CN102744060B - BaTiO3-supported ruthenium ammonia synthesis catalyst, and preparation method thereof - Google Patents
BaTiO3-supported ruthenium ammonia synthesis catalyst, and preparation method thereof Download PDFInfo
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Abstract
The invention provides a BaTiO3-supported ruthenium ammonia synthesis catalyst, and a preparation method thereof, belonging to the technical field of fertilizer catalyst. The ruthenium-based ammonia synthesis catalyst is prepared from perovskite type BaTiO3 as support and metal ruthenium as active component at Ru/support weight ratio of (2-10):100 by isovolumetric impregnation method, sol-gel method or impregnation-atmospheric calcination method. The preparation method has the advantages of simple and convenient process, simple equipment, and easily controlled preparation process conditions. The prepared catalyst has the advantages of high low-temperature low-pressure activity, and stable performance.
Description
Technical field
The invention belongs to chemical fertilizer catalyst technical field, be specifically related to a kind of BaTiO
3negative ruthenium carrying catalyst for ammonia synthesis and preparation method thereof.
Background technology
Load ruthenium catalyst has all obtained studying widely and applying in fields such as organic synthesis, Industrial Catalysis and electro-catalysis as a kind of efficient noble metal catalyst.Wherein absorbent charcoal material loading ruthenium ammonia synthesis catalyst has just been realized industrial applications abroad as far back as last century Mo, but because Carbon Materials, with contacting of ruthenium, methanation reaction easily occurs under ammonia synthesis condition, has affected stability and the life-span of catalyst.Therefore, with high stability oxide material, substitute active carbon and prepare the focus that high activity ruthenium-based ammonia synthetic catalyst becomes this area research.But, with oxide material and other nano material load ruthenium, obtain ammonia synthesis activity under the activity, particularly low-temp low-pressure condition of catalyst also generally lower than carbon system so far.
The common preparation method of ruthenium-based ammonia synthetic catalyst is impregnated into ruthenium presoma in the carrier material of the porous such as active carbon, molecular sieve or aluminium oxide by infusion process or deposition-precipitation method, then adds alkali metal, alkaline-earth metal or rare earth metal again and obtain highly active ruthenium-based ammonia synthetic catalyst after reduction.Chinese patent CN101362080A, CN101053834A and CN101322947 all disclose a kind ofly take active carbon as carrier, the ammonia synthesis catalyst that the alkali and alkaline earth metal ions of take is auxiliary agent.Patent has improved respectively ammonia synthesis activity and the cost performance of catalyst from the improvement of the simplification of catalyst preparation section and the performances such as dispersion of active component.Although the ammonia synthesis activity of this catalyst series is considerably beyond industrial fused iron catalyst, but these patents all fail to solve the industrialized bottleneck problem of ruthenium-based ammonia synthetic catalyst, under ammonia synthesis condition, easily there is methanation, greatly reduce stability and the service life of catalyst, unsuitable industry is promoted.Oxide itself has the features such as heat endurance height and pore structure prosperity, and it also causes researcher's very big interest as catalyst carrier.Patent CN101322938 has reported a kind ofly take magnesia as carrier, take the ruthenium-based ammonia synthetic catalyst that alkali metal, alkaline-earth metal or rare earth metal be auxiliary agent, but the low-temp low-pressure ammonia synthesis activity of this catalyst is poor, substantially there is no industrial value.Patent CN1389295 is also used for catalysis ammonia synthesis reaction by the stable carbon nanotube loaded ruthenium of Nano carbon fibers peacekeeping.Although the stability of this catalyst and activity are all comparatively excellent, it is lower that such carrier material belongs to fine chemicals output, expensive, is difficult to support extensive ammonia synthesis industrial expansion.Patent CN1820843A is also coupled the electrical conductivity performance of magnesian strong basicity and CNT excellence and has prepared a kind of novel ammonia synthesis catalyst Ru/MgO-CNT.Although the catalyst better performances that this method obtains, the price of its complicated process of preparation and CNT is higher, is also difficult to realize industrial applications.
Recently, and foreign scholar (Inorgnic chemistry, 2007,46:5084-5092) finding to have the multiple transition metal oxide with multiple titanium oxide just has activation N at normal temperatures as tantalum and titanium
2performance.Catalysis journal, 2010,31 (4): 377-379 and Catalysis Commnications, 2010,11:867-870 has reported with BaCeO
3and BaCe
0.9y
0.1o
3-Xfor carrier loaded ruthenium is for catalysis ammonia synthesis reaction, found that catalyst is at 3 MPa, under 350 ℃ of conditions, just there is excellent catalytic activity
.
Oxide carried ruthenium ammonia synthesis catalyst research field, common carrier mainly contains Al
2o
3, MgO, rare earth oxide and other porous nanometer material.Compare with material with carbon element carrier, activity is totally relatively low, has limited applying of oxide carried ruthenium catalyst course of industrialization.The barium titanate supported ruthenium catalyst that the present invention announces, when catalysis ammonia synthesis reaction, is compared with other oxide carried form under low-temp low-pressure condition, shows obvious advantage aspect catalytic activity.Under identical reaction temperature and air speed, Ru/BaTiO when system pressure is 3 MPa
3outlet ammonia concentration be obviously greater than the activity of Ba-Ru/MgO under the uniform pressure of previous bibliographical information and condition, Ru/MgO while being even also greater than 10 MPa (Catal Commn, 2010,12:251-254), Sm-Ru/Al
2o
3and Sm-Ru/CCA (Catal Commn, 2007,8:1838-184 and Catal Commn, 2011,12:1452-1457), Ru/Sm
2o
3(Catal Commn, 2010,15:23-26) and K-Ru/ γ-Fe
2o
3(catalysis journal 2007,27:62-66) ammonia synthesis catalyst; Under cryogenic conditions, the Ru/Sm that adopts redox coprecipitation to prepare during with 10MPa
2o
3-CeO
2(Catal Commn, 2010,15:23-2; Chemistry journal 2012,70:137-142) compares, and all has obvious activity advantage.
Summary of the invention
The object of the present invention is to provide a kind of BaTiO
3negative ruthenium carrying catalyst for ammonia synthesis and preparation method thereof, preparation method of the present invention is easy, and equipment is simple, and preparation process condition is easy to control, and it is high that prepared catalyst has low-temp low-pressure activity, steady performance.
For achieving the above object, the present invention adopts following technical scheme:
A kind of BaTiO
3negative ruthenium carrying catalyst for ammonia synthesis is with BaTiO
3for carrier, take Ru as active component, Ru content is 2～10% of carrier quality by weight.Described BaTiO
3in carrier, the precursor of Ba is Ba (NO
3)
2, Ba (CH
3cOO)
2, Ba (OH)
2in a kind of; The presoma of described active component Ru is K
2ruO
4, Ru (NO) (NO
3)
3in a kind of.
A kind of BaTiO as above
3the preparation method of negative ruthenium carrying catalyst for ammonia synthesis comprises equi-volume impregnating, sol-gel process and dipping-atmosphere roasting method.
The concrete steps of described equi-volume impregnating are as follows:
(1) butyl titanate is poured in the acid and absolute ethyl alcohol mixed solution that pH is 3.0-5.5, under 30 ℃ of-90 ℃ of conditions, mix and blend 0.5-4 h, obtains yellow solution; Described acid is one or both in nitric acid, acetic acid;
(2) by molar concentration, be that the Ba precursor solution of 0.01-5 mol/L adds in the solution of step (1), regulate the pH value 6.0-7.8 of mixed solution;
(3) by adding ammoniacal liquor, regulate the collaborative of one or more methods in heating, ultrasonic processing under pH, stirring condition, promote the hydrolysis of butyl titanate in mixed solution, obtain white gels;
(4) white gels is put into Muffle furnace, in air atmosphere, be warming up to roasting 0.5-12 h under 300 ℃ of-1500 ℃ of conditions, obtain BaTiO
3carrier;
(5) the ruthenium precursor solution that is 5% by mass concentration is impregnated into BaTiO prepared by step (4)
3in carrier;
(6) will after step (5) gained solid reduction, be BaTiO
3negative ruthenium carrying catalyst for ammonia synthesis; Described method of reducing comprises H
2high temperature reduction and absolute ethyl alcohol, formaldehyde, boron hydride and hydrazine hydrate liquid-phase reduction.
The concrete steps of described sol-gel process are as follows:
(1) butyl titanate is poured in the acid and absolute ethyl alcohol mixed solution that pH is 3.0-5.5, under 30 ℃ of-90 ℃ of conditions, mix and blend 0.5-4 h, obtains yellow solution; Described acid is one or both in nitric acid, acetic acid;
(2) by molar concentration, be that the Ba precursor solution of 0.01-5 mol/L adds in the solution of step (1), regulate the pH value 6.0-7.8 of mixed solution, after stirring, ruthenium precursor solution is directly added;
(3) by adding ammoniacal liquor, regulate the collaborative of one or more methods in heating, ultrasonic processing under pH, stirring condition, promote the hydrolysis of butyl titanate in mixed solution, obtain maroon gel;
(4) maroon gel is put into Muffle furnace, in hydrogen mixed gas atmosphere, be warming up to roasting 0.5-12 h under 300 ℃ of-1500 ℃ of conditions, obtain BaTiO
3negative ruthenium carrying catalyst for ammonia synthesis.
The concrete steps of described dipping-atmosphere roasting method are as follows:
(1) butyl titanate is poured in the acid and absolute ethyl alcohol mixed solution that pH is 3.0-5.5, under 30 ℃ of-90 ℃ of conditions, mix and blend 0.5-4 h, obtains yellow solution; Described acid is one or both in nitric acid, acetic acid;
(2) by molar concentration, be that the Ba precursor solution of 0.01-5 mol/L adds in the solution of step (1), regulating the pH value of mixed solution is 6.0-7.8;
(3) by adding ammoniacal liquor, regulate the collaborative of one or more methods in heating, ultrasonic processing under pH, stirring condition, promote the hydrolysis of butyl titanate in mixed solution, obtain white gels;
(4) white gels is put into Muffle furnace, in air atmosphere, be warming up to roasting 0.5-12 h under 300 ℃ of-1500 ℃ of conditions, obtain BaTiO
3carrier;
(5)the carrying method of active component adopts equi-volume impregnating, and the solid after dipping is dried and is placed in hydrogen mixed gas atmosphere, is placed in after baking 3-24 h under 400 ℃ of-600 ℃ of conditions, obtains BaTiO after naturally cooling
3negative ruthenium carrying catalyst for ammonia synthesis.
Described hydrogen mixed gas atmosphere comprises pure H
2, H
2/ Ar gaseous mixture and H
2/ N
2gaseous mixture.
Beneficial effect of the present invention: the present invention adopts P-type semiconductor material B aTiO
3for Supports of Ruthenium-based Catalyst for Ammonia Synthesis, adopting equi-volume impregnating, sol-gel process and dipping-atmosphere roasting method is preparation method.Without dipping auxiliary agent, preparation technology is simple, without significant loss, under low-temp low-pressure condition, both can show excellent catalytic activity.Ruthenium content is the Ru/BaTiO of 4wt %
3catalyst is at 3 MPa, and air speed is 10000 h
-1time, at 375 ℃, outlet ammonia concentration when 400 ℃ and 425 ℃ is respectively 2.92%, 5.36% and 7.13%.And < < Journal of Molecular Catalysis > > (2012,26(1): 1-9) report Ba-Ru/MgO at 400 ℃, 5 MPa, air speed is 5000 h
-1outlet ammonia concentration be 3.0%.Catalysis Commnications(2010,11:867-870) the ammonia synthesis catalyst Ru/Al of 5 wt% ruthenium contents of report
2o
3, Ru/MgO and Ru/CeO
2at 400 ℃, 3MPa and 5000 h
-1outlet ammonia concentration under condition is respectively 0.15%, 1.46% and 0.88%.
The specific embodiment
Below in conjunction with instantiation in detail, the present invention is described in detail.But protection scope of the present invention is not limited in this, all equalizations according to doing in the scope of the claims of the present invention change and modify, and all should belong to covering scope of the present invention.
embodiment 1:
Butyl titanate is poured in the mixed solution that pH is 1.2 ethanol and acetic acid, stirred 2 h and obtain faint yellow mixed solution.Then, by the Ba (NO of 1 mol/L
3)
2solution slowly adds in above-mentioned solution, is placed in ultrasonic generator ultrasonic 1 h under 60 ℃ of conditions and obtains white gels.By after dry 12 h under 90 ℃ of conditions of this white gels, then roasting 5 h obtain BaTiO at 750 ℃
3carrier material.Adopt equi-volume impregnating that active component ruthenium is impregnated in carrier and is gone, then, with absolute ethyl alcohol reduction, active component Ru accounts for the mass fraction 4% of carrier.This catalyst of this catalysis is at 3 MPa, and air speed is 10000 h
-1time, at 375 ℃, outlet ammonia concentration when 400 ℃ and 425 ℃ is respectively 2.92%, 5.36% and 7.13%.
embodiment 2:
BaTiO
3the carrying method of carrier and ruthenium is with embodiment 1, but in preparation process, the presoma of Ba is Ba (CH
3cOO)
2.Under condition of the same race, the outlet ammonia concentration of detecting catalyst is respectively ammonia concentration and is respectively 3. 12%, 5.84% and 7.42%.
embodiment 3:
BaTiO
3the carrying method of carrier and ruthenium is with embodiment 1, but in preparation process, the presoma of Ru is Ru (NO) (NO
3)
3.Under condition of the same race, the outlet ammonia concentration of detecting catalyst is respectively 1.82%, 3.94% and 4.86%.
embodiment 4:
The preparation method of catalyst, with embodiment 1, is adding Ba (NO
3)
2during presoma, by Ru (NO) (NO
3)
3add together, adopt sol-gel process Kaolinite Preparation of Catalyst.Under condition of the same race, the outlet ammonia concentration of detecting catalyst is respectively 2.76%, 4.42% and 6.96%.
embodiment 5:
BaTiO
3the preparation of carrier adopts sol-gel process with embodiment 1.But the sintering temperature of gel is reduced to 650 ℃, dipping K
2ruO
4after drying, be 500 ℃ of H
2/ N
2roasting 8 h in mixed atmosphere.Under condition of the same race, the outlet ammonia concentration of detecting catalyst is respectively 3.46 %, 6.10% and 7.42%.
embodiment 6:
BaTiO
3the preparation of carrier adopts sol-gel process with embodiment 5.But the sintering temperature of gel is reduced to 500 ℃, dipping K
2ruO
4after drying, be 450 ℃ of H
2/ N
2roasting 8 h in mixed atmosphere.Under condition of the same race, the outlet ammonia concentration of detecting catalyst is respectively 2.12 %, 3.94% and 5.32%.
embodiment 7:
The preparation method of catalyst carrier is with embodiment 1, promotes the mode of mixed solution gelation to adopt under 60 ℃ of constant temperatures and continues to stir, and the pH of ammoniacal liquor regulator solution of take is 8.2, and follow-up method, as embodiment 1, obtains catalyst at 3 MPa, and air speed is 10000 h
-1time, at 375 ℃, outlet ammonia concentration when 400 ℃ and 425 ℃ is respectively 2.21%, 5.23% and 6.92%.
embodiment 8:
The preparation method of catalyst carrier, with embodiment 1, changes anhydrous and mixed solution acetic acid into the mixed solution of absolute ethyl alcohol and nitric acid, and follow-up method is as embodiment 1.Obtain catalyst at 3 MPa, air speed is 10000 h
-1time, at 375 ℃, outlet ammonia concentration when 400 ℃ and 425 ℃ is respectively 1.88%, 3.95% and 5.12%.
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. a BaTiO
3the preparation method of negative ruthenium carrying catalyst for ammonia synthesis, is characterized in that: described catalyst is with BaTiO
3for carrier, take Ru as active component, Ru content is 2～10% of carrier quality by weight;
Described BaTiO
3in carrier, the precursor of Ba is Ba (NO
3)
2, Ba (CH
3cOO)
2, Ba (OH)
2in a kind of; The presoma of described active component Ru is K
2ruO
4, Ru (NO) (NO
3)
3in a kind of;
Described preparation method is equi-volume impregnating, sol-gel process or dipping-atmosphere roasting method;
The concrete steps of described equi-volume impregnating are as follows:
(1) butyl titanate is poured in the acid and absolute ethyl alcohol mixed solution that pH is 3.0-5.5, under 30 ℃ of-90 ℃ of conditions, mix and blend 0.5-4 h, obtains yellow solution; Described acid is one or both in nitric acid, acetic acid;
(2) by molar concentration, be that the Ba precursor solution of 0.01-5 mol/L adds in the solution of step (1), regulating the pH value of mixed solution is 6.0-7.8;
(3) by adding ammoniacal liquor, regulate the collaborative of one or more methods in heating, ultrasonic processing under pH, stirring condition, promote the hydrolysis of butyl titanate in mixed solution, obtain white gels;
(4) white gels is put into Muffle furnace, in air atmosphere, be warming up to roasting 0.5-12 h under 300 ℃ of-1500 ℃ of conditions, obtain BaTiO
3carrier;
(5) the ruthenium precursor solution that is 5% by mass concentration is impregnated into BaTiO prepared by step (4)
3in carrier;
(6) will after step (5) gained solid reduction, be BaTiO
3negative ruthenium carrying catalyst for ammonia synthesis; Described method of reducing comprises H
2high temperature reduction and absolute ethyl alcohol, formaldehyde, boron hydride and hydrazine hydrate liquid-phase reduction;
The concrete steps of described sol-gel process are as follows:
(1) butyl titanate is poured in the acid and absolute ethyl alcohol mixed solution that pH is 3.0-5.5, under 30 ℃ of-90 ℃ of conditions, mix and blend 0.5-4 h, obtains yellow solution; Described acid is one or both in nitric acid, acetic acid;
(2) by molar concentration, be that the Ba precursor solution of 0.01-5 mol/L adds in the solution of step (1), regulating the pH value of mixed solution is 6.0-7.8, after stirring, ruthenium precursor solution is directly added;
(3) by adding ammoniacal liquor, regulate the collaborative of one or more methods in heating, ultrasonic processing under pH, stirring condition, promote the hydrolysis of butyl titanate in mixed solution, obtain maroon gel;
(4) maroon gel is put into Muffle furnace, in hydrogen mixed gas atmosphere, be warming up to roasting 0.5-12 h under 300 ℃ of-1500 ℃ of conditions, obtain BaTiO
3negative ruthenium carrying catalyst for ammonia synthesis;
The concrete steps of described dipping-atmosphere roasting method are as follows:
(1) butyl titanate is poured in the acid and absolute ethyl alcohol mixed solution that pH is 3.0-5.5, under 30 ℃ of-90 ℃ of conditions, mix and blend 0.5-4 h, obtains yellow solution; Described acid is one or both in nitric acid, acetic acid;
(2) by molar concentration, be that the Ba precursor solution of 0.01-5 mol/L adds in the solution of step (1), regulating the pH value of mixed solution is 6.0-7.8;
(3) by adding ammoniacal liquor, regulate the collaborative of one or more methods in heating, ultrasonic processing under pH, stirring condition, promote the hydrolysis of butyl titanate in mixed solution, obtain white gels;
(4) white gels is put into Muffle furnace, in air atmosphere, be warming up to roasting 0.5-12 h under 300 ℃ of-1500 ℃ of conditions, obtain BaTiO
3carrier;
(5) carrying method of active component adopts equi-volume impregnating, and the solid after dipping is dried and is placed in hydrogen mixed gas atmosphere, is placed in after baking 3-24 h under 400 ℃ of-600 ℃ of conditions, obtains BaTiO after naturally cooling
3negative ruthenium carrying catalyst for ammonia synthesis;
Described hydrogen mixed gas atmosphere is H
2/ Ar gaseous mixture or H
2/ N
2gaseous mixture.
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| CN103464151B (en) * | 2013-09-29 | 2016-01-20 | 福州大学 | A kind of composite oxide supported ruthenium ammonia synthesis catalyst and preparation method thereof |
| JP6556695B2 (en) | 2014-03-13 | 2019-08-07 | 国立研究開発法人科学技術振興機構 | Ammonia synthesis catalyst and ammonia synthesis method |
| CN105772024B (en) * | 2016-04-15 | 2019-03-05 | 浙江工业大学 | A kind of compound ammonia synthesis catalyst of iron ruthenium and preparation method thereof |
| CN110075832B (en) * | 2019-04-12 | 2022-02-15 | 济南大学 | NOx storage reduction catalyst and preparation method and application thereof |
| JP7388776B2 (en) * | 2020-02-26 | 2023-11-29 | 国立研究開発法人科学技術振興機構 | Catalyst for ammonia synthesis and method for producing ammonia |
| JP7487971B2 (en) * | 2020-02-27 | 2024-05-21 | ▲東▼南大学 | Method for producing tetragonal phase barium titanate nanoparticles |
| CN112121794B (en) * | 2020-10-19 | 2023-05-30 | 万华化学集团股份有限公司 | Selective hydrogenation catalyst and preparation method and application thereof |
| CN114433057B (en) * | 2020-10-31 | 2023-09-01 | 中国石油化工股份有限公司 | Solid acid catalyst and preparation method thereof |
| CN112619644A (en) * | 2021-01-14 | 2021-04-09 | 福州大学 | Ru-based catalyst with tetragonal barium titanate as carrier and preparation and application thereof |
| CN113694922B (en) * | 2021-09-29 | 2023-08-18 | 石河子大学 | Supported catalyst for ammonia decomposition and preparation method thereof |
| CN115364851A (en) * | 2021-10-27 | 2022-11-22 | 福州大学 | Size-controllable Ru-based nanocluster catalyst, preparation method thereof and application thereof in low-temperature and low-pressure ammonia synthesis |
| CN115607569B (en) * | 2022-12-02 | 2023-03-28 | 四川大学 | Barium titanate-loaded ruthenium cluster artificial enzyme material and preparation method and application thereof |
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