CN106881133A - A kind of catalyst for synthesizing ammonia - Google Patents
A kind of catalyst for synthesizing ammonia Download PDFInfo
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- CN106881133A CN106881133A CN201510933395.5A CN201510933395A CN106881133A CN 106881133 A CN106881133 A CN 106881133A CN 201510933395 A CN201510933395 A CN 201510933395A CN 106881133 A CN106881133 A CN 106881133A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
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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 present invention relates to a kind of catalyst for synthesizing ammonia, the carrier and additive of nitride of the catalyst comprising manganese and correlation.The present invention shows good catalysis activity as a kind of new catalysis material in ammonia synthesis reaction.
Description
Technical field
The present invention relates to catalyst technology, a kind of catalyst for synthesizing ammonia and its application in ammonia synthesis reaction are specifically provided.
Background technology
Ammonia is the base stock for producing the important chemical products such as chemical fertilizer, nitric acid, plastics, and Haber-Bosch realizes the high-pressure synthesis of ammonia for the first time, and synthesis ammonia has highly important meaning in the industrial production.The catalyst for being industrially widely used in synthesis ammonia at present is iron-based and ruthenium-based catalyst.A.Mittasch is found that the Fe base catalyst that K promotes;Be supported on metal Ru on MgO carriers by M.Muhler, and addition alkali (soil) metal promoter Ba, Cs are used for ammonia synthesis reaction, achieves preferably synthesis ammonia activity [H.Bielawa, O.Hinrichsen, A.Birkner, M.MulerAngew.Chem.Int.Ed, 2001,40,6].Although iron-based and ruthenium-based catalyst have been realized in industrialization for ammonia synthesis reaction, how the process high energy consumption improves the harsh conditions of the HTHP needed for reacting, and is that ammonia synthesizing industry develops faced subject matter.According to the thermodynamical equilibrium of reaction, ammonia synthesis reaction can be carried out at normal temperatures and pressures, jump out the limitation of iron-based and ruthenium-based catalyst, explore other metal-based catalysts, be the effective way of exploitation synthetic ammonia catalyst of new generation.
The content of the invention
After MnN and the abundant ball millings of LiH, 1:3 N2/H2More than 250 DEG C are warming up in gaseous mixture, excellent synthesis ammonia performance is shown, as shown in Figure 1.In ammonia synthesis reaction, the catalyst provided using the present invention can obtain ideal effect, and the reactivity worth is better than the 5%Ru/MgO catalyst under equal conditions.Reacted XRD results show the nitride and LiH that sample is Mn, further demonstrate the synthesis ammonia catalytic action of Mn bases catalyst and its auxiliary agent.
Further study showed that, nitride (MnN, Mn of manganese3N2、Mn2N、Mn4N、Li7MnN4Deng) catalyst that combines to form with carrier or additive, it is respectively provided with similar synthesis ammonia catalysis activity.
Provided by the present invention for synthesizing the catalyst carrier of ammonia, being made up of main body and additive, aforementioned body is the nitrogen-containing compound of manganese, and additive includes one or two or more kinds in alkali/alkaline earth metal hydride, carrier or metal alloy;
Above-mentioned catalyst body is 1000 with the scope of the mass ratio of additive:1 to 1:500.
The nitrogen-containing compound of described manganese is MnN, Mn3N2、Mn4N、Mn2N、Li7MnN4In one or more mixture.
Described carrier is Li2O、MgO、CaO、SrO、BaO、Al2O3、BN、Si3N4、Mg3N2、Ca3N2, AlN, molecular sieve, carbon material, the combination of one or two or more kinds in metal-organic framework materials (MOFs).
Described alkali/alkaline earth metal hydride is LiH, NaH, KH, CsH, MgH2、CaH2、BaH2In the mixture of one or two or more kinds.
Described metal alloy is:One or two or more kinds two-spot formed between Mn in IV B, V B, VI B, VII B or VIII B races element or alloy more than ternary;Above-mentioned IV B, V B, VI B, VII B or VIII B races element are one or two or more kinds in Ti, Zr, Cr, Mo, W, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt.
The catalyst body is 200 with the scope of the mass ratio of additive:1 to 1:100.
The operating condition that the catalyst is used for when synthesizing ammonia is:Sample rises to certain reaction temperature in reaction atmosphere, and product composition carries out on-line analysis using conductivity meter;Above-mentioned reaction atmosphere is N2、H2Gaseous mixture.
Brief description of the drawings
(mol ratio is 1 to MnN/LiH prepared by Fig. 1 embodiments 1:5) the ammonia synthesis reaction activity under condition of normal pressure.
Li prepared by Fig. 2 embodiments 27MnN4Ammonia synthesis reaction activity under condition of normal pressure.
MnCl prepared by Fig. 3 embodiments 32Ammonia synthesis reaction activity under/LiH condition of normal pressure.
Specific embodiment
To further illustrate the present invention, specific examples below is enumerated, but it is not intended to limit invention scope defined in each accessory claim.
Embodiment 1:
In argon gas glove box, nitrogenized manganese (MnN) 1.0000g, LiH 0.5797g is accurately weighed, be placed in self-control stainless steel jar mill.After closing ball grinder, load planetary ball mill (Fischt PM400), ball milling condition is 150rpm ball millings 3 hours.Obtain final product sample MnN/LiH (mol ratios 1:5).
In argon gas glove box, MnN/LiH (mol ratios 1 are accurately weighed:5) 0.0690g, is placed in fixed bed quartz tube reactor.Sample is (1 in reaction atmosphere:3N2/H2Gaseous mixture) be warming up to required temperature, reaction gas flow control in 20mL/min, sampling analysis after 30 minutes.Test result is as shown in Figure 1.Ammonia generating rate reaches maximum at 275 DEG C, and hereafter temperature raises ammonia generating rate and declines.
Embodiment 2:
In argon gas glove box, Li is accurately weighed3N 0.1598g, Mn powder 0.1082g in stainless steel reactor, N210MPa is forced into, 750 DEG C is warming up to and 24h is reacted in enclosed system.Collecting reaction product obtains Li7MnN4。
In argon gas glove box, Li is accurately weighed7MnN40.0200g, is placed in fixed bed quartz tube reactor.Sample is (1 in reaction atmosphere:3N2/H2Gaseous mixture) be warming up to required temperature, reaction gas flow control in 33mL/min, sampling analysis after 30 minutes.Test result is as shown in Figure 2.Since 300 DEG C, ammonia generating rate is raised and increased with temperature, and 375 DEG C reach maximum generating rate.
Embodiment 3:
In argon gas glove box, MnCl is accurately weighed20.504g, LiH 0.192g, are placed in self-control stainless steel jar mill.After closing ball grinder, load planetary ball mill (Fischt PM400), ball milling condition is 200rpm ball millings 3 hours.Obtain final product sample MnCl2/LiH.In argon gas glove box, MnCl is accurately weighed2/ LiH 0.0400g, are placed in fixed bed quartz tube reactor.Sample is (1 in reaction atmosphere:3N2/H2Gaseous mixture) be warming up to required temperature, reaction gas flow control in 30mL/min, sampling analysis after 30 minutes.Test result is as shown in Figure 3.The catalyst is have synthesis ammonia activity well in low-temperature space, and reactivity is raised and increased with temperature.
Claims (7)
1. a kind of catalyst for synthesizing ammonia, it is characterised in that:The catalyst by main body and
Additive is constituted, and aforementioned body is the nitrogen-containing compound of manganese, and additive includes alkali/alkaline earth metal
One or two or more kinds in hydride, carrier or metal alloy;
Above-mentioned catalyst body is 1000 with the scope of the mass ratio of additive:1 to 1:500.
2. catalyst as claimed in claim 1, it is characterised in that:The nitrogen of described manganese
Compound is MnN, Mn3N2、Mn4N、Mn2N、Li7MnN4In one or more mixed
Compound.
3. catalyst as claimed in claim 1, it is characterised in that:Described carrier is Li2O、
MgO、CaO、SrO、BaO、Al2O3、BN、Si3N4、Mg3N2、Ca3N2, AlN, molecular sieve,
The combination of one or two or more kinds in carbon material, metal-organic framework materials.
4. catalyst as claimed in claim 1, it is characterised in that:Described alkali/alkaline earth gold
Category hydride is LiH, NaH, KH, CsH, MgH2、CaH2、BaH2In one kind or two kinds with
On mixture.
5. catalyst as claimed in claim 1, it is characterised in that:Described metal alloy is:
One or two or more kinds in IV B, V B, VI B, the VII B or VIII B races element shape between Mn
Into two-spot or ternary more than alloy;Above-mentioned IV B, V B, VI B, VII B or VIII B races element
It is the one kind in Ti, Zr, Cr, Mo, W, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt
Or more than two kinds.
6. as claimed in claim 1, it is characterised in that:The catalyst body and additive
The scope of mass ratio is 200:1 to 1:100.
7. the application of catalyst described in a kind of claim 1, it is characterised in that:The catalyst
It is for synthesizing operating condition during ammonia:Sample rises to certain reaction temperature in reaction atmosphere,
Product composition carries out on-line analysis using conductivity meter;Above-mentioned reaction atmosphere is N2、H2Gaseous mixture.
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108080014A (en) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | A kind of vanadium base ammonia synthesis and ammonia decomposition catalyzer and application |
CN109225222A (en) * | 2017-07-11 | 2019-01-18 | 中国科学院上海硅酸盐研究所 | A kind of composite photo-catalyst and its application |
JP2019126776A (en) * | 2018-01-24 | 2019-08-01 | 国立研究開発法人科学技術振興機構 | Catalyst for ammonia synthesis and method for ammonia synthesis using the same |
CN111408393A (en) * | 2020-01-20 | 2020-07-14 | 福州大学 | Ru-based catalyst based on association hydrogenation and chemical chain synthetic ammonia path and preparation method and application thereof |
CN111790428A (en) * | 2020-07-13 | 2020-10-20 | 福州大学 | Co-based interstitial compound catalyst, preparation method and application thereof in ammonia synthesis |
CN112645353A (en) * | 2021-01-27 | 2021-04-13 | 复旦大学 | Method for enhancing selectivity of synthetic ammonia by ball milling nitrogen-hydrogen mixed gas under normal temperature and pressure water phase |
CN112973749A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Catalyst, preparation method and application |
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CN103977828A (en) * | 2013-12-10 | 2014-08-13 | 中国科学院大连化学物理研究所 | Catalyst for ammonia synthesis and ammonia decomposition |
CN104936899A (en) * | 2013-01-22 | 2015-09-23 | 株式会社日本触媒 | Ammonia synthesis method and catalyst for ammonia synthesis |
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EP0490382A1 (en) * | 1990-12-14 | 1992-06-17 | Hoechst Aktiengesellschaft | Process for the preparation of saturated primary fatty amines by hydrogenation of unsaturated fatty nitriles |
CN104936899A (en) * | 2013-01-22 | 2015-09-23 | 株式会社日本触媒 | Ammonia synthesis method and catalyst for ammonia synthesis |
CN103977828A (en) * | 2013-12-10 | 2014-08-13 | 中国科学院大连化学物理研究所 | Catalyst for ammonia synthesis and ammonia decomposition |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108080014A (en) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | A kind of vanadium base ammonia synthesis and ammonia decomposition catalyzer and application |
CN109225222A (en) * | 2017-07-11 | 2019-01-18 | 中国科学院上海硅酸盐研究所 | A kind of composite photo-catalyst and its application |
CN109225222B (en) * | 2017-07-11 | 2021-03-16 | 中国科学院上海硅酸盐研究所 | Composite photocatalyst and application thereof |
JP2019126776A (en) * | 2018-01-24 | 2019-08-01 | 国立研究開発法人科学技術振興機構 | Catalyst for ammonia synthesis and method for ammonia synthesis using the same |
JP7023457B2 (en) | 2018-01-24 | 2022-02-22 | 国立研究開発法人科学技術振興機構 | Ammonia synthesis catalyst and ammonia synthesis method using the catalyst |
CN112973749B (en) * | 2019-12-13 | 2022-04-29 | 中国科学院大连化学物理研究所 | Catalyst, preparation method and application |
CN112973749A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Catalyst, preparation method and application |
CN111408393A (en) * | 2020-01-20 | 2020-07-14 | 福州大学 | Ru-based catalyst based on association hydrogenation and chemical chain synthetic ammonia path and preparation method and application thereof |
CN111408393B (en) * | 2020-01-20 | 2021-06-25 | 福州大学 | Ru-based catalyst based on association hydrogenation and chemical chain synthetic ammonia path and preparation method and application thereof |
CN111790428B (en) * | 2020-07-13 | 2021-09-28 | 福州大学 | Co-based interstitial compound catalyst, preparation method and application thereof in ammonia synthesis |
CN111790428A (en) * | 2020-07-13 | 2020-10-20 | 福州大学 | Co-based interstitial compound catalyst, preparation method and application thereof in ammonia synthesis |
CN112645353A (en) * | 2021-01-27 | 2021-04-13 | 复旦大学 | Method for enhancing selectivity of synthetic ammonia by ball milling nitrogen-hydrogen mixed gas under normal temperature and pressure water phase |
CN112645353B (en) * | 2021-01-27 | 2022-05-20 | 复旦大学 | Method for enhancing selectivity of synthetic ammonia by ball milling nitrogen-hydrogen mixed gas under normal temperature and normal pressure water phase |
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