CN102698749B - Ruthenium ammonia synthesis catalyst taking ruthenium ammonia complex as precursor - Google Patents
Ruthenium ammonia synthesis catalyst taking ruthenium ammonia complex as precursor Download PDFInfo
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- CN102698749B CN102698749B CN201210194772.4A CN201210194772A CN102698749B CN 102698749 B CN102698749 B CN 102698749B CN 201210194772 A CN201210194772 A CN 201210194772A CN 102698749 B CN102698749 B CN 102698749B
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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
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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 ammonia synthesis catalyst taking a ruthenium ammonia complex as a precursor and a preparation method thereof. The ruthenium ammonia synthesis catalyst comprises the following components: one of 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 soluble ruthenium complex generated from reaction of potassium ruthenate and ammonia; M1 is one of or a mixture of more of barium nitrate, barium acetate, magnesium nitrate, ammonium nitrate, aluminum nitrate and zirconium nitrate; M2 is one of or a mixture of more of alkali metals such as sodium, potassium, rubidium and caesium, nitrates of rare earth metals, acetates, hydroxides or oxides; and AC is a carrier, namely active carbon or graphitized active carbon. According to the method, the graphitized active carbon is used as the carrier, and the ammonia synthesis catalyst is prepared by the following steps of preparing the potassium ruthenate, preparing the precursor, preparing mixed solution, preparing the catalyst, drying and the like. The preparation method has the advantages of simple equipment and procedure, short preparation period, high efficiency, energy conservation and environmental protection; large-scale production is easy to realize; and the prepared catalyst has high performance price ratio.
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 ruthenium ammino-complex is presoma be ammonia synthesis catalyst and preparation method thereof.
Background technology
Ammonia synthesis is the pillar industry of chemical industry, and ruthenium is that ammonia synthesis catalyst is considered to second generation ammonia synthesis catalyst after iron catalyst.The 80s and 90s in last century, people just after deliberation the application in ruthenium-based ammonia synthetic catalyst of the presoma of various rutheniums, and the preparation method of the corresponding different catalyst of corresponding different ruthenium presomas, 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 that different ruthenium complex presomas make, good water-soluble because presoma has, be conducive to the design of experimental technique, can be by obtaining the ammonia synthesis catalyst of high activity and high stability to the change of experiment condition.
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 ruthenium ammino-complex is presoma be ammonia synthesis catalyst and preparation method thereof, equipment of the present invention, 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 ruthenium ammino-complex of take is presoma be ammonia synthesis catalyst consist of RuL+ M1+ M2/AC, M1-(RuL+ M1+ M2)/AC, (RuL+ M1+ M2)-M1/AC, a kind of in (RuL+ M1+ M2)-M2-M1/AC; Wherein RuL is the water miscible ruthenium complex that potassium ruthenate and ammonia react generate; M1 is one or more the mixture in barium nitrate, barium acetate, magnesium nitrate, ammonium nitrate, aluminum nitrate, zirconium nitrate; M2 is one or more the mixture in nitrate, acetate, hydroxide or the oxide of alkali metallic sodium, potassium, rubidium, caesium, rare earth metal; AC is carrier, i.e. active carbon or graphitization active carbon.
A kind of as above take ruthenium that ruthenium ammino-complex is presoma be ammonia synthesis catalyst preparation method concrete steps as:
(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 the potassium ruthenate aqueous solution to make ruthenium-ammino-complex solution in ammonia spirit, the mass fraction of ammoniacal liquor is 5～25%;
(3) mixed solution preparation: use pH value to 0～8 of ruthenium-ammino-complex solution of one or more regulating steps (2) in nitric acid, acetic acid, oxalic acid, citric acid, tartaric acid or ammoniacal liquor, then add nitrate, acetate or the oxide of alkaline-earth metal or rare earth metal to be made into mixed solution; Described nitric acid, acetic acid, oxalic acid, citric acid, tartaric mass fraction are 10～65%, and the mass fraction of ammoniacal liquor is 5～25%;
(4) catalyst preparation: active carbon or graphitization active carbon are 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 ℃.
The described ruthenium powder of step (1) is pure ruthenium powder, reclaim a kind of in ruthenium powder, ruthenic oxide or hydroxide ruthenium.
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 ammoniacal liquor reaction temperature are at 0～100 ℃.
The ammonia that step (2) is described and the mol ratio of ruthenium are 0.5:1-8:1.
The ruthenium that the ruthenium ammino-complex of take is presoma is that the presoma of ammonia synthesis catalyst is RuL; Described RuL adds potassium ruthenate solution to make in ammonia spirit.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 ammoniacal liquor and potassium ruthenate, directly react the water miscible ruthenium complex of preparation 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 potassium ruthenate and ammonia, 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; Described RuL is that potassium ruthenate reacts the water miscible ruthenium complex generating with ammoniacal liquor.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, hydroxide or oxide; 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.
Described RuL adds potassium ruthenate solution to make in ammonia spirit.
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 ammonia spirit, the mass fraction of ammoniacal liquor is 5～25%;
(3) mixed solution preparation: use pH value to 0～8 of the ruthenium complex solution of one or more regulating steps (2) in nitric acid, acetic acid, oxalic acid, citric acid, tartaric acid or ammoniacal liquor, then add nitrate, acetate, hydroxide or the oxide of alkaline-earth metal or rare earth metal 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 5～25%;
(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 ammoniacal liquor 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 ammonia spirit, (ammonia is 6:1 with the ratio of the amount of substance of ruthenium, 2 milliliters of ammonia spirits), 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:
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 ammonia spirit, (ammonia is 6:1 with the ratio of the amount of substance of ruthenium, 2 milliliters of ammonia spirits), dropwise rear with nitric acid and ammoniacal liquor tune pH value of solution=4, 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 17.32%.
embodiment 3:
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 ammonia spirit, (ammonia is 6:1 with the ratio of the amount of substance of ruthenium, 2 milliliters of ammonia spirits), dropwise rear with nitric acid and ammoniacal liquor tune pH value of solution=6, 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 16.17%.
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 (1)
1. the ruthenium that the ruthenium ammino-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, potassium hydroxide or potassium acetate; The mol ratio of described sylvite and ruthenium is 1:1～10:1; Described ruthenium powder is pure ruthenium powder, reclaim a kind of in ruthenium powder, ruthenic oxide or hydroxide ruthenium;
(2) presoma preparation: add while stirring the potassium ruthenate aqueous solution to make ruthenium-ammino-complex solution in ammonia spirit, the mass fraction of ammoniacal liquor is 5～25%; The described potassium ruthenate aqueous solution is that potassium ruthenate that step (1) is made is dissolved in the distilled water of 0～80 ℃; Potassium ruthenate and ammoniacal liquor reaction temperature are at 0～100 ℃; Described ammonia and the mol ratio of ruthenium are 0.5:1-8:1;
(3) mixed solution preparation: use pH value to 0～8 of ruthenium-ammino-complex solution of one or more regulating steps (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; Described nitric acid, acetic acid, oxalic acid, citric acid, tartaric mass fraction are 10～65%, and the mass fraction of ammoniacal liquor is 5～25%;
(4) catalyst preparation: 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 ℃.
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| KR20180066907A (en) * | 2016-12-09 | 2018-06-20 | 코아텍주식회사 | Adsorbent for acid exhaust gas removal and its manufacturing method |
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| US10131545B2 (en) | 2013-01-22 | 2018-11-20 | Nippon Shokubai Co., Ltd. | Ammonia synthesis method and catalyst for ammonia synthesis |
| JP6285101B2 (en) * | 2013-03-06 | 2018-02-28 | 株式会社日本触媒 | Catalyst for ammonia synthesis |
| JP6234681B2 (en) * | 2013-01-22 | 2017-11-22 | 株式会社日本触媒 | Ammonia synthesis method |
| CN108525663B (en) * | 2018-05-02 | 2020-12-25 | 福建省福大百阳化工科技有限公司 | Active carbon loaded ruthenium-based ammonia synthesis catalyst and preparation method thereof |
| CN115532255A (en) * | 2021-06-29 | 2022-12-30 | 厦门大学 | Preparation method and application of Ru-based catalyst |
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| CN1954910A (en) * | 2005-10-28 | 2007-05-02 | 厦门大学 | Preparation method of ruthenium-base ammonia synthetic catalyst |
| 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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| JP2007029858A (en) * | 2005-07-27 | 2007-02-08 | Honda Motor Co Ltd | Catalyst for synthesizing ammonia |
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| CN1954910A (en) * | 2005-10-28 | 2007-05-02 | 厦门大学 | Preparation method of ruthenium-base ammonia synthetic catalyst |
| 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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| KR20180066907A (en) * | 2016-12-09 | 2018-06-20 | 코아텍주식회사 | Adsorbent for acid exhaust gas removal and its manufacturing method |
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Effective date of registration: 20151223 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: 20180426 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. |