CN106693977A - Preparation method of high-efficiency ammonia decomposition catalyst - Google Patents
Preparation method of high-efficiency ammonia decomposition catalyst Download PDFInfo
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- CN106693977A CN106693977A CN201710029812.2A CN201710029812A CN106693977A CN 106693977 A CN106693977 A CN 106693977A CN 201710029812 A CN201710029812 A CN 201710029812A CN 106693977 A CN106693977 A CN 106693977A
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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
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/047—Decomposition of ammonia
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a preparation method of a meerschaum-supported nickel-base catalyst. By using natural meerschaum as the support, simple acid treatment is carried out to improve the pore structure of the natural meerschaum and enhance the specific area of the meerschaum; urea is used as a precipitant to prepare the high-dispersity nickel/meerschaum catalyst; since the urea is gradually hydrolyzed to release hydroxyl groups at high temperature, the precipitation process can proceed slowly, so that the high-dispersity nickelous hydroxide nanoparticles are uniformly supported on the support surface; and roasting is carried out to obtain the high-efficiency nickel/meerschaum catalyst for catalyzing ammonia decomposition reaction. The raw material meerschaum is a natural compound, and thus, has the advantages of wide sources, environment friendliness and low price. The catalyst preparation process is simple, is short in the technical procedure and suitable for industrial production, and has very high application value.
Description
Technical field
The present invention relates to field of catalyst preparation, catalyst and its preparation that more particularly to a kind of preparing hydrogen by ammonia decomposition reacts
Method, specifically a kind of preparation method of sepiolite supported nickel-base catalyst.
Background technology
With the increasingly exhaustion of fossil fuel, energy problem has turned into the theme of current era.Exploitation more cleaning, cheap
The energy be current facing mankind huge challenge.Hydrogen Energy is a kind of energy for cleaning very much, and substantial amounts of heat can be produced after burning
Amount, and there was only water in product, it is considered to be a kind of very promising alternative energy source.In recent years, recognized by preparing hydrogen by ammonia decomposition
For be it is a kind of it is effective obtain Hydrogen Energy method.Because ammonia has hydrogen content (17.6wt%) and significant energy very high close
Spend (3000W/kg), and ammonia can exist in liquid form by pressurization, be conducive to storing and transport, thus obtain extensively
Concern.At present, common ammonia decomposition catalyzer is mainly including Ru, Fe, Ni etc..Wherein, Ru bases catalyst activity highest
(J.Am.Chem.Soc., 2009,131,12230-12239), but Ru is expensive, and catalyst preparation is relatively costly, it is impossible to
Large-scale production.Fe base catalyst is although cheap, but activity is poor, is also not suitable for doing ammonia decomposition catalyzer.And Ni bases
A kind of the characteristics of catalyst has cheap and active high simultaneously, it is considered to be very promising ammonia decomposition catalyzer
(Energy Environ.Sci., 2012,5,6278).In general, pure Ni catalysis activities are relatively low, because at high temperature, Ni receives
Rice grain is easy to reunite, and catalyst is susceptible to sintering causes exposed avtive spot to greatly reduce.So, it is Ni-based preparing
During catalyst, generally require by Ni specific surface area is big and resistant to elevated temperatures carrier on.Because by load can well by
Nano nickel particles are dispersed in carrier surface, and these small nano nickel particles have catalysis activity higher to ammonia decomposition reaction.
At present, common porous carrier includes SBA-15, Al2O3, SiO2, MCM-41 and CNT etc., these carrier ratios
Surface area is big, and duct is flourishing, but preparation process is complicated, relatively costly.Cheap, preparation process is simple the porous carrier of exploitation
Load high activated catalyst component is the huge challenge faced in ammonia decomposition catalyzer preparation process.The present invention is by a series of
Experiment finds that by natural sepiolite by simple acid treatment, can further improve its specific surface area, gained is catalyzed after nickel-loaded
Agent shows catalysis activity very high in preparing hydrogen by ammonia decomposition reaction.And, sepiolite is a kind of natural products, and source is wide
It is general, it is cheap, thus the preparation cost of catalyst can substantially reduce, and be conducive to industrialized production.
The content of the invention
It is an object of the invention to provide a kind of preparation method of sepiolite supported Raney nickel.The present invention is from cheap
And the big native compound sepiolite of specific surface area, by simple acid treatment, further improves its specific surface area as carrier.
Then, the sepiolite after nickel presoma, urea and treatment is added in deionized water in varing proportions, is carried out in oil bath pan
Class hydro-thermal reaction.Because under the high temperature conditions, urea can gradually be hydrolyzed and discharge hydroxyl, these hydroxyls can be with nickel ion
With reference to so that forming the nickel hydroxide nano particle that particle is small, dispersiveness is high homogeneously precipitates in sepiolite carrier surface.By control
Heat time processed and the ratio for feeding intake, finally can effectively control the size and dispersiveness of Ni nano particles, and then explore catalysis
The optimum preparating condition of agent.Nano nickel particles are small in the Ni base catalyst obtained due to the preparation method, and dispersiveness is high, thus
Excellent catalysis activity is shown in ammonolysis craft catalytic reaction.Importantly, the catalyst is cheap, prepare simply, have
Very big industrial production value.
The invention provides a kind of preparation method of sepiolite supported Raney nickel, the specific implementation process of the invention is such as
Under：
(1) natural sepiolite is added to certain density hydrochloric acid solution first, 6~24h is stirred at room temperature, then mistake
Filter, sample is washed till neutrality with deionized water, and be dried treatment in an oven；
(2) sample obtained in (1) is ground, sieved, obtain final modified sepiolite carrier；
(3) sample in step (2) is added in deionized water, is subsequently adding the nickel presoma and urine of different content
Element, the mixture for obtaining persistently stirs 1~24h, then washed, filtered, dried in 60~120 DEG C of oil bath pan；
(4) sample that will be obtained in step (3), with the heating rate of 1~10 DEG C/min to 400~900 in Muffle furnace
DEG C 1~6h of roasting is carried out, be finally cooled to room temperature, obtain final nickel/sepiolite catalyst；
(5) ammonolysis craft catalytic perfomance test：Obtained 0.1~0.5g of catalyst sample is added admittedly in taking step (4)
In fixed bed reactor, H is passed through2(10~50mL/min) reduces 1h at 400~700 DEG C；Then, it is cooled to less than 100 DEG C, then
Ammonolysis craft active testing is carried out, 300~700 DEG C of test temperature, 1~20h of reaction time is catalyzed.
The preparation method of a kind of nickel/sepiolite catalyst of the present invention, it is characterised in that in the experimental procedure
Concentration of hydrochloric acid solution is 1~6mol/L, and sepiolite is 1: 5~1: 20 with the solid-liquid mass ratio of hydrochloric acid solution.
The preparation method of a kind of nickel/sepiolite catalyst of the present invention, it is characterised in that described nickel presoma is
Nickel nitrate, nickel chloride, nickel acetate, the nickel presoma addition cause Ni2+It is 1: 1~1: 6 with the molar ratio of urea, catalysis
The theoretical content of nickel is 0~40% in agent
Benefit of the invention is, from natural sepiolite as carrier, by simple acid treatment, improves its specific surface
Product.Due to sepiolite, specific surface area is big in itself, and pore passage structure is excellent, and with heat endurance higher, is entered by acid treatment
One step improves its pore passage structure, increases its specific surface area.Then, the principle system for gradually being hydrolyzed under the high temperature conditions using urea
For the nickel of high dispersive/sepiolite catalyst has been gone out, the catalyst shows catalysis very high and lives in preparing hydrogen by ammonia decomposition reaction
Property.The prominent advantage of the present invention is exactly relatively low material therefor cost, and wherein sepiolite is a kind of natural products, wide material sources and ring
Border is friendly, with very big potential value.In addition, the catalyst preparation process is simple, it is easy to operate, process conditions are convenient
It is easy, it is very beneficial for industrialized production.
Brief description of the drawings
Fig. 1 is the scanning electron microscope diagram (SEM) of prepared sample in the embodiment of the present invention 1；
Fig. 2 is the transmission electron microscope figure (TEM) of prepared sample in the embodiment of the present invention 1；
Fig. 3 is nitrogen adsorption isotherm figure (a) and the corresponding aperture point of prepared sample in the embodiment of the present invention 1,7,8
Butut (b)；
Fig. 4 is the ammonolysis craft activity figure of sample prepared by the embodiment of the present invention 1~6.
Specific embodiment
It is below embodiment, it is as follows in detail to providing specific embodiment according to the present invention：
Embodiment 1
Sepiolite Vehicle element：Choose 10g sepiolites to be positioned in the beaker of 250mL, add 100mL 4mol/L's
HCl solution, and 12h is stirred at room temperature.Then, it is washed with deionized water to neutrality, filtering dries 12h at 110 DEG C.Will be dry
Dry good sample is ground, and crosses 100 mesh sieves, finally gives the sepiolite carrier (SP) after treatment.
Catalyst preparation：Ni (the NO of 1.982g are weighed first3)2·6H2O is added to the beaker containing 100mL deionized waters
In, it is stirred vigorously, treat Ni (NO3)2·6H2After O is completely dissolved, the urea for weighing 1.636g is added in the solution, and stirring is to complete
CL.Then, weigh the sepiolite sample after 2g treatment to be added in the mixed solution, be stirred vigorously after 30min at 90 DEG C
10h, and ultrasonically treated 30min are processed under the conditions of oil bath.The sample that will be obtained again is cleaned with substantial amounts of deionized water, suction filtration, and
12h is dried in 110 DEG C of baking ovens.Finally, the sample is ground, crosses 100 mesh sieves, in Muffle kiln roasting 3h, roasting temperature
It is 700 DEG C to spend, and obtained sample is sepiolite supported Raney nickel (20%N/SP-700).Fig. 1 and Fig. 2 are respectively the sample
Scanning electron microscope diagram and transmission electron microscope figure.From figure 1 it appears that sepiolite has filamentary structure, these
Filamentary structure is interweaved, and forms some loose ducts.After supported nickel catalyst, the knot of the catalyst is not destroyed
Structure.From figure 2 it can be seen that the sepiolite sample after supported nickel catalyst still keeps filamentary structure, in these threadinesss
The Dispersion on surface of structure has some tiny nano particles.It can be seen that these small nanometers from high-resolution lens (Fig. 2 d)
Particle has obvious lattice fringe, is tested to be 0.21nm, is nickel oxide (200) crystal face, shows that nickel is successfully loaded on
Sepiolite carrier surface is arrived.
Embodiment 2
Sepiolite Vehicle element：Choose 10g sepiolites to be positioned in the beaker of 250mL, add 100mL 4mol/L's
HCl solution, and 12h is stirred at room temperature.Then, it is washed with deionized water to neutrality, suction filtration dries 12h at 110 DEG C.Will be dry
Dry good sample, is ground, and crosses 100 mesh sieves, finally gives the sepiolite carrier (SP) after treatment.
Catalyst preparation：Ni (the NO of 0.496g are weighed first3)2·6H2O is added to the beaker containing 100mL deionized waters
In, it is stirred vigorously, treat Ni (NO3)2·6H2After O is completely dissolved, the urea for weighing 0.468g is added in the solution, and stirring is to complete
CL.Then, weigh the sepiolite sample after 2g treatment to be added in the mixed solution, be stirred vigorously after 30min at 90 DEG C
10h, and ultrasonically treated 30min are processed under the conditions of oil bath.The sample that will be obtained again is cleaned with substantial amounts of deionized water, suction filtration, and
12h is dried in 110 DEG C of baking ovens.Finally, the sample is ground, crosses 100 mesh sieves, in Muffle kiln roasting 3h, roasting temperature
It is 700 DEG C to spend, and obtained sample is sepiolite supported Raney nickel (5%N/SP-700).
Embodiment 3
Sepiolite Vehicle element：Choose 10g sepiolites to be positioned in the beaker of 250mL, add 100mL 4mol/L's
HCl solution, and 12h is stirred at room temperature.Then, it is washed with deionized water to neutrality, suction filtration dries 12h at 110 DEG C.Will be dry
Dry good sample, is ground, and crosses 100 mesh sieves, finally gives the sepiolite carrier (SP) after treatment.
Catalyst preparation：Ni (the NO of 0.99g are weighed first3)2·6H2O is added to the beaker containing 100mL deionized waters
In, it is stirred vigorously, treat Ni (NO3)2·6H2After O is completely dissolved, the urea for weighing 0.938g is added in the solution, and stirring is to complete
CL.Then, weigh the sepiolite sample after 2g treatment to be added in the mixed solution, be stirred vigorously after 30min at 90 DEG C
10h, and ultrasonically treated 30min are processed under the conditions of oil bath.The sample that will be obtained again is cleaned with substantial amounts of deionized water, suction filtration, and
12h is dried in 110 DEG C of baking ovens.Finally, the sample is ground, crosses 100 mesh sieves, in Muffle kiln roasting 3h, roasting temperature
It is 700 DEG C to spend, and obtained sample is sepiolite supported Raney nickel (10%N/SP-700).
Embodiment 4
Sepiolite Vehicle element：Choose 10g sepiolites to be positioned in the beaker of 250mL, add 100mL 4mol/L's
HCl solution, and 12h is stirred at room temperature.Then, it is washed with deionized water to neutrality, suction filtration dries 12h at 110 DEG C.Will be dry
Dry good sample, is ground, and crosses 100 mesh sieves, finally gives the sepiolite carrier (SP) after treatment.
Catalyst preparation：Ni (the NO of 1.486g are weighed first3)2·6H2O is added to the beaker containing 100mL deionized waters
In, it is stirred vigorously, treat Ni (NO3)2·6H2After O is completely dissolved, the urea for weighing 1.226g is added in the solution, and stirring is to complete
CL.Then, weigh the sepiolite sample after 2g treatment to be added in the mixed solution, be stirred vigorously after 30min at 90 DEG C
10h, and ultrasonically treated 30min are processed under the conditions of oil bath.The sample that will be obtained again is cleaned with substantial amounts of deionized water, suction filtration, and
12h is dried in 110 DEG C of baking ovens.Finally, the sample is ground, crosses 100 mesh sieves, in Muffle kiln roasting 3h, roasting temperature
It is 700 DEG C to spend, and obtained sample is sepiolite supported Raney nickel (15%N/SP-700).
Embodiment 5
Sepiolite Vehicle element：Choose 10g sepiolites to be positioned in the beaker of 250mL, add 100mL 4mol/L's
HCl solution, and 12h is stirred at room temperature.Then, it is washed with deionized water to neutrality, suction filtration dries 12h at 110 DEG C.Will be dry
Dry good sample, is ground, and crosses 100 mesh sieves, finally gives the sepiolite carrier (SP) after treatment.
Catalyst preparation：Ni (the NO of 2.477g are weighed first3)2·6H2O is added to the beaker containing 100mL deionized waters
In, it is stirred vigorously, treat Ni (NO3)2·6H2After O is completely dissolved, the urea for weighing 2.044g is added in the solution, and stirring is to complete
CL.Then, weigh the sepiolite sample after 2g treatment to be added in the mixed solution, be stirred vigorously after 30min at 90 DEG C
10h, and ultrasonically treated 30min are processed under the conditions of oil bath.The sample that will be obtained again is cleaned with substantial amounts of deionized water, suction filtration, and
12h is dried in 110 DEG C of baking ovens.Finally, the sample is ground, crosses 100 mesh sieves, in Muffle kiln roasting 3h, roasting temperature
It is 700 DEG C to spend, and obtained sample is sepiolite supported Raney nickel (25%N/SP-700).
Embodiment 6
Sepiolite Vehicle element：Choose 10g sepiolites to be positioned in the beaker of 250mL, add 100mL 4mol/L's
HCl solution, and 12h is stirred at room temperature.Then, it is washed with deionized water to neutrality, suction filtration dries 12h at 110 DEG C.Will be dry
Dry good sample, is ground, and crosses 100 mesh sieves, finally gives the sepiolite carrier (SP) after treatment.
Catalyst preparation：Ni (the NO of 2.972g are weighed first3)2·6H2O is added to the beaker containing 100mL deionized waters
In, it is stirred vigorously, treat Ni (NO3)2·6H2After O is completely dissolved, the urea for weighing 2.452g is added in the solution, and stirring is to complete
CL.Then, weigh the sepiolite sample after 2g treatment to be added in the mixed solution, be stirred vigorously after 30min at 90 DEG C
10h, and ultrasonically treated 30min are processed under the conditions of oil bath.The sample that will be obtained again is cleaned with substantial amounts of deionized water, suction filtration, and
12h is dried in 110 DEG C of baking ovens.Finally, the sample is ground, crosses 100 mesh sieves, in Muffle kiln roasting 3h, roasting temperature
It is 700 DEG C to spend, and obtained sample is sepiolite supported Raney nickel (30%N/SP-700).
Embodiment 7
Sepiolite Vehicle element：Choose 10g sepiolites to be positioned in the beaker of 250mL, add 100mL 4mol/L's
HCl solution, and 12h is stirred at room temperature.Then, it is washed with deionized water to neutrality, suction filtration dries 12h at 110 DEG C.Will be dry
Dry good sample, is ground, and crosses 100 mesh sieves, finally gives the sepiolite carrier (SP) after treatment.
Catalyst preparation：Ni (the NO of 1.982g are weighed first3)2·6H2O is added to the beaker containing 100mL deionized waters
In, it is stirred vigorously, treat Ni (NO3)2·6H2After O is completely dissolved, the urea for weighing 1.636g is added in the solution, and stirring is to complete
CL.Then, weigh the sepiolite sample after 2g treatment to be added in the mixed solution, be stirred vigorously after 30min at 90 DEG C
10h, ultrasonically treated 30min are processed under the conditions of oil bath.The sample that will be obtained again is cleaned with substantial amounts of deionized water, suction filtration, and
12h is dried in 110 DEG C of baking ovens.Finally, the sample is ground, 100 mesh sieves is crossed, in Muffle kiln roasting 3h, sintering temperature
It it is 600 DEG C, obtained sample is sepiolite supported Raney nickel (20%N/SP-600).
Embodiment 8
Sepiolite Vehicle element：Choose 10g sepiolites to be positioned in the beaker of 250mL, add 100mL 4mol/L's
HCl solution, and 12h is stirred at room temperature.Then, it is washed with deionized water to neutrality, suction filtration dries 12h at 110 DEG C.Will be dry
Dry good sample, is ground, and crosses 100 mesh sieves, finally gives the sepiolite carrier (SP) after treatment.
Catalyst preparation：Ni (the NO of 1.982g are weighed first3)2·6H2O is added to the beaker containing 100mL deionized waters
In, it is stirred vigorously, treat Ni (NO3)2·6H2After O is completely dissolved, the urea for weighing 1.636g is added in the solution, and stirring is to complete
CL.Then, weigh the sepiolite sample after 2g treatment to be added in the mixed solution, be stirred vigorously after 30min at 90 DEG C
10h, and ultrasonically treated 30min are processed under the conditions of oil bath.The sample that will be obtained again is cleaned with substantial amounts of deionized water, suction filtration, and
12h is dried in 110 DEG C of baking ovens.Finally, the sample is ground, crosses 100 mesh sieves, in Muffle kiln roasting 3h, roasting temperature
It is 800 DEG C to spend, and obtained sample is sepiolite supported Raney nickel (20%N/SP-800).
Fig. 3 is embodiment 1, example 7 and nitrogen adsorption figure (a) of prepared sample and corresponding graph of pore diameter distribution in example 8
(b).It can be seen that the adsorption isotherm and pore size distribution curve of these three samples are much like, these samples are illustrated
Pore passage structure is similar, also illustrates that the catalyst has heat endurance very high, pore passage structure of the sintering temperature to catalyst
Influence is little.
The nickel sepiolite catalyst of different Ni load capacity is prepared by embodiment 1-6, its ammonolysis craft catalysis activity figure is such as
Shown in Fig. 4.It can be seen that its activity of the sepiolite of unsupported nickel is very poor, when reaction temperature reaches 700 DEG C, ammonia
Conversion ratio only has 24.2%.After supported ni catalyst, its catalysis activity is obviously improved.Load 5,10,15,20,25 and 30%
Ni after, when reaction temperature be 700 DEG C when its conversion ratio be respectively 70.1,85.6,94.2,100,98.0 and 92.3%.The hair
The bright preparation condition to sepiolite supported Ni catalyst is probed into and optimized, and is obtained optimal preparation condition and is：Sepiolite
2g, Ni (NO3)2·6H2O 1.982g, urea 1.636g, 700 DEG C of sintering temperature, roasting time 3h, catalyst is urged under the conditions of this
Change the conversion ratio highest of ammonolysis craft.When reaction temperature is 600 DEG C, the conversion ratio of ammonia can reach 75.4%, when reaction temperature is
The conversion ratio of ammonia is close to 100% at 700 DEG C.
One embodiment of the present of invention has been described in detail above, but the content is only preferable implementation of the invention
Example, it is impossible to be considered as limiting practical range of the invention.All impartial changes made according to the present patent application scope and improvement
Deng all should still belong within patent covering scope of the invention.
Claims (3)
1. a kind of preparation method of high-efficiency ammonia decomposition catalyst, its preparation process be mainly use the sepiolite of high-specific surface area for
Carrier, with nickel nitrate as presoma, prepares a kind of nickel/sepiolite composite catalyst for ammonia, specific experiment step to be catalytically decomposed
It is as follows：
A () processes dry natural sepiolite sample with certain density hydrochloric acid solution, 6~24h is stirred at room temperature, then
Filter, be washed with deionized to neutrality, dry, then be fully ground, sieve, obtain modified sepiolite；
B in aqueous be well mixed for the nickel presoma of modified sepiolite and different content, urea by (), in oil bath pan
1~24h of stir process at a temperature of 60~120 DEG C, then filters, washs, dries, and with the heating rate of 1~10 DEG C/min
To 400~900 DEG C of 1~6h of calcining, room temperature is finally cooled to, has obtained the nickel/sepiolite catalyst of high dispersive.
2. the preparation method of a kind of nickel/sepiolite catalyst as claimed in claim 1, it is characterised in that in the experimental procedure
Concentration of hydrochloric acid solution be 1~6mol/L, the solid-liquid mass ratio of sepiolite and hydrochloric acid solution is 1: 5~1: 20.
3. the preparation method of a kind of nickel/sepiolite catalyst as claimed in claim 1, it is characterised in that in the experimental procedure
Nickel presoma be nickel nitrate, nickel chloride, nickel acetate, the molar ratio of the nickel presoma Ni2+ and urea is 1: 1~1: 6,
The theoretical content of nickel is 0~40% in catalyst.
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| CN110042408A (en) * | 2019-04-23 | 2019-07-23 | 陕西科技大学 | A kind of Ni/SiCNWs/CNFs flexible composite electrode material and its preparation method and application |
| CN110042408B (en) * | 2019-04-23 | 2021-04-16 | 陕西科技大学 | Ni/SiCNWs/CNFs flexible composite electrode material and preparation method and application thereof |
| CN114100695A (en) * | 2020-08-31 | 2022-03-01 | 中国石油化工股份有限公司 | Sulfur-tolerant shift catalyst protective agent and preparation method thereof |
| CN114100695B (en) * | 2020-08-31 | 2023-10-20 | 中国石油化工股份有限公司 | Sulfur-tolerant shift catalyst protective agent and preparation method thereof |
| CN115007125A (en) * | 2022-07-08 | 2022-09-06 | 湘潭大学 | Sepiolite-loaded manganese-cerium composite catalyst and preparation method and application thereof |
| CN115301279A (en) * | 2022-08-17 | 2022-11-08 | 西南石油大学 | Low-temperature high-efficiency ammonia decomposition catalyst and preparation method and application thereof |
| CN115301279B (en) * | 2022-08-17 | 2023-10-27 | 西南石油大学 | Low-temperature ammonia decomposition catalyst and preparation method and application thereof |
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Application publication date: 20170524 |