CN102580778B - 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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- CN102580778B CN102580778B CN201210024788.0A CN201210024788A CN102580778B CN 102580778 B CN102580778 B CN 102580778B CN 201210024788 A CN201210024788 A CN 201210024788A CN 102580778 B CN102580778 B CN 102580778B
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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
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 ammonia synthesis catalyst preparing technical field, more specifically relate to that a kind of to take the ruthenium that polyhydroxy ruthenium complex is presoma be ammonia synthesis catalyst and preparation method thereof.
Background technology
Ammonia synthesis catalyst is most important catalyst in 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, the Introduction of Literatures that some are early stage 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, in ruthenium catalyst, adopt Ru
3(CO)
12or other is commercial without chlorine presoma, because of lower the promoting the use of of affecting ruthenium catalyst of its cost performance.And though the catalyst cost performance that relatively cheap ruthenic chloride is prepared as presoma is higher, but in catalyst, residual chlorion may affect the activity of catalyst and the safety of ammonia synthesis production equipment, and the catalyst preparation efficiency that the ruthenic chloride of take is prepared as presoma is lower, in complex process, preparation process the loss of ruthenium larger, to the ruthenium of preparation high performance-price ratio, be that ammonia synthesis catalyst is unfavorable.In research, find, the catalyst making by different ruthenium complex presomas, may form and have the nanocrystalline of high miller index surface, and it has active influence to the raising of catalyst activity and stability thereof.
The United States Patent (USP) that the ruthenic chloride of take is presoma (U. S. Patent 4 600 571; U. S. Patent 4 142 993) preparation technology is more loaded down with trivial details, and preparation facilities is complicated, and industrialization difficulty is larger; Chinese patent (CN161148A, CN1270081A, CN101053834A, 200810071876.X) take ruthenic chloride as presoma, 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 larger, preparation efficiency is lower, has affected 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 that a kind of to take the ruthenium that polyhydroxy ruthenium complex is presoma be ammonia synthesis catalyst and preparation method thereof, its production equipment, flow process are simple, and manufacturing cycle is short, and efficiency is high, and energy-conserving and environment-protective are easy to accomplish scale production; The catalyst cost performance of preparation is high.
For achieving the above object, the present invention adopts following technical scheme:
The ruthenium that the polyhydroxy ruthenium complex of take is presoma is that the presoma of ammonia synthesis catalyst is RuL; Described RuL is that ruthenium reacts the water miscible ruthenium complex generating with polyhydroxy-acid, polyhydroxy phenol, polyhydroxy ethers, polyhydroxy aldehyde, polyhydroxyketone, polyhydroxy benzenes, polyhydroxy quinone, multi-hydroxy ester.Described polyhydroxy ethers is a kind of in methylcellulose, carboxymethyl cellulose, ethyl cellulose.Described polyhydroxy aldehyde is glucose, wood sugar, mannose, arabinose, galactolipin, a kind of in glyceraldehyde, galactolipin, lactose, maltose, gossypose.Described polyhydroxyketone is a kind of in fructose, sorbose, ribulose.
Described RuL adds potassium ruthenate solution to make in polyol solution.
Described catalyst consist of RuL+ M1+ M2/AC, M1-(RuL+ M1+ M2)/AC, a kind of in (RuL+ M1+M2-M1)/AC or (RuL+ M1+ M2)-M2-M1/AC; Wherein for M1 is one or more the composition in barium nitrate, barium acetate, magnesium nitrate, ammonium nitrate; M2 is one or more the composition in alkali metallic sodium, potassium, rubidium, caesium and rare earth nitrades, acetate or hydroxide; AC is carrier, i.e. graphitization active carbon.Catalyst is to take graphitization active carbon as carrier, through potassium ruthenate preparation, presoma preparation, mixed solution preparation, catalyst preparation, dry these steps, makes described ammonia synthesis catalyst.
The concrete preparation process of described catalyst is:
(1) potassium ruthenate preparation: weigh ruthenium powder, sylvite, be placed in nickel crucible and mix, 400-650 ℃ of processing 1-4h obtain potassium ruthenate in Muffle furnace; Described sylvite is one or both the composition in potassium nitrate, potassium hydroxide or potassium acetate; The mol ratio of described sylvite and ruthenium is 1:1～10:1;
(2) presoma preparation: add while stirring potassium ruthenate solution to make ruthenium complex in polyol solution;
(3) mixed solution preparation: use pH value to 0～8 of the ruthenium complex solution of a kind of regulating step (2) in nitric acid, acetic acid, oxalic acid, citric acid, tartaric acid or ammoniacal liquor, then add the nitrate of alkaline-earth metal or rare earth metal or acetate to be made into mixed solution; The mass fraction of the acid solution of described adjusting use is 10～65%, and the mass fraction of ammoniacal liquor is 10～25%;
(4) catalyst preparation: graphitization active carbon is immersed in 0～60 ℃ of mixed solution, and each dip time is 3～60 minutes;
(5) dry: the product after dipping is dried and within 20～60 minutes, made described ammonia synthesis catalyst at 50-120 ℃.
Wherein the described ruthenium powder of step (1) is pure ruthenium powder, reclaims a kind of in ruthenium powder, hydroxide ruthenium or ruthenic oxide; The described potassium ruthenate aqueous solution of step (2) is that potassium ruthenate that step (1) is made is dissolved in the distilled water of 0～80 ℃; 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 described 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 ruthenium powder or reclaim metal Ru be that starting material is prepared potassium ruthenate intermediate in the present invention, with polyhydroxy ethers or polyhydroxy aldehyde or polyhydroxyketone, directly react the water miscible ruthenium complex of preparation with potassium ruthenate at ambient temperature again, the preparation of ruthenium complex presoma is simply efficient, is suitable for extensive preparation.
(2) preparation process that the present invention is ammonia synthesis catalyst for ruthenium does not need hydrogen reduction or washing dechlorination step, and the preparation efficiency of catalyst increases substantially, and the utilization rate of ruthenium is higher, and catalyst has higher cost performance.
(3) in the catalyst that prepared by the present invention, ruthenium presoma is the complex compound of ruthenium and polyhydroxy ethers/aldehyde/ketone, in reactor, just need be reduced to ruthenium nano particle during reduction reaction, and therefore, the stability of preparation, use and transportation catalyst is better.
(4) in catalyst preparation process, described presoma RuL can with the auxiliary agent mixed load such as barium potassium, make ruthenium barium potassium in activated carbon surface high degree of dispersion, isolation mutually, 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 use procedure, are a kind of Green Chemistry chemical processes.
The specific embodiment
Described catalyst consist of RuL+ M1+ M2/AC, M1-(RuL+ M1+ M2)/AC, a kind of in (RuL+ M1+ M2)-M1/AC or (RuL+ M1+ M2)-M2-M1/AC; Wherein for M1 is one or more the composition in barium nitrate, barium acetate, magnesium nitrate, ammonium nitrate; M2 is one or more the composition in alkali metallic sodium, potassium, rubidium, caesium and rare earth nitrades, acetate or hydroxide; AC is carrier, i.e. graphitization active carbon.Catalyst is to take graphitization active carbon as carrier, through potassium ruthenate preparation, presoma preparation, mixed solution preparation, catalyst preparation, dry these steps, makes described ammonia synthesis catalyst.
The presoma that is ammonia synthesis catalyst containing polyhydric ruthenium is RuL; Described RuL is that ruthenium reacts the water miscible ruthenium complex generating with carboxylic acid, polyhydroxy phenol, polyhydroxy ethers, polyhydroxy aldehyde, polyhydroxyketone, polyhydroxy benzenes, polyhydroxy quinone, multi-hydroxy ester.Described 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 to make in polyol solution.
The concrete preparation process of described catalyst is:
(1) potassium ruthenate preparation: weigh ruthenium powder, sylvite, be placed in nickel crucible and mix, 400-650 ℃ of processing 1-4 h obtain potassium ruthenate in Muffle furnace; Described sylvite is one or both the composition in potassium nitrate, potassium hydroxide or potassium acetate; The mol ratio of described sylvite and ruthenium is 1:1～10:1;
(2) presoma preparation: add while stirring potassium ruthenate solution to make ruthenium complex in polyol solution;
(3) mixed solution preparation: use pH value to 0～8 of the ruthenium complex solution of a kind of regulating step (2) in nitric acid, acetic acid, oxalic acid, citric acid, tartaric acid or ammoniacal liquor, then add the nitrate of alkaline-earth metal or rare earth metal or acetate to be made into mixed solution; The mass fraction of the acid solution of described adjusting use is 10～65%, and the mass fraction of ammoniacal liquor is 10～25%;
(4) catalyst preparation: graphitization active carbon is immersed in 0～60 ℃ of mixed solution, and each dip time is 3～60 minutes;
(5) dry: the product after dipping is dried and within 20～60 minutes, made described ammonia synthesis catalyst at 50-120 ℃.
Wherein the described ruthenium powder of step (1) is pure ruthenium powder, reclaims a kind of in ruthenium powder, hydroxide ruthenium or ruthenic oxide; The described potassium ruthenate aqueous solution of step (2) is that potassium ruthenate that step (1) is made is dissolved in the distilled water of 0～80 ℃; 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 described ruthenium complex solution of step (3) is 0～8.
Below by embodiment in detail the present invention is described in detail:
embodiment 1:
Get the ruthenium powder of 0.40 gram, after adding 1.15 grams of potassium nitrate and 0.64 gram of potassium hydroxide to mix in nickel crucible, being placed in 600 ℃ of Muffle furnaces processes 1 hour, after being cooled to room temperature, by 10 ml deionized water, dissolve potassium ruthenate, under room temperature condition, the potassium ruthenate aqueous solution is joined in glucose solution, (glucose is 2:1 with the ratio of the amount of substance of ruthenium, 2 milliliters of D/Ws), dropwise and with nitric acid, adjust pH value of solution=2 afterwards, add 10% barium (to take quality of activated carbon as benchmark, barium nitrate is presoma), incipient impregnation after dissolving, dries.Change the addition of ruthenium complex and auxiliary agent, can make the serial ammonia synthesis catalyst of different barium ruthenium ratios.At hydrogen mixed gas nitrogen, than being 3:1, air speed is 10000 h
-1, reaction pressure is 10 MPa, and reaction temperature is under 400 ℃ of conditions, and 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.At hydrogen mixed gas nitrogen, than being 3:1, air speed is 10000 h
-1, reaction pressure is 10 MPa, and reaction temperature is under 400 ℃ of conditions, and 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.At hydrogen mixed gas nitrogen, than being 3:1, air speed is 10000 h
-1, reaction pressure is 10 MPa, and reaction temperature is under 400 ℃ of conditions, and 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.At hydrogen mixed gas nitrogen, than being 3:1, air speed is 10000 h
-1, reaction pressure is 10 MPa, and reaction temperature is under 400 ℃ of conditions, and ammonia synthesis activity is 15.15%.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (6)
1. the ruthenium that the polyhydroxy ruthenium complex of take is presoma is a preparation method for ammonia synthesis catalyst, it is characterized in that: described preparation method's concrete steps are:
(1) potassium ruthenate preparation: weigh ruthenium powder, sylvite, be placed in nickel crucible and mix, 400-650 ℃ of processing 1-4h obtain potassium ruthenate in Muffle furnace; Described sylvite is one or both the composition in potassium nitrate or potassium acetate; The mol ratio of described sylvite and ruthenium is 1:1～10:1;
(2) presoma preparation: add while stirring the potassium ruthenate aqueous solution to make ruthenium-polyhydroxy ethers, ruthenium-polyhydroxy aldehyde or ruthenium-polyhydroxyketone complex solution in polyhydroxy ethers, polyhydroxy aldehyde or polyhydroxyketone-aqueous solution; The mol ratio of described polyhydroxy ethers, polyhydroxy aldehyde or polyhydroxyketone and ruthenium is 0.5:1-8:1;
(3) mixed solution preparation: use pH value to 0～8 of ruthenium-polyhydroxy ethers, ruthenium-polyhydroxy aldehyde or ruthenium-polyhydroxyketone complex solution of a kind of regulating step (2) in nitric acid, acetic acid, oxalic acid, citric acid, tartaric acid or ammoniacal liquor, then add barium nitrate to be made into mixed solution; The mass fraction of the acid solution of described adjusting use is 10～65%, and the mass fraction of ammoniacal liquor is 10～25%;
(4) catalyst preparation: graphitization active carbon is immersed in 0～60 ℃ of mixed solution, and each dip time is 3～60 minutes;
(5) dry: the product after dipping is dried and within 20～60 minutes, made described ammonia synthesis catalyst at 50-120 ℃.
2. according to claim 1 to take the ruthenium that polyhydroxy ruthenium complex is presoma be the preparation method of ammonia synthesis catalyst, 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 hydroxide ruthenium.
3. according to claim 1 to take the ruthenium that polyhydroxy ruthenium complex is presoma be the preparation method of ammonia synthesis catalyst, it is characterized in that: the described potassium ruthenate aqueous solution of step (2) is that potassium ruthenate that step (1) is made is dissolved in the distilled water of 0～80 ℃; Potassium ruthenate and polyhydroxy ethers, polyhydroxy aldehyde or polyhydroxyketone reaction temperature are at 0～100 ℃.
4. according to claim 1 to take the ruthenium that polyhydroxy ruthenium complex is presoma be the preparation method of ammonia synthesis catalyst, it is characterized in that: described polyhydroxy ethers is a kind of in methylcellulose, carboxymethyl cellulose, ethyl cellulose.
It is 5. according to claim 1 that to take the ruthenium that polyhydroxy ruthenium complex is presoma be the preparation method of ammonia synthesis catalyst, it is characterized in that: described polyhydroxy aldehyde is glucose, wood sugar, mannose, arabinose, galactolipin a kind of in glyceraldehyde, lactose, maltose, gossypose.
6. according to claim 1 to take the ruthenium that polyhydroxy ruthenium complex is presoma be the preparation method of ammonia synthesis catalyst, it is characterized in that: described polyhydroxyketone is a kind of in fructose, sorbose, ribulose.
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| 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 |
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| CN101322947B (en) * | 2008-08-07 | 2011-12-14 | 福州大学 | Active carbon supported ruthenium-based ammonia synthetic catalyst and preparation thereof |
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Effective date of registration: 20151216 Address after: 350002 Fuzhou, Gulou District, Fujian Industrial Road, No. 523 Patentee after: Fujian Sanju Fuda Fertilizer Catalyst National Engineering Research Center Co., Ltd. Address before: 350001 No. 523, industrial road, Gulou District, Fujian, Fuzhou Patentee before: Fuzhou University |
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Effective date of registration: 20180502 Address after: 350002 Industrial Road, Drum Tower District, Fuzhou, Fujian Province, No. 523 Co-patentee after: China Petroleum & Natural Gas Co., Ltd. Patentee after: Fujian Sanju Fuda Fertilizer Catalyst National Engineering Research Center Co., Ltd. Address before: 350002 Industrial Road, Drum Tower District, Fuzhou, Fujian Province, No. 523 Patentee before: Fujian Sanju Fuda Fertilizer Catalyst National Engineering Research Center Co., Ltd. |