CN108262034A - A kind of catalyst and preparation method thereof and the application in atmospheric low-temperature synthesizes ammonia - Google Patents
A kind of catalyst and preparation method thereof and the application in atmospheric low-temperature synthesizes ammonia Download PDFInfo
- Publication number
- CN108262034A CN108262034A CN201710001631.9A CN201710001631A CN108262034A CN 108262034 A CN108262034 A CN 108262034A CN 201710001631 A CN201710001631 A CN 201710001631A CN 108262034 A CN108262034 A CN 108262034A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- rhenium
- auxiliary agent
- platinum
- transition metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/36—Rhenium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6567—Rhenium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of synthetic ammonia catalyst under the conditions of atmospheric low-temperature and preparation method thereof, catalyst, which includes, is dispersed in internal diameter as the transition metal nanocluster and main group metal electronic auxiliary in the carbon nanotubes lumen of 1 4nm or so.The unique confinement environment formed due to 1-dimention nano grade straight channels possessed by carbon nanotube, so that the transition metal nanocluster catalyst of its package has high synthesis ammonia activity and stability under the conditions of atmospheric low-temperature, lay a good foundation for the synthetic ammonia catalyst under further exploitation temperate condition.
Description
Technical field
The present invention relates to catalyst technologies, provide a kind of preparation of 25-350 DEG C of ammonia synthesis reaction catalyst of atmospheric low-temperature
Method and its application in atmospheric low-temperature ammonia synthesis reaction.
Background technology
Ammonia is a kind of important inorganic chemical product, and industrial year output is about 0.16 hundred million tons, higher than other any one
Kind chemicals [M.Kitano, etal., Ammonia synthesis using a stable electride as an
electron donor and reversible hydrogen store,Nat.Chem.2012,4(11):934-940],
In 80% for producing chemical fertilizer, 20% for producing the raw material of other chemicals.N2It is most stable of several in nature
One of simple material, N ≡ N bond energys are up to 945kJ/mol, and being broken the key needs high energy, therefore by N2Molecule directly turns
Being melted into ammonia kinetically has greatly obstruction.At present, industrially synthesis ammonia mainly using Harber-Bosch techniques, that is, exists
Under the conditions of high temperature (300-500 DEG C) and high pressure (200-300bar), N2And H2Ammonia is generated in Fe bases catalyst surface, it is extremely harsh
Reaction condition cause this technique huge energy consumption, the energy consumed every year is the 1.4% of world energy consumption total amount
[Cornelis J.M., et al., Challenges in reduction of dinitrogen by proton and
electron transfer,Chem.Soc.Rev.2014,43(15),5183-5191].Therefore it develops a kind of novel mild
Under the conditions of the ammonia catalyst that efficiently synthesizes be of great significance, an also always significant challenge of region of chemistry.
About the synthetic ammonia catalyst under temperate condition, some progress have been obtained in recent years.In nature, the micro- life of fixed nitrogen
Nitrogen in air can be reduced directly to ammonia by object using internal azotase under conditions of normal temperature and pressure.Biological nitrogen fixation no matter from
Condition or production capacity needed for it all greatly exceed chemical nitrogen fixation, therefore from the sixties in last century, grind both at home and abroad
Study carefully personnel and a series of further investigations have been carried out to chemical simulation biological nitrogen fixation.Wherein the most successful catalyst system and catalyzing is molybdenum base dinitrogen
Complex systems, Schrock report a kind of monokaryon molybdenum base dinitrogen complex catalyst using triamido amine as ligand in 2003,
Under suitable proton source and the auxiliary of reducing agent, the direct catalysis reduction of nitrogen under normal temperature and pressure conditions is realized for the first time
[D.V.Yandulov, et al., Catalytic Reduction of Dinitrogen to Ammonia at a Single
Molybdenum Center,Science.2003,301(5629),76-78].Using similar method, Nishibayashi in
A kind of double molybdenum dinitrogen complex catalysts with PNP pincer ligands are reported within 2011, successfully by nitrogen on single molybdenum center
Turn over number is increased to 12 [K.Arashiba, et al., A molybdenum complex bearing from the 4 of Schrock systems
PNP-type pincer ligands leads to the catalytic reduction of dinitrogen into
ammonia,Nat.Chem.2011,3(2),120-125].Although these homogeneous systems realize the direct of nitrogen under normal temperature and pressure
Catalyzed conversion, but its conversion is stoichiometric relative to metal center.In addition, the proton source and reducing agent that use according to it,
The energy that unit mole of nitrogen is reduced to needed for two moles of ammonia calculated is respectively 580kJ mol-1(Schrock systems) and
700kJ mol-1(Nishibayashi systems) [F.Neese, et al., The Yandulov/Schrock Cycle and
the Nitrogenase Reaction:Pathways of Nitrogen Fixation Studied byDensity
Functional Theory, Angew.Chem., Int.Ed., 2006,45 (2), 196-199], it is above Harber-Bosch
Technique (485kJ mol-1).In addition to homogeneous catalysis system, the heterogeneous catalysis synthesis ammonia under temperate condition also achieves certain grind
Study carefully progress.Kitano etc. reports a series of Ru catalyst that electron compounds support in recent years, the table in ordinary-pressure synthesis of ammonia reaction
Excellent catalytic activity [Ammonia synthesis using a stable electride as an are revealed
electron donor and reversible hydrogen store,Nat.Chem.2012,4(11):934-940；
Essential role of hydride ion in ruthenium-based ammonia synthesis catalysts,
Chem.Sci.2016,7,4036-4043].Ordinary-pressure synthesis of ammonia reaction (can detect ammonia, the ratio of catalyst down to 200 DEG C
Activity reaches 0.71mol NH3mol Ru-1h-1, hence it is evident that better than other Ru base catalyst reported in the past.But ruthenium is higher
Price is its widely applied big obstacle.
Patent application CN106064097A discloses a kind of room temperature synthetic ammonia catalyst, is related to using basic bismuth carbonate BSC
Gold-supported Au catalyst, but the content of noble metal gold is up to 20%-80%, and method for preparing catalyst is numerous in catalyst
It is trivial, it is related to five steps, production cost is excessively high, and therefore, application industrially has significant limitation.
Patent application CN103977828A discloses a kind of nitrogenous compound of major element and relevant carriers and additive
Synthetic ammonia catalyst, but involved ammonia synthesis reaction temperature is very high (400 DEG C), high energy consumption.
In conclusion the synthetic ammonia catalyst research under temperate condition has obtained some progress, but can not also much realize
Industrialization.How existing basic theory and technology are used for reference, and R ＆ D design goes out the superior synthetic ammonia catalyst of performance, and reduces
Catalyst cost need further to study.
Carbon nanotube due to its unique 1-dimention nano grade straight channels, high-graphitized tube wall, high-specific surface area with
And good conductor electrically and thermally and receive the researcher concern of catalytic field.Carbon nanotube maximum compared with other carbon materials
Difference lies in its quasi-one-dimensional nanoscale luminal structures, and metallic catalyst is assembled into the nano pore and can obtain by carbonaceous material
Expect the nano-reactor formed.The metallic catalyst of multi-walled carbon nanotube package reported on document in recent years is in a series of catalysis
It is all shown in reaction compared to the superior catalytic performance of catalyst outside pipe, shows collaboration confinement effect
[X.L.Pan,X.H.Bao,Reactions over catalysts confined in carbon nanotubes,
Chem.Commun.,2008,6271—6281；X.L.Pan,X.H.Bao,The Effects of Confinement
inside Carbon Nanotubes on Catalysis,Acc.Chem.Res.,2011,553-562.].This collaboration limit
Domain effect is caused by the unique structure of carbon nanotube, is that its space restriction effect makes its packet first including several aspects
The metal nanoparticle wrapped up in is not easy to grow up during the reaction, keeps the stabilization of particle at a higher temperature；Further, since stone
The curvature in black alkene face makes pi-electron to pipe external migration, a unique electronics confinement environment being formd in pipe, passes through phase in pipe
Interaction can modify a series of structure of metals or metal oxide and property [W Chen, X.L.Pan, X.H.Bao, Tuning
of Redox Properties of Iron and Iron Oxides via Encapsulation within Carbon
Nanotubes,J.Am.Chem.Soc.2007,129,7421-7426；J.P.Xiao,X.L.Pan,X.H.Bao,Toward
Fundamentals of Confined Catalysis in Carbon Nanotubes,J.Am.Chem.Soc.2015,
137,477-482]；It is furthermore interesting that in the space of carbon nanotube confinement, reactant molecule can selectively be enriched with [J,
Guan,X.L.Pan,Syngas Segregation Induced by Confinement in Carbon Nanotubes:A
Combined First-Principles and Monte Carlo Study,J.Phys.Chem.C.2009,113(52),
21687-21692；H.B.Zhang,X.L.Pan,X.H.Bao,Enhancing chemical reactions in a
confined hydrophobic environment:an NMR study of benzene hydroxylation in
Carbon nanotubes, Chem.Sci., 2012,4 (3), 1075-1078], so as to reduce the apparent pressure of reaction.Pipe with small pipe diameter
Carbon nanotube has smaller caliber compared to multi-walled pipes, and the curvature of bigger shows stronger confinement effect in catalysis is reacted
[J.P.Xiao,X.L.Pan,X.H.Bao,Size-dependence of carbon nanotube confinement in
catalysis,Chem.Sci.2016].However, pipe with small pipe diameter carbon pipe confinement catalyst is limited by technology of preparing and is rarely had at present
Report is also always a bottleneck.
Invention content
Present invention solves the technical problem that one of be to provide a kind of catalyst and can be used for synthesis under the conditions of atmospheric low-temperature
In ammonia reaction, high activity and high stability are shown, catalyst specific activity is up to 1279- under the conditions of normal pressure and 25-350 DEG C
47631mmol NH3mol metal-1h-1, and monitor 140 hours or more catalyst activities on-line and keep stablizing.
Present invention solves the technical problem that two be to provide a kind of efficient preparation method, prepare main group metal doping
The transition metal nanocluster catalyst of pipe with small pipe diameter carbon nanotube confinement.
One of to solve above-mentioned technical problem, the technical solution adopted by the present invention is as follows：
A kind of catalyst, including：
Carbon nanotube is carrier；(carbon nanotube is surplus)
Transition metal nanocluster inside carbon nanotubes lumen is scattered in for catalytically-active metals, mass content 0.1-
10%；The transition metal refers to the one or two or more kinds in iron, ruthenium, rhenium, platinum；
Main group metal simple substance or main group metal alloy are auxiliary agent, mass content 5-50%.
The catalytically-active metals, mass content are preferably 0.1-2%；Auxiliary agent mass content is preferably 20-30%.
The carbon nanotube is lumen diameter in the thin wall carbon nano-tube of 1-4nm, preferably 1-2nm.
The auxiliary agent refers to I A, II A, III A races element, including one kind in Li, Na, K, Rb, Cs, Mg, Ca, Ba, Al or
It is two or more；For transition metal iron, preferred auxiliary agent is Na, K；For rhenium, platinum, preferred auxiliary agent is Na, K, Rb, Cs；It is right
In ruthenium, preferred auxiliary agent is Ca, Ba, Cs.
A kind of preparation method of catalyst, includes the following steps：
A) original carbon nanotubes are dispersed in the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid, are ultrasonically treated 4-7h, are purified
It truncates, vacuum freeze drying 70-100h is open and truncated carbon nanotube, labeled as s-TWCNT.
B) s-TWCNT is handled into 3-5h for 700-1000 DEG C in H2 or Ar, to go surface generation in deacidification processing procedure
Oxygen-containing functional group.
C) load of transition metal：By the processed carriers of step b), with a certain amount of organometallic compounds or its
He is sealed in Filled with Quartz device metal salt presoma, as a vapor carry out gas phase filling, wherein metal precursor and
The mass ratio 0.5-20 of carbon pipe obtains being filled with the carbon pipe compound of metal precursor in pipe, by compound methanol, ethyl alcohol or first
Benzene solvent elutes, and outer metal precursor is managed, then compound is carried out heat point in oxidation, reduction or inert atmosphere with preliminary removal
Solution, it is the inert atmosphere that amount containing O2 is 20-100% (volumn concentration) to thermally decompose required oxidizing atmosphere；Reducing atmosphere
To contain the inert atmosphere that H2 is 10-100% (volumn concentration)；Inert atmosphere be one kind in N2, Ar, He or it is a kind of with
On；It is normal pressure -8MPa to thermally decompose pressure；Heat decomposition temperature is 100-400 DEG C.
D) rear catalyst will be decomposed at 200-500 DEG C, with a certain amount of hydrogen reducing 1-5h, the catalysis restored
Agent.Hydrogen flowing quantity 20-50mL/min.
E) doping of co-catalyst：The catalyst seal that step d) has been restored is placed in argon gas glove box, by certain ratio
Example is uniform with main group metal simple substance or alloy ground and mixed and small in 100-200 DEG C of stir-activating 10-16 in an inert atmosphere
When, obtain activated catalyst.
The metal precursor is the one or two or more kinds of volatile organometallic compound or metal salt.
It is that ferrocene, tertiary butyl ferrocene, ring are pungent to prepare volatile organometallic compound used by ferrum-based catalyst
One or two or more kinds in tetraene iron tricarbonyl, cyclohexadiene iron tricarbonyl, carbonyl iron；Ferrum-based catalyst is prepared (to be used
Volatile metal salt refer to one or two or more kinds in iron chloride, ferric nitrate；Prepare volatility used by rhenium-based catalyst
Organometallic compounds be three oxygen rhenium of methyl, ten carbonyls, two rhenium, one kind in cyclopentadiene rhenium tri carbonyl compound or two kinds with
On；It prepares volatile metal salt used by rhenium-based catalyst and refers to chlorination rhenium (III), one kind in chlorination rhenium (V) or two kinds；
It is acetylacetone,2,4-pentanedione platinum (II) to prepare volatile organometallic compound used by platinum based catalyst, 1,1,1,5,5,5- hexafluoro second
Acyl acetone platinum (II), Π-cyclopentadiene (trimethyl) platinum (IV), (trimethyl) methyl cyclopentadiene close one kind in platinum (IV) or
Two kinds or more.
For the application in atmospheric low-temperature ammonia synthesis reaction, the atmospheric low-temperature ammonia synthesis reaction method is catalyst：
By the catalyst in the hydrogen atmosphere of 300-400 DEG C of normal pressure in-situ reducing 30-120min, be down in hydrogen atmosphere certain
Temperature after rise to reaction temperature, be switched to normal pressure nitrogen and hydrogen mixture, the nitrogen and hydrogen mixture volume compares N2：H2=1:3-3:1,
Reaction gas flow velocity is 1-50mL/min, and reaction temperature is 25-350 DEG C, obtains ammonia product.
The advantages of the present invention over the prior art are that：
(1) existing industry synthetic ammonia is mainly using molten iron and carbon supported precious metal ruthenium catalyst, involved reaction
Condition is extremely harsh, generally requires high temperature (400-500 DEG C) and high pressure (20-40MPa), high energy consumption, simultaneously because fuel disappears
It consumes and gives off great amount of carbon dioxide.In contrast, the carbon nanotube of great specific surface area by the use of internal diameter less than 4nm is as carrier,
The transition metal nanocluster that packed height is disperseed in its tube chamber, and carries out the doping of main group metal auxiliary agent, prepared by carbon
Nanotube confinement transition metal nanocluster catalyst has very high reaction under the mild reaction conditions of atmospheric low-temperature
Activity.Compared to other traditional synthetic ammonia catalysts, the transition metal nanometer of this unique texture by carbon nanotube package
Cluster catalyst, since carbon pipe tube chamber acts on the selective enrichment of gas molecule, i.e., nitrogen molecule can be effectively in pipe
Preferential adsorption, and ammonia molecule is then mainly distributed on outside pipe and carbon nanotube is to the electricity of transition metal nanocluster catalyst
Sub- promotor action can effectively accelerate the progress of reaction.Under the reaction condition of 25-350 DEG C of normal pressure, gained activity is current institute
4-8 times of the active optimal noble metal ruthenium-based catalyst of report, significantly improves ammonia synthesis reaction efficiency, with patent application
CN103977828A improves catalyst activity compared to reaction temperature is significantly reduced.
(2) the transition metal nanocluster catalyst of carbon nanotube package of the present invention is a kind of nanometer with new structure
Catalyst, during the reaction can utilize carbon nanotubes lumen, transition metal nanocluster and reactant molecule three it
Between cooperative interaction and modulation response path, so as to change reaction rate, improve catalyst stability.
(3) the transition metal nanocluster catalyst of carbon nanotube package of the present invention reacts shown catalysis to catalysis
Confinement effect often enhances with the reduction of lumen diameter, therefore thin wall carbon nano-tube of the lumen diameter less than 4nm is compared
It is more advantageous to improving the performance of catalyst for multi-walled carbon nanotube of the lumen diameter more than 4-10nm.
(4) it is that the preprocess method of (a) carbon nanotube is efficient the advantages of method for preparing catalyst of the present invention, through nitration mixture
After processing it is obtained opening and truncated carbon nanotube yield be up to more than 90%；(b) transition metal nanocluster load side
Method can be selectively in hollow carbon nanotubes lumen internal load transition metal nanocluster, and gained produces after oxidized reduction
More than 85% transition metal nanocluster confinement is inside carbon nanotubes lumen in product；(c) preparation method is simple, efficiently, can criticize
Amount prepares the gram quantity grade for being catalyzed reaction evaluating.
Description of the drawings
Fig. 1 (A) is the angle of elevation annular dark (HAADF-STEM) of Fe@TWCNT catalyst；(B) high score of Ru@TWCNT
Distinguish transmission electron microscope (HRTEM) figure；(C) high-resolution-ration transmission electric-lens (HRTEM) figure of Re@TWCNT；
Fig. 2 is K-Fe@TWCNT, K-PtRe@TWCNT, K-Fe/TWCNT, K-Fe@CB, K-Fe@MWCNT, K-Fe/MWCNT
And Ru/Ca2N:e-Catalyze and synthesize the test of ammonia reactivity；
Fig. 3 is stability tests of the K-Fe@TWCNT at 200 DEG C of normal pressure.
Specific embodiment
To further illustrate the present invention, specific examples below is enumerated, but scope of the presently claimed invention is not by this
The limitation of a little embodiments.Meanwhile embodiment has been merely given as realizing the partial condition of this purpose, but does not mean that and must satisfy this
A little conditions can just reach this purpose.
Embodiment 1
4 parts of 60mg few-wall carbon nanotubes (TWCNTs) are respectively put into four 100 milliliters of round-bottomed flasks, are separately added into
60mL nitration mixture (the concentrated sulfuric acids：Concentrated nitric acid=3:1) it, while is put into ultrasonic water bath, is ultrasonically treated 5.5 hours, bath temperature maintains
Each 45mL of supernatant is taken after 40-50 DEG C, supersound process, is eluted to neutrality, and vacuum freeze drying 90h.By dry sample
4h, argon flow amount 50mL/min are handled in 1000 DEG C of argon gas, it is for use to be cooled to room temperature taking-up.
220mg few-wall carbon nanotubes (s-TWCNTs) are obtained after purification by truncating, and yield is up to 96%, and truncated carbon
Length of tube is evenly distributed on 0.4-1.0 μm, and tube chamber is hollow, and purity is higher than more than 95%.
The preparation of 2 K-Fe@TWCNT catalyst of embodiment
(1) the truncated carbon nanotubes of 100mg (s-TWCNTs) are put into vacuum-filling device, tri- carbonyl rings of 38mg is pungent
Tetraene iron is put into the vacuum plant other end.1 × 10-4The program of device for being placed with carbon nanotube is warming up under Pa vacuum conditions
450 DEG C, heating rate is 5 DEG C/min, 450 DEG C of constant temperature 16 hours.Carbon nanotube and presoma are mixed under vacuum after cooling,
Again in 80 DEG C of oven 72h.
(2) filled sample is fully eluted with toluene, after removing the outer remaining Fe presomas of pipe, filtering, 60 DEG C of bakings
Dry 100 DEG C of high pressure oxygens aoxidized 24 hours overnight, then with 2M nitric acid stir process 1 hour, filtering, again 60 DEG C of drying overnight,
450 DEG C of hydrogen reducing 5h obtain the 1wt.%Fe@TWCNTs catalyst of reduction.
(3) catalyst seal restored is placed in argon gas glove box, takes 50mg, add in 26 μ L KNa alloys, grinding
It is uniformly mixed, and obtains activated catalyst K-Fe@TWCNT in 150 DEG C of stir-activatings 12 hours in an inert atmosphere.
The pattern of catalyst morphology and middle Fe are as shown in the A in Fig. 1, by electromicroscopic photograph it can be seen that Fe nanometer particles are in pipe
For diameter to have carried out efficient filling in few-wall carbon nanotube, filling rate is up to more than 85%.Its ammonia synthesis reaction active testing result
As shown in Fig. 2, activity is up to 1279-47631mmol NH at 160-320 DEG C of normal pressure3mol metal-1h-1, it is carbon nanotube
5-15 times of the outer transition metal nanocluster catalyst K-Fe/TWCNT loaded of pipe.The results are shown in Figure 3 for its stability test,
At 200 DEG C of normal pressure, monitor 140 hours or more catalyst activities on-line and keep stablizing.
The preparation of embodiment 3Cs-Ru@TWCNT catalyst
(1) the truncated carbon nanotubes of 100mg (s-TWCNTs) are put into vacuum-filling device, by 2.5mg bis- (2,4- bis-
Methylpentadiene) ruthenium is put into the vacuum plant other end.1.5 × 10-4The device journey that will be placed with carbon nanotube under Pa vacuum conditions
Sequence is warming up to 450 DEG C, and heating rate is 5 DEG C/min, 450 DEG C of constant temperature 16 hours.By carbon nanotube and presoma true after cooling
Sky is lower to be mixed, then in 120 DEG C of oven 48h.
(2) filled sample is fully eluted with toluene, after removing the outer remaining Ru presomas of pipe, filtering, 60 DEG C of bakings
It does overnight, 450 DEG C of hydrogen reducing 5h, obtains the 1wt.%Ru@TWCNT catalyst of reduction.
(3) catalyst seal restored is placed in argon gas glove box, takes 50mg, added in 26 μ L Cs metal simple-substances, grind
Mill is uniformly mixed, and obtains activated catalyst Cs-Ru@TWCNT in 100 DEG C of stir-activating 12h in an inert atmosphere.
The pattern of catalyst morphology and middle Ru are as shown in the B in Fig. 1, by electromicroscopic photograph it can be seen that ruthenium nano particle is few
Efficient filling has been carried out in wall carbon nano tube and has been uniformly dispersed, filling rate is up to more than 85%.
The preparation of embodiment 4K-Re@TWCNT catalyst
(1) the truncated carbon nanotubes of 100mg (s-TWCNTs) are put into vacuum-filling device, by three oxygen rhenium of 3mg methyl
It is put into the vacuum plant other end.1.5 × 10-4The program of device for being placed with carbon nanotube is warming up to 450 DEG C under Pa vacuum conditions,
Heating rate is 5 DEG C/min, 450 DEG C of constant temperature 16 hours.Carbon nanotube and presoma are mixed under vacuum after cooling, then 90
DEG C oven 48h.
(2) filled sample is fully eluted with toluene, after removing the outer remaining Re presomas of pipe, filtering, 60 DEG C of bakings
It does overnight, 450 DEG C of hydrogen reducing 5h, obtains the 2wt.%Re@TWCNT catalyst of reduction.
(3) catalyst seal restored is placed in argon gas glove box, takes 50mg, add in 26 μ L KNa alloys, grinding
It is uniformly mixed, and obtains activated catalyst K-Re@TWCNT in 100 DEG C of stir-activating 12h in an inert atmosphere.
The pattern of catalyst morphology and middle Re are as shown in the C in Fig. 1, by electromicroscopic photograph it can be seen that rhenium nano-particle is few
Efficient filling has been carried out in wall carbon nano tube and has been uniformly dispersed, filling rate is up to more than 85%.
The preparation of embodiment 5K-Pt@TWCNT catalyst
(1) the truncated carbon nanotubes of 100mg (s-TWCNTs) are put into vacuum-filling device, by 2mg cyclopentadiene (three
Methyl) platinum is put into the vacuum plant other end.1.5 × 10-4The program of device for being placed with carbon nanotube is heated up under Pa vacuum conditions
To 450 DEG C, heating rate is 5 DEG C/min, 450 DEG C of constant temperature 16 hours.Carbon nanotube and presoma are mixed under vacuum after cooling
It closes, then in 80 DEG C of oven 48h.
(2) filled sample is fully eluted with toluene, after removing the outer remnants Pt presomas of pipe, filtering, 60 DEG C of drying
Overnight, 450 DEG C of hydrogen reducing 5h obtain the 1.5wt.%Pt@TWCNT catalyst of reduction.
(3) catalyst seal restored is placed in argon gas glove box, takes 50mg, add in 26 μ L KNa alloys, grinding
It is uniformly mixed, and obtains activated catalyst K-Pt@TWCNT in 100 DEG C of stir-activating 12h in an inert atmosphere.
Nano platinum particle carried out in few-wall carbon nanotube it is efficient fill and uniformly disperse, filling rate be up to 85% with
On.
6 K-Re of embodiment2Ru1The preparation of@TWCNT catalyst
(1) the truncated carbon nanotubes of 100mg (s-TWCNTs) are put into vacuum-filling device, by three oxygen rhenium of 3mg methyl
The vacuum plant other end is put into bis- (2,4- dimethyl pentadienes) rutheniums of 2.5mg.1.5 × 10-4It will be placed under Pa vacuum conditions
The program of device of carbon nanotube is warming up to 450 DEG C, and heating rate is 5 DEG C/min, 450 DEG C of constant temperature 16 hours.Carbon is received after cooling
Mitron and presoma mix under vacuum, then in 120 DEG C of oven 48h.
(2) filled sample is fully eluted with toluene, after removing the outer remaining Re and Ru presomas of pipe, filtering, 60
Overnight, 450 DEG C of hydrogen reducing 5h obtain the Re of reduction for DEG C drying2Ru1@TWCNT catalyst.
(3) catalyst seal restored is placed in argon gas glove box, takes 50mg, add in 26 μ L KNa alloys, grinding
It is uniformly mixed, and obtains activated catalyst K-Re in 100 DEG C of stir-activating 12h in an inert atmosphere2Ru1@TWCNT。
Ruthenium rhenium alloys nano-particle has carried out efficient filling and has been uniformly dispersed in few-wall carbon nanotube, and filling rate is up to
More than 85%, it measures two kinds of metal molars through EDX power spectrums and compares Re：Ru=2：1.
7 K-Pt of embodiment1Re1The preparation of@TWCNT catalyst
(1) the truncated carbon nanotubes of 100mg (s-TWCNTs) are put into vacuum-filling device, by three oxygen of 1.5mg methyl
Rhenium and 1.5mg cyclopentadiene (trimethyl) platinum are put into the vacuum plant other end.1.5 × 10-4Carbon will be placed under Pa vacuum conditions
The program of device of nanotube is warming up to 450 DEG C, and heating rate is 5 DEG C/min, 450 DEG C of constant temperature 16 hours.By carbon nanometer after cooling
Pipe and presoma mix, then under vacuum in 90 DEG C of oven 48h.
(2) filled sample is fully eluted with toluene, after removing the outer remaining Re and Pt presomas of pipe, filtering, 60
Overnight, 450 DEG C of hydrogen reducing 5h obtain the Pt of reduction for DEG C drying1Re1@TWCNT catalyst.
(3) catalyst seal restored is placed in argon gas glove box, takes 50mg, add in 26 μ L KNa alloys, grinding
It is uniformly mixed, and obtains activated catalyst K-Pt in 100 DEG C of stir-activating 12h in an inert atmosphere1Re1@TWCNT。
Platinum rhenium alloys nano-particle has carried out efficient filling and has been uniformly dispersed in few-wall carbon nanotube, and filling rate is up to
More than 85%, it measures two kinds of metal molars through EDX power spectrums and compares Pt：Re=1：1, ammonia synthesis reaction active testing result such as Fig. 2
It is shown, ammonia reactivity is catalyzed and synthesized at 160-320 DEG C of normal pressure as 40-7010mmol NH3mol metal-1h-1。
8 ammonia synthesis reaction performance test of embodiment
The activity rating of ammonia synthesis reaction K-Fe@TWCNT catalyst, carries out in continuous fixed bed.It is anti-in miniature quartz
Ying Guanzhong is added in【Embodiment 1】10 milligrams of Fe catalyst, after the reduction 80 minutes of 400 DEG C of atmospheric hydrogen, cool to 160 DEG C,
It is switched to normal pressure nitrogen and hydrogen mixture (volume ratio N2：H2=1:3), reaction gas flow velocity is 5mL/min, is existed with flight time mass spectrum
Line continuously detects the production quantity of ammonia, and after 160 DEG C of reactions carry out 9 hours, reaction reaches balance, is warming up to 200 DEG C, 6h activity
After stabilization, 240 DEG C, after 2h is activity stabilized are warming up to, is warming up to 280 DEG C, after activity stabilized after 1h, is warming up to 320 DEG C, it is living after 6h
Property stablize.The NH generated using unit interval unit mass metal3Molal quantity reflect the catalyst at different temperatures
Active (as shown in Figure 2).
The preparation of 1 K-Fe/TWCNT catalyst of comparative example
(1) the truncated carbon nanotubes of 100mg (s-TWCNTs) are added in beaker, instill dropwise contain three under stiring
The toluene solution (mass percentage of Fe relative to TWCNT be 0.1-2%) of carbonyl cyclo-octatetraene iron is stirred to dry, 60 DEG C
Overnight, 450 DEG C of hydrogen reducings 5 hours obtain the Fe/TWCNTs catalyst of reduction for drying.
(2) catalyst seal restored is placed in argon gas glove box, takes 50mg, add in 26 μ L KNa alloys, grinding
It is uniformly mixed, and obtains activated catalyst K-Fe/TWCNT in 150 DEG C of stir-activatings 12 hours in an inert atmosphere.
Comparative catalyst of the K-Fe/TWCNT catalyst for the load iron nanocluster outside few-wall carbon nanotube pipe, synthesis
Ammonia reactivity test result at 160-320 DEG C of normal pressure as shown in Fig. 2, catalyze and synthesize ammonia reactivity as 27-9203mmol
NH3mol metal-1h-1, the 2-18% of the transition metal nanocluster catalyst only loaded in carbon nanotube pipe, efficiency pole
It is low.
The preparation of 2 K-Fe@CB catalyst of comparative example
(1) 100mg carbon blacks (Carbon Black) addition is put into vacuum-filling device, tri- carbonyl rings of 4.5mg is pungent
Tetraene iron is put into the vacuum plant other end.1 × 10-4The program of device for being placed with carbon black is warming up to 450 DEG C under Pa vacuum conditions,
Heating rate is 5 DEG C/min, 450 DEG C of constant temperature 16 hours.Carbon black and presoma are mixed under vacuum after cooling, then in 80 DEG C of bakings
Case handles 72h.450 DEG C of hydrogen reducing 5h obtain the 1wt.%Fe@CB catalyst of reduction.
(2) catalyst seal restored is placed in argon gas glove box, takes 50mg, add in 26 μ L KNa alloys, grinding
It is uniformly mixed, and obtains activated catalyst K-Fe@CB in 150 DEG C of stir-activatings 12 hours in an inert atmosphere.
K-Fe@CB catalyze and synthesize ammonia reactivity as 17-1370mmol NH at 160-280 DEG C of normal pressure3mol metal- 1h-1, the 1-5% of the transition metal nanocluster catalyst of load, extremely inefficient only in carbon nanotube pipe.
The preparation of 3 K-Fe@MWCNT catalyst of comparative example
(1) 4 parts of 60mg multi-walled carbon nanotubes (MWCNTs) are respectively put into four 100 milliliters of round-bottomed flasks, added respectively
Enter 60 milliliters of nitration mixture (concentrated sulfuric acids：Concentrated nitric acid=3:1) it, while is put into ultrasonic water bath, is ultrasonically treated 5.5 hours, bath temperature
40-50 DEG C is maintained, each 45 milliliters of supernatant is taken after supersound process, is eluted to neutrality, and vacuum freeze drying 90h.By drying
Sample 4h, argon flow amount 50mL/min are handled in 1000 DEG C of argon gas.
(2) the truncated carbon nanotubes of 100mg (s-MWCNTs) are put into vacuum-filling device, tri- carbonyl rings of 38mg is pungent
Tetraene iron is put into the vacuum plant other end.1 × 10-4The program of device for being placed with carbon nanotube is warming up under Pa vacuum conditions
450 DEG C, heating rate is 5 DEG C/min, 450 DEG C of constant temperature 16 hours.Carbon nanotube and presoma are mixed under vacuum after cooling,
Again in 80 DEG C of oven 72h.
(3) filled sample is fully eluted with toluene, after removing the outer remaining Fe presomas of pipe, filtering, 60 DEG C of bakings
Dry 100 DEG C of high pressure oxygens aoxidized 24 hours overnight, then with 2M nitric acid stir process 1 hour, filtering, again 60 DEG C of drying overnight,
450 DEG C of hydrogen reducing 5h obtain the 1wt.%Fe@MWCNTs catalyst of reduction.
(4) catalyst seal restored is placed in argon gas glove box, takes 50mg, add in 26 μ L KNa alloys, grinding
It is uniformly mixed, and obtains activated catalyst K-Fe@MWCNT in 150 DEG C of stir-activatings 12 hours in an inert atmosphere.
Comparative catalyst of the K-Fe@MWCNT catalyst for the load iron nanocluster in multi-walled carbon nanotube pipe, synthesis
Ammonia reactivity test result at 160-320 DEG C of normal pressure as shown in Fig. 2, catalyze and synthesize ammonia reactivity as 0-1396mmol
NH3mol metal-1h-1, the 0-2% of the transition metal iron nanocluster catalyst only loaded in carbon nanotube pipe, efficiency pole
It is low.
The preparation of 4 K-Fe/MWCNT catalyst of comparative example
(1) 4 parts of 60mg multi-walled carbon nanotubes (MWCNTs) are respectively put into four 100 milliliters of round-bottomed flasks, added respectively
Enter 60 milliliters of nitration mixture (concentrated sulfuric acids：Concentrated nitric acid=3:1) it, while is put into ultrasonic water bath, is ultrasonically treated 5.5 hours, bath temperature
40-50 DEG C is maintained, each 45 milliliters of supernatant is taken after supersound process, is eluted to neutrality, and vacuum freeze drying 90h.By drying
Sample 4h, argon flow amount 50mL/min are handled in 1000 DEG C of argon gas.
(2) the truncated carbon nanotubes of 100mg (s-MWCNTs) are added in beaker, instill dropwise contain three under stiring
The toluene solution (mass percentage of Fe relative to MWCNT be 0.1-2%) of carbonyl cyclo-octatetraene iron is stirred to dry, 60 DEG C
Overnight, 450 DEG C of hydrogen reducings 5 hours obtain the Fe/MWCNTs catalyst of reduction for drying.
(3) catalyst seal restored is placed in argon gas glove box, takes 50mg, add in 26 μ L KNa alloys, grinding
It is uniformly mixed, and obtains activated catalyst K-Fe/MWCNT in 150 DEG C of stir-activatings 12 hours in an inert atmosphere.
Comparative catalyst of the K-Fe/MWCNT catalyst for the load iron nanocluster outside multi-walled carbon nanotube pipe, synthesis
Ammonia reactivity test result at 160-320 DEG C of normal pressure as shown in Fig. 2, catalyze and synthesize ammonia reactivity as 0-956mmol
NH3mol metal-1h-1, the 0-2% of the transition metal iron nanocluster catalyst only loaded in carbon nanotube pipe, efficiency pole
It is low.
As a comparison, K-Fe/TWCNT, K-Fe@CB, K-Fe@MWCNT, it is anti-that K-Fe/MWCNT catalyzes and synthesizes ammonia to comparative example 5
The test condition for answering performance is identical with embodiment 8, is carried out in continuous fixed bed.Phase is added in miniature quartz reaction tube
10 milligrams of the catalyst answered after the reduction 80 minutes of 400 DEG C of atmospheric hydrogen, cools to 160 DEG C, is switched to normal pressure nitrogen and hydrogen mixture
(volume ratio N2：H2=1:3), reaction gas flow velocity is 5mL/min, with the generation of flight time mass spectrum on-line continuous detection ammonia
Amount, after 160 DEG C of reactions carry out 9 hours, reaction reaches balance, is warming up to 200 DEG C, after 6h is activity stabilized, is warming up to 240 DEG C,
After 2h is activity stabilized, 280 DEG C are warming up to, after activity stabilized after 1h, is warming up to 320 DEG C, it is activity stabilized after 6h.Utilize the unit interval
The NH that unit mass metal is generated3Molal quantity reflect the activity (as shown in Figure 2) of catalyst at different temperatures.
It is dispersed in it can be seen from above example 8 and comparative example 5 in carbon nanotubes lumen of the internal diameter for 1-4nm or so
Transition metal nanocluster catalyst under the reaction condition of 160-320 DEG C of normal pressure activity be significantly higher than multi-walled carbon nanotube
The transition metal nanocluster catalyst loaded outside interior, carbon black and carbon nanotube pipe, shows by using pipe with small pipe diameter carbon nanotube
Intraluminal confinement effect can significantly improve the ammonia synthesis reaction efficiency under temperate condition, and ammonia is efficiently synthesized for further exploitation
Catalyst provides thinking and method.
Above example is provided just for the sake of the description purpose of the present invention, and is not intended to limit the scope of the present invention.This
The range of invention is defined by the following claims.It the various equivalent replacements that do not depart from spirit and principles of the present invention and make and repaiies
Change, should all cover within the scope of the present invention.
Claims (14)
1. a kind of catalyst, it is characterised in that including：
Carbon nanotube is carrier；
The transition metal nanocluster being scattered in inside carbon nanotubes lumen is catalytically-active metals, and mass percentage content is
0.1-10%, filling rate is more than 85% in carbon pipe tube chamber；The transition metal refers to one kind or two kinds in iron, ruthenium, rhenium, platinum
More than；
Main group metal simple substance or main group metal alloy are auxiliary agent, mass percentage content 5-50%.
2. catalyst according to claim 1, it is characterised in that：The catalytically-active metals, mass content are preferably
0.1-2%；Auxiliary agent mass content is preferably 20-30%.
3. catalyst according to claim 1 or 2, it is characterised in that：The carbon nanotube is lumen diameter 1-4nm's
Thin wall carbon nano-tube, preferably 1-2nm.
4. catalyst according to claim 1 or 2, it is characterised in that：The auxiliary agent refers to I A, II A, III A races element, packet
Include one or more of Li, Na, K, Rb, Cs, Mg, Ca, Ba, Al；For transition metal iron, preferred auxiliary agent for Na,
K；For rhenium, platinum, preferred auxiliary agent is Na, K, Rb, Cs；For ruthenium, preferred auxiliary agent is Ca, Ba, Cs.
5. a kind of preparation method of catalyst, it is characterised in that include the following steps：
(1) pretreatment of carbon nanotube：Original carbon nanotubes are dispersed in the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid, at ultrasound
Reason, filtering elute to neutrality, vacuum freeze-drying, hydrogen or argon gas high temperature processing 3-5h, obtain nozzle and open and cut
Short carbon nanotube；
(2) transition metal nanocluster carrying method：Spare carbon pipe is encapsulated in container, container is made to evacuate dehydration, vacuum degree
Reach 10-2Pa is hereinafter, transition metal precursor gasification is passed into carbon pipe, and is maintained 24-50 hours at 70-100 DEG C, by institute
Obtained product heat resolve in oxidizing atmosphere, reducing atmosphere or inert atmosphere, then be catalyzed after reduction is made in hydrogen reducing
Agent；The transition metal refers to the one or two or more kinds in iron, ruthenium, rhenium, platinum；
(3) main group metal simple substance or the doping of alloy auxiliary agent：Catalyst after reduction is placed in inert atmosphere, by a certain percentage with
Main group metal simple substance or alloy ground and mixed are uniform, and are obtained in an inert atmosphere in 100-200 DEG C of stir-activating 10-16 hours
To activated catalyst.
6. according to the method described in claim 5, it is characterized in that：The inert atmosphere is one in nitrogen, argon gas, helium
Kind.
7. according to the method described in claim 5, it is characterized in that：The concentrated sulfuric acid of mixed solution and dense nitre in the step (1)
The volume ratio of acid is 1:10-10:1.
8. according to the method described in claim 5, it is characterized in that：The metal precursor is volatile organometallic compound
Or the one or two or more kinds of volatile metal salt.
9. according to the method described in claim 5, it is characterized in that：The auxiliary agent refers to I A, II A, III A races element, including Li,
One or more of Na, K, Rb, Cs, Mg, Ca, Ba, Al；For transition metal iron, preferred auxiliary agent is Na, K；For
Rhenium, platinum, preferred auxiliary agent are Na, K, Rb, Cs；For ruthenium, preferred auxiliary agent is Ca, Ba, Cs.
10. according to the method described in claim 9, it is characterized in that：Prepare the organic gold of volatility used by ferrum-based catalyst
It is one in ferrocene, tertiary butyl ferrocene, cyclo-octatetraene iron tricarbonyl, cyclohexadiene iron tricarbonyl, carbonyl iron to belong to compound
Kind or two kinds or more；It prepares volatile metal salt used by ferrum-based catalyst and refers to one kind in iron chloride, ferric nitrate or two kinds
More than；Volatile organometallic compound is three oxygen rhenium of methyl, ten carbonyls, two rhenium, ring penta 2 used by preparing rhenium-based catalyst
One or two or more kinds in alkene rhenium tri carbonyl compound；Volatile metal salt refers to chlorination rhenium used by preparing rhenium-based catalyst
(III), one kind in chlorination rhenium (V) or two kinds；Volatile organometallic compound is second used by preparing platinum based catalyst
Acyl acetone platinum (II), 1,1,1,5,5,5- hexafluoroacetylacetones platinum (II), Π-cyclopentadiene (trimethyl) platinum (IV), (front three
Base) methyl cyclopentadiene closes one or two or more kinds in platinum (IV).
11. according to the method described in claim 5, it is characterized in that：In the step (2), O in oxidizing atmosphere2Volume basis
Content is 20-100%, remaining is inert gas；H in the reducing atmosphere2Volumn concentration for 10-100%, remaining is
Inert gas；The inert atmosphere is N2, one or more in Ar, He.
12. according to the method described in claim 5, it is characterized in that：In the step (2), heat resolve pressure for be normal pressure-
8MPa；Heat decomposition temperature is 100-400 DEG C.
13. a kind of application of the catalyst described in claim 1-4 is one of arbitrary, it is characterised in that：It is synthesized for atmospheric low-temperature
In ammonia reaction.
14. the application according to requiring 13, it is characterised in that：The atmospheric low-temperature ammonia synthesis reaction method is：It is urged described
Agent in-situ reducing 30-120min in the hydrogen atmosphere of 300-400 DEG C of normal pressure, is down to certain temperature in hydrogen atmosphere
Afterwards, reaction temperature is risen to, is switched to normal pressure nitrogen and hydrogen mixture, the nitrogen and hydrogen mixture volume compares N2：H2=1:3-3:1, reaction gas
Body flow velocity is 1-50mL/min, and reaction temperature is 25-350 DEG C, obtains ammonia product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710001631.9A CN108262034B (en) | 2017-01-03 | 2017-01-03 | Catalyst, preparation method thereof and application thereof in ammonia synthesis under normal pressure and low temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710001631.9A CN108262034B (en) | 2017-01-03 | 2017-01-03 | Catalyst, preparation method thereof and application thereof in ammonia synthesis under normal pressure and low temperature |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108262034A true CN108262034A (en) | 2018-07-10 |
| CN108262034B CN108262034B (en) | 2021-03-30 |
Family
ID=62770600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710001631.9A Active CN108262034B (en) | 2017-01-03 | 2017-01-03 | Catalyst, preparation method thereof and application thereof in ammonia synthesis under normal pressure and low temperature |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108262034B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110252376A (en) * | 2019-07-01 | 2019-09-20 | 吉林大学 | A kind of metal-semiconductor composite photo-catalyst, the preparation method and applications of photocatalysis nitrogen and hydrogen synthesis ammonia |
| CN111167443A (en) * | 2020-01-20 | 2020-05-19 | 武汉大学 | Novel ruthenium-based catalyst and preparation method and application thereof |
| CN111545219A (en) * | 2020-05-01 | 2020-08-18 | 赵玉平 | Catalyst for preparing acrolein by propylene oxidation and preparation method thereof |
| CN111871412A (en) * | 2020-07-30 | 2020-11-03 | 天津大学 | Pt-CNTs/diatomite and preparation method and application thereof |
| CN112675918A (en) * | 2021-01-08 | 2021-04-20 | 陕西师范大学 | Method for reducing migration of ferrocene burning rate catalyst |
| CN112774674A (en) * | 2019-11-08 | 2021-05-11 | 中国科学院大连化学物理研究所 | Supported ruthenium cluster catalyst for ammonia synthesis, and preparation method and application thereof |
| CN114126755A (en) * | 2019-04-01 | 2022-03-01 | 加利福尼亚大学董事会 | Electrochemical conversion |
| CN114618481A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Synthetic ammonia catalyst, preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104056622A (en) * | 2013-03-20 | 2014-09-24 | 中国科学院大连化学物理研究所 | Rhodium/carbon nanotube catalyst and preparation method and application |
| CN105597739A (en) * | 2014-11-20 | 2016-05-25 | 中国科学院大连化学物理研究所 | Pt-coated CNTs catalyst and preparation and application thereof |
| CN106064097A (en) * | 2016-06-08 | 2016-11-02 | 南京科技职业学院 | A kind of room temperature synthetic ammonia catalyst and preparation method thereof |
| CN106111201A (en) * | 2016-06-23 | 2016-11-16 | 北京化工大学常州先进材料研究院 | A kind of catalyst for electrochemical synthesis ammonia and preparation method thereof |
-
2017
- 2017-01-03 CN CN201710001631.9A patent/CN108262034B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104056622A (en) * | 2013-03-20 | 2014-09-24 | 中国科学院大连化学物理研究所 | Rhodium/carbon nanotube catalyst and preparation method and application |
| CN105597739A (en) * | 2014-11-20 | 2016-05-25 | 中国科学院大连化学物理研究所 | Pt-coated CNTs catalyst and preparation and application thereof |
| CN106064097A (en) * | 2016-06-08 | 2016-11-02 | 南京科技职业学院 | A kind of room temperature synthetic ammonia catalyst and preparation method thereof |
| CN106111201A (en) * | 2016-06-23 | 2016-11-16 | 北京化工大学常州先进材料研究院 | A kind of catalyst for electrochemical synthesis ammonia and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| HONG-BO CHEN ET AL.: "Novel multi-walled nanotubes-supported and alkali-promoted Ru catalysts for ammonia synthesis under atmospheric pressure", 《APPLIED SURFACE SCIENCE》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114126755A (en) * | 2019-04-01 | 2022-03-01 | 加利福尼亚大学董事会 | Electrochemical conversion |
| CN110252376A (en) * | 2019-07-01 | 2019-09-20 | 吉林大学 | A kind of metal-semiconductor composite photo-catalyst, the preparation method and applications of photocatalysis nitrogen and hydrogen synthesis ammonia |
| CN112774674A (en) * | 2019-11-08 | 2021-05-11 | 中国科学院大连化学物理研究所 | Supported ruthenium cluster catalyst for ammonia synthesis, and preparation method and application thereof |
| CN111167443A (en) * | 2020-01-20 | 2020-05-19 | 武汉大学 | Novel ruthenium-based catalyst and preparation method and application thereof |
| CN111545219A (en) * | 2020-05-01 | 2020-08-18 | 赵玉平 | Catalyst for preparing acrolein by propylene oxidation and preparation method thereof |
| CN111871412A (en) * | 2020-07-30 | 2020-11-03 | 天津大学 | Pt-CNTs/diatomite and preparation method and application thereof |
| CN114618481A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Synthetic ammonia catalyst, preparation method and application thereof |
| CN112675918A (en) * | 2021-01-08 | 2021-04-20 | 陕西师范大学 | Method for reducing migration of ferrocene burning rate catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108262034B (en) | 2021-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108262034A (en) | A kind of catalyst and preparation method thereof and the application in atmospheric low-temperature synthesizes ammonia | |
| Zhu et al. | Aqueous electrocatalytic N 2 reduction for ambient NH 3 synthesis: recent advances in catalyst development and performance improvement | |
| Xue et al. | Self-catalyzed growth of Cu@ graphdiyne core–shell nanowires array for high efficient hydrogen evolution cathode | |
| Zhang et al. | Decorating ZIF-67-derived cobalt–nitrogen doped carbon nanocapsules on 3D carbon frameworks for efficient oxygen reduction and oxygen evolution | |
| Wang et al. | Insights into efficient transition metal-nitrogen/carbon oxygen reduction electrocatalysts | |
| Huang et al. | Activating C–H bonds by tuning Fe sites and an interfacial effect for enhanced methanol oxidation | |
| Zhang et al. | Carbon-based material-supported single-atom catalysts for energy conversion | |
| Huang et al. | Highly dispersed Pt clusters encapsulated in MIL-125-NH 2 via in situ auto-reduction method for photocatalytic H 2 production under visible light | |
| Guo et al. | Steam pretreatment-mediated catalytic activity modulation for ammonia borane hydrolysis over ruthenium nanoclusters on nitrogen/oxygen-rich carbon nanotubes | |
| Akbayrak et al. | Rhodium (0), Ruthenium (0) and Palladium (0) nanoparticles supported on carbon-coated iron: Magnetically isolable and reusable catalysts for hydrolytic dehydrogenation of ammonia borane | |
| Feng et al. | A mixed-ion strategy to construct CNT-decorated Co/N-doped hollow carbon for enhanced oxygen reduction | |
| Shen et al. | Breaking the N-limitation with N-enriched porous submicron carbon spheres anchored Fe single-atom catalyst for superior oxygen reduction reaction and Zn-air batteries | |
| CN105536835A (en) | Heteroatom-doped carbon-load iron carbide/ molybdenum or tungsten carbide catalyst and preparation method and application thereof | |
| CN108927185B (en) | Oxygen reduction catalyst of heteroatom-doped carbon nanotube-loaded iron phosphide nanoparticles and preparation method thereof | |
| CN113289653A (en) | g-C of load metal monoatomic3N4Method for preparing photocatalyst | |
| CN106362719B (en) | A kind of modified activated carbon and preparation method and applications | |
| CN106475122B (en) | A kind of Ni of low temperature preparation three-dimensional step pore structure2The method of P catalyst | |
| Wang et al. | Single-atom catalysts for energy conversion | |
| CN109647408B (en) | Preparation method and application of Co-MOF-based porous composite self-supporting catalyst | |
| Jiang et al. | Synergistic heat treatment derived hollow-mesoporous-microporous Fe–N–C-SHT electrocatalyst for oxygen reduction reaction | |
| CN107597162A (en) | A kind of nitrogen-doped carbon material rich in CNTs and Co particles with difunctional oxygen catalytic performance and its preparation method and application | |
| Wu et al. | Improved atomic hydrogen desorption by Cu3N with suitable electronic structure to enhance photocatalytic H2 evolution | |
| Huang et al. | Fe–N–C nanostick derived from 1D Fe-ZIFs for electrocatalytic oxygen reduction | |
| Liu et al. | Oxygen vacancy modulation in interfacial engineering Fe3O4 over carbon nanofiber boosting ambient electrocatalytic N2 reduction | |
| CN110571440B (en) | FeN4-CNT oxygen reduction catalyst preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |