, mixed solution preparation, catalyst preparation, drying and the like. The method has the advantages that devices and the process flow are simple, the preparation period is short, the efficiency is high, the effects of energy saving and environment protection can be realized, and the large-scale production can be implemented easily; and the prepared catalyst is high in cost performance.
Description
Technical field
The invention belongs to the ammonia synthesis catalyst preparing technical field, more specifically relating to a kind of is that the ruthenium of presoma is ammonia synthesis catalyst and preparation method thereof with the polyhydroxy ruthenium complex.
Background technology
Ammonia synthesis catalyst is a most important catalyst in the ammonia synthesizing industry.The 80s and 90s in last century, people just after deliberation the application of various oxides in ruthenium-based ammonia synthetic catalyst, some early stage documents have been introduced the achievement in research of this part: the main presoma of ruthenium catalyst is Ru
3(CO)
12,RuCl
3, Ru (acac)
3(acac=acetylacetone,2,4-pentanedione), RuNO (NO
3)
3, RuCl
3Deng, but in ruthenium catalyst the input of noble metal too high be the biggest obstacle that hinders its extensive use.Generally speaking, adopt Ru in the ruthenium catalyst
3(CO)
12Or other commercial no chlorine presoma, influenced promoting the use of of ruthenium catalyst because of its cost performance is low.Though and that relatively cheap ruthenic chloride is made the catalyst cost performance of presoma preparation is higher; But residual chlorion possibly influence the safety of activity of such catalysts and ammonia synthesis production equipment in the catalyst; And the Preparation of Catalyst efficient that with the ruthenic chloride is the presoma preparation is lower, in the complex process, preparation process the loss of ruthenium bigger, be that ammonia synthesis catalyst is unfavorable to the ruthenium of preparation high performance-price ratio.Find in the research,, possibly form and have the nanocrystalline of high index crystal face that it all has active influence to the raising of catalyst activity and stability thereof through the catalyst that different ruthenium complex presomas make.
With the ruthenic chloride is United States Patent (USP) (the U. S. Patent 4 600 571 of presoma; U. S. Patent 4 142 993) preparation technology is more loaded down with trivial details, and preparation facilities is complicated, and the industrialization difficulty is bigger; Chinese patent (CN161148A, CN1270081A, CN101053834A; 200810071876.X) be presoma with the ruthenic chloride, adopt hydrogen or hydrazine hydrate reduction, or to adopt the precipitation method to prepare ruthenium be ammonia synthesis catalyst; The residual quantity of chlorion is bigger; Preparation efficiency is lower, has influenced the production efficiency of catalyst, and the cost performance of catalyst is lower.
Summary of the invention
The object of the present invention is to provide a kind of is that the ruthenium of presoma is ammonia synthesis catalyst and preparation method thereof with the polyhydroxy ruthenium complex, and its production equipment, flow process are simple, and manufacturing cycle is short, and efficient is high, and energy-conserving and environment-protective are easy to accomplish scale production; The catalyst cost performance of preparation is high.
For realizing above-mentioned purpose, the present invention adopts following technical scheme:
With the polyhydroxy ruthenium complex is that the ruthenium of presoma is that the presoma of ammonia synthesis catalyst is RuL; Described RuL is the water miscible ruthenium complex that ruthenium and polyhydroxy-acid, polyhydroxy phenol, polyhydroxy ethers, polyhydroxy aldehyde, polyhydroxyketone, polyhydroxy benzenes, polyhydroxy quinone, multi-hydroxy ester reaction generate.Described polyhydroxy ethers is a kind of in methylcellulose, carboxymethyl cellulose, the ethyl cellulose.Described polyhydroxy aldehyde is glucose, wood sugar, mannose, arabinose, galactolipin, a kind of in glyceraldehyde, galactolipin, lactose, maltose, the gossypose.Described polyhydroxyketone is a kind of in fructose, sorbose, the ribulose.
Described RuL adds potassium ruthenate solution and makes in polyol solution.
Said catalyst consist of RuL+ M1+ M2/AC, M1-(RuL+ M1+ M2)/AC, a kind of among (RuL+ M1+M2-M1)/AC or (RuL+ M1+ the M2)-M2-M1/AC; Be one or more the composition in barium nitrate, barium acetate, magnesium nitrate, the ammonium nitrate wherein for M1; M2 is one or more the composition in alkali metallic sodium, potassium, rubidium, caesium and rare earth nitrades, acetate or the hydroxide; AC is a carrier, i.e. the graphitization active carbon.Catalyst is to be carrier with the graphitization active carbon, makes described ammonia synthesis catalyst through potassium ruthenate preparation, presoma preparation, mixed solution preparation, Preparation of Catalyst, these steps of drying.
The concrete preparation process of said catalyst is:
(1) potassium ruthenate preparation: weighing ruthenium powder, sylvite, place nickel crucible to mix, 400-650 ℃ of processing 1-4h promptly gets potassium ruthenate in Muffle furnace; Described sylvite is one or both the composition in potassium nitrate, potassium hydroxide or the potassium acetate; The mol ratio of said sylvite and ruthenium is 1:1～10:1;
(2) presoma preparation: in polyol solution, add potassium ruthenate solution while stirring and make ruthenium complex;
(3) mixed solution preparation: with pH value to 0～8 of the ruthenium complex solution of a kind of regulating step (2) in nitric acid, acetate, oxalic acid, citric acid, tartaric acid or the ammoniacal liquor, the nitrate or the acetate that add alkaline-earth metal or rare earth metal again are made into mixed solution; The mass fraction of the acid solution that said adjusting is used is 10～65%, and the mass fraction of ammoniacal liquor is 10～25%;
(4) Preparation of Catalyst: be immersed in the graphitization active carbon in 0～60 ℃ of mixed solution, each dip time is 3～60 minutes;
(5) drying: the product behind the dipping is dried down at 50-120 ℃ and was processed described ammonia synthesis catalyst in 20～60 minutes.
Wherein the described ruthenium powder of step (1) is pure ruthenium powder, reclaims a kind of in ruthenium powder, hydroxide ruthenium or the ruthenic oxide; The described potassium ruthenate aqueous solution of step (2) is that the potassium ruthenate that step (1) makes is dissolved in 0～80 ℃ the distilled water; The reaction temperature of potassium ruthenate and polyol is at 0～100 ℃, and the mol ratio of polyol and ruthenium is 0.5:1-8:1; The pH value of the said ruthenium complex solution of step (3) is 0～8.
Catalyst bulk density 0.55～0.65 g/ml of the present invention.
Remarkable advantage of the present invention is:
(1) to adopt the ruthenium powder or reclaim metal Ru be that starting material prepares the potassium ruthenate intermediate in the present invention; Again at ambient temperature with polyhydroxy ethers or polyhydroxy aldehyde or polyhydroxyketone and the water miscible ruthenium complex of the direct prepared in reaction of potassium ruthenate; The preparation of ruthenium complex presoma is simply efficient, is suitable for mass preparation.
(2) to be used for ruthenium be that the preparation process of ammonia synthesis catalyst does not need hydrogen reduction or washing dechlorination step in the present invention, and Preparation of catalysts efficient increases substantially, and the utilization rate of ruthenium is higher, and catalyst has higher cost performance.
(3) the ruthenium presoma is the complex compound of ruthenium and polyhydroxy ethers/aldehyde/ketone in the catalyst of the present invention preparation, in reactor, just need be reduced to ruthenium nano particle during reduction reaction, and therefore, the stability of preparation, use and transportation catalyst better.
(4) in the catalyst preparation process, said presoma RuL can with auxiliary agent mixed load such as barium potassium, make ruthenium barium potassium in the activated carbon surface high degree of dispersion, isolate each other, the anti-caking power of catalyst is strong, the methanation resisting ability of catalyst is strong.
(5) energy-saving and environmental protection in presoma preparation and the use are a kind of Green Chemistry chemical processes.
The specific embodiment
Said catalyst consist of RuL+ M1+ M2/AC, M1-(RuL+ M1+ M2)/AC, a kind of among (RuL+ M1+ M2)-M1/AC or (RuL+ M1+ the M2)-M2-M1/AC; Be one or more the composition in barium nitrate, barium acetate, magnesium nitrate, the ammonium nitrate wherein for M1; M2 is one or more the composition in alkali metallic sodium, potassium, rubidium, caesium and rare earth nitrades, acetate or the hydroxide; AC is a carrier, i.e. the graphitization active carbon.Catalyst is to be carrier with the graphitization active carbon, makes described ammonia synthesis catalyst through potassium ruthenate preparation, presoma preparation, mixed solution preparation, Preparation of Catalyst, these steps of drying.
The presoma that contains polyhydric ruthenium and be ammonia synthesis catalyst is RuL; Described RuL is the water miscible ruthenium complex that ruthenium and carboxylic acid, polyhydroxy phenol, polyhydroxy ethers, polyhydroxy aldehyde, polyhydroxyketone, polyhydroxy benzenes, polyhydroxy quinone, multi-hydroxy ester reaction generate.Said polyhydroxy ethers is methylcellulose, carboxymethyl cellulose, ethyl cellulose; Described polyhydroxy aldehyde is glucose, wood sugar, mannose, arabinose, galactolipin, glyceraldehyde, galactolipin, lactose, maltose, gossypose etc.; Described polyhydroxyketone is sorbose, ribulose.
Described RuL adds potassium ruthenate solution and makes in polyol solution.
The concrete preparation process of said catalyst is:
(1) potassium ruthenate preparation: weighing ruthenium powder, sylvite, place nickel crucible to mix, 400-650 ℃ of processing 1-4 h promptly gets potassium ruthenate in Muffle furnace; Described sylvite is one or both the composition in potassium nitrate, potassium hydroxide or the potassium acetate; The mol ratio of said sylvite and ruthenium is 1:1～10:1;
(2) presoma preparation: in polyol solution, add potassium ruthenate solution while stirring and make ruthenium complex;
(3) mixed solution preparation: with pH value to 0～8 of the ruthenium complex solution of a kind of regulating step (2) in nitric acid, acetate, oxalic acid, citric acid, tartaric acid or the ammoniacal liquor, the nitrate or the acetate that add alkaline-earth metal or rare earth metal again are made into mixed solution; The mass fraction of the acid solution that said adjusting is used is 10～65%, and the mass fraction of ammoniacal liquor is 10～25%;
(4) Preparation of Catalyst: be immersed in the graphitization active carbon in 0～60 ℃ of mixed solution, each dip time is 3～60 minutes;
(5) drying: the product behind the dipping is dried down at 50-120 ℃ and was processed described ammonia synthesis catalyst in 20～60 minutes.
Wherein the described ruthenium powder of step (1) is pure ruthenium powder, reclaims a kind of in ruthenium powder, hydroxide ruthenium or the ruthenic oxide; The described potassium ruthenate aqueous solution of step (2) is that the potassium ruthenate that step (1) makes is dissolved in 0～80 ℃ the distilled water; The reaction temperature of potassium ruthenate and polyol is at 0～100 ℃, and the mol ratio of polyol and ruthenium is 0.5:1-8:1; The pH value of the said ruthenium complex solution of step (3) is 0～8.
Through embodiment the present invention is detailed below:
Embodiment 1:
Get the ruthenium powder of 0.40 gram, after adding 1.15 gram potassium nitrate and 0.64 gram potassium hydroxide mix in nickel crucible, place Muffle furnace to handle 1 hour for 600 ℃; Be cooled to after the room temperature with 10 ml deionized water dissolving potassium ruthenate, under the room temperature condition, the potassium ruthenate aqueous solution joined (glucose is 2:1 with the ratio of the amount of substance of ruthenium in the glucose solution; 2 milliliters of D/Ws); Dropwise the back and transfer pH value of solution=2, add 10% barium (with the quality of activated carbon is benchmark, and barium nitrate is a presoma) with nitric acid; Dissolving back incipient impregnation, oven dry.Change the addition of ruthenium complex and auxiliary agent, can make the serial ammonia synthesis catalyst of different barium ruthenium ratios.Than being 3:1, air speed is 10000 h at hydrogen mixed gas nitrogen
-1, reaction pressure is 10 MPa, and reaction temperature is under 400 ℃ of conditions, and the ammonia synthesis activity is 18.50%.
Embodiment 2:
Repeat embodiment 1, just glucose changes sucrose into.Change the addition of ruthenium complex and auxiliary agent, can make the serial ammonia synthesis catalyst of different barium ruthenium ratios.Than being 3:1, air speed is 10000 h at hydrogen mixed gas nitrogen
-1, reaction pressure is 10 MPa, and reaction temperature is under 400 ℃ of conditions, and the ammonia synthesis activity is 14.23%.
Embodiment 3:
Repeat embodiment 1, just glucose changes fructose into.Change the addition of ruthenium complex and auxiliary agent, can make the serial ammonia synthesis catalyst of different barium ruthenium ratios.Than being 3:1, air speed is 10000 h at hydrogen mixed gas nitrogen
-1, reaction pressure is 10 MPa, and reaction temperature is under 400 ℃ of conditions, and the ammonia synthesis activity is 18.01%.
Embodiment 4:
Repeat embodiment 1, just glucose changes methylcellulose into.Change the addition of ruthenium complex and auxiliary agent, can make the serial ammonia synthesis catalyst of different barium ruthenium ratios.Than being 3:1, air speed is 10000 h at hydrogen mixed gas nitrogen
-1, reaction pressure is 10 MPa, and reaction temperature is under 400 ℃ of conditions, and the ammonia synthesis activity is 15.15%.
The above is merely preferred embodiment of the present invention, and all equalizations of doing according to claim of the present invention change and modify, and all should belong to covering scope of the present invention.
Claims (8)
1. be that the ruthenium of presoma is an ammonia synthesis catalyst with the polyhydroxy ruthenium complex; It is characterized in that: described ruthenium be ammonia synthesis catalyst consist of RuL+ M1+ M2/AC; M1-(RuL+ M1+ M2)/AC; (RuL+ M1+ M2)-M1/AC, a kind of among (RuL+ M1+ M2)-M2-M1/AC; Wherein RuL is the water miscible ruthenium complex that ruthenium and polyhydroxy ethers, polyhydroxy aldehyde or polyhydroxyketone reaction generate; M1 is one or more the mixture in barium nitrate, barium acetate, magnesium nitrate, ammonium nitrate, aluminum nitrate, the zirconium nitrate; M2 is one or more the mixture in nitrate, acetate or the hydroxide of alkali metallic sodium, potassium, rubidium, caesium, rare earth metal; AC is a carrier, i.e. active carbon or graphitization active carbon.
2. according to claim 1 is that the ruthenium of presoma is an ammonia synthesis catalyst with the polyhydroxy ruthenium complex, it is characterized in that: described polyhydroxy ethers is a kind of in methylcellulose, carboxymethyl cellulose, the ethyl cellulose.
3. according to claim 1 is that the ruthenium of presoma is an ammonia synthesis catalyst with the polyhydroxy ruthenium complex; It is characterized in that: described polyhydroxy aldehyde is glucose, wood sugar, mannose, arabinose, galactolipin, a kind of in glyceraldehyde, galactolipin, lactose, maltose, the gossypose.
4. according to claim 1 is that the ruthenium of presoma is an ammonia synthesis catalyst with the polyhydroxy ruthenium complex, it is characterized in that: described polyhydroxyketone is a kind of in fructose, sorbose, the ribulose.
One kind as claimed in claim 1 be that the ruthenium of presoma is the preparation method of ammonia synthesis catalyst with the polyhydroxy ruthenium complex, it is characterized in that: described preparation method's concrete steps are:
(1) potassium ruthenate preparation: weighing ruthenium powder, sylvite, place nickel crucible to mix, 400-650 ℃ of processing 1-4h promptly gets potassium ruthenate in Muffle furnace; Described sylvite is one or both the composition in potassium nitrate, potassium hydroxide or the potassium acetate; The mol ratio of said sylvite and ruthenium is 1:1～10:1;
(2) presoma preparation: in polyhydroxy ethers/aldehyde/ketone-aqueous solution, add the potassium ruthenate aqueous solution while stirring and make ruthenium-polyhydroxy ethers/aldehyde/ketone complex solution;
(3) mixed solution preparation: with pH value to 0～8 of the ruthenium-polyhydroxy ethers/aldehyde/ketone/ester complex solution of a kind of regulating step (2) in nitric acid, acetate, oxalic acid, citric acid, tartaric acid or the ammoniacal liquor, the nitrate or the acetate that add alkaline-earth metal or rare earth metal again are made into mixed solution; The mass fraction of the acid solution that said adjusting is used is 10～65%, and the mass fraction of ammoniacal liquor is 10～25%;
(4) Preparation of Catalyst: be immersed in the graphitization active carbon in 0～60 ℃ of mixed solution, each dip time is 3～60 minutes;
(5) drying: the product behind the dipping is dried down at 50-120 ℃ and was processed described ammonia synthesis catalyst in 20～60 minutes.
6. according to claim 5 is that the ruthenium of presoma is the preparation method of ammonia synthesis catalyst with the polyhydroxy ruthenium complex, it is characterized in that: the described ruthenium powder of step (1) is pure ruthenium powder, reclaim a kind of in ruthenium powder, ruthenic oxide or the hydroxide ruthenium.
7. according to claim 5 is that the ruthenium of presoma is the preparation method of ammonia synthesis catalyst with the polyhydroxy ruthenium complex, it is characterized in that: the described potassium ruthenate aqueous solution of step (2) is that the potassium ruthenate that step (1) makes is dissolved in 0～80 ℃ the distilled water; Potassium ruthenate and polyhydroxy ethers/aldehyde/reactive ketone temperature is at 0～100 ℃.
8. according to claim 5 is that the ruthenium of presoma is the preparation method of ammonia synthesis catalyst with the polyhydroxy ruthenium complex, and it is characterized in that: the mol ratio of the described polyhydroxy ethers/aldehyde of step (2)/ketone and ruthenium is 0.5:1-8:1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104084197A (en) * | 2014-07-15 | 2014-10-08 | 福州大学化肥催化剂国家工程研究中心 | Ruthenium system ammonia synthesis catalyst using graphitization activated carbon as carrier and preparation method of catalyst |
| CN108261793A (en) * | 2017-12-27 | 2018-07-10 | 中国石油天然气股份有限公司 | A kind of method of purification of Water-soluble Ru complex compound |
| CN117049613A (en) * | 2023-10-10 | 2023-11-14 | 苏州擎动动力科技有限公司 | Branched noble metal oxide and preparation method thereof |
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| CN101322947A (en) * | 2008-08-07 | 2008-12-17 | 福州大学 | Active carbon supported ruthenium-based ammonia synthetic catalyst and preparation thereof |
| CN101579627A (en) * | 2008-05-15 | 2009-11-18 | 中国石油天然气股份有限公司 | Catalyst for synthesizing ammonia through activated-carbon-loading ruthenium, and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101579627A (en) * | 2008-05-15 | 2009-11-18 | 中国石油天然气股份有限公司 | Catalyst for synthesizing ammonia through activated-carbon-loading ruthenium, and preparation method thereof |
| CN101322947A (en) * | 2008-08-07 | 2008-12-17 | 福州大学 | Active carbon supported ruthenium-based ammonia synthetic catalyst and preparation thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104084197A (en) * | 2014-07-15 | 2014-10-08 | 福州大学化肥催化剂国家工程研究中心 | Ruthenium system ammonia synthesis catalyst using graphitization activated carbon as carrier and preparation method of catalyst |
| CN104084197B (en) * | 2014-07-15 | 2016-04-06 | 福州大学化肥催化剂国家工程研究中心 | A kind of be carrier ruthenium system ammonia synthesis catalyst and the preparation thereof of graphitization active carbon |
| CN108261793A (en) * | 2017-12-27 | 2018-07-10 | 中国石油天然气股份有限公司 | A kind of method of purification of Water-soluble Ru complex compound |
| CN117049613A (en) * | 2023-10-10 | 2023-11-14 | 苏州擎动动力科技有限公司 | Branched noble metal oxide and preparation method thereof |
| CN117049613B (en) * | 2023-10-10 | 2024-01-19 | 苏州擎动动力科技有限公司 | Branched noble metal oxide and preparation method thereof |
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