CN103041839A - Nickel-based bi-metallic catalyst with SBA-15 serving as a carrier and preparation method and application of catalyst - Google Patents
Nickel-based bi-metallic catalyst with SBA-15 serving as a carrier and preparation method and application of catalyst Download PDFInfo
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Abstract
The invention relates to a nickel-based bi-metallic catalyst with SBA-15 serving as a carrier, a preparation method and application of the catalyst, and belongs to the field of mesoporous silica based composites. The preparation method comprises the following steps: by adopting the SBA-15 as the carrier, blending nickel nitrate and nitrate of rare-earth metal by water to be added into an SBA-15 molecular sieve; and carrying out dipping, drying and roasting, so as to obtain the nickel-based bi-metallic catalyst with the SBA-15 serving as the carrier. The nickel-based bi-metallic catalyst containing rare metals, namely, yttrium, cerium or lanthanum can be prepared by using the preparation method provided by the invention and can be shown as: Ni-Y-SBA-15, Ni-Ce-SBA-15 and Ni-La-SBA-15. The method for preparing the nickel-based bi-metallic catalyst with the SBA-15 serving as the carrier is simple and convenient, the process is easy to operate, and the obtained catalyst is high in catalyzing activity; and the nickel-based bi-metallic catalyst with the SBA-15 serving as the carier can be applied to a functionalized molecular sieve required by the petrochemical industry fields such as the methane reforming field.
Description
Technical field
The invention belongs to the mesoporous silicon-dioxide-substrate field of compound material, relate to a kind of Ni-based bimetallic catalyst take SBA-15 as carrier and preparation method thereof and application.
Background technology
Mesoporous material has that high specific surface area, structural arrangement are regular in order, pore size homogeneous, surface, duct can carry out the remarkable advantages such as physical absorption or chemical modification.Use first the nanostructured self-assembling technique to synthesize mesoporous SiO from Kresge in 1992
2(MCM-41) since, the preparation of mesoporous material, performance and application are study hotspots both domestic and external always, its catalysis, absorption, separation, senser element, nano material are synthetic, large biological molecule is immobilized and the field such as medicament slow release in shown advantageous characteristic, caused the extensive concern of international physics, chemistry and material educational circles.The mesoporous molecular sieve SBA-15 specific surface is large, and the channel diameter of homogeneous distributes, but the aperture modulation, and wall thickness and hydrothermal stability are very high, so SBA-15 has wide practical use in fields such as catalysis, separation, biology and nano materials.From atomic level, the skeleton of the silicon-based mesoporous material of broad research mainly is by amorphous Si O at present
2Form, lack the activated centre, the application aspect catalysis is extremely restricted.Therefore, in the hole wall of mesoporous material or duct, introduce specific catalytic active center (as: some transition metal and rare element etc.) by some synthesis strategies, namely mesoporous material is carried out chemical modification, be intended to improve its catalytic performance.A kind of metal of load on mesoporous material only in most of research, such as: Mihai etc. are take zinc acetate as precursor, ZnO is incorporated in the duct of SBA-15 molecular sieve, obtain the ZnO-SBA-15 catalyst of high-load (ZnO content 38%), its in the photocatalytic degradation of dyestuff, show excellent activity (G.D.Mihai et al.Journal of Materials Science 2010,45:5786-5794).Yet for some reaction, the catalytic activity that the mesoporous material of these one-component metals shows generally all allows of no optimist.For example, Nichele etc. Ni in the SBA-15 molecular sieve, obtain the Ni/SBA-15 catalyst, because the gathering of nickel particles, this catalyst in the steam reforming reaction of glycerine, show relatively poor stability and catalytic activity (V.Nichele et al.Applied Catalysis B:Environment 2012,111:225-232).Therefore, be necessary to add the second active component to improve catalytic performance.Wu etc. have introduced CeO in the Rh of SBA-15 load catalyst
2As second component, synthesized the Rh/Ce-SBA-15 catalyst with regular structure, this catalyst in the reaction of the vapor reforming hydrogen production of ethanol, have higher catalytic activity and stability (X.S.Wu et al.Catalysis Today 2009,148,251-259).
In the building-up process of introducing metal ion, usually adopt infusion process, one-step synthesis, Graft Method and ion-exchange etc.Wherein infusion process, load capacity simple to operate because of it is easy to control becomes mesoporous material is carried out one of effective way of chemical modification.Infusion process is to be presoma with the inorganic salts of transition metal/rare element or organic salt, by equi-volume impregnating or excessive infusion process transition metal is assembled in the mesopore molecular sieve duct, then the processing such as drying, roasting obtains containing the mesoporous molecular sieve catalyst of transition metal/rare element.When needs load to mesoporous material to two kinds of metals simultaneously, general all the employing introduced a kind of metal wherein in the mesoporous molecular sieve framework forming process in the lump, that is: a kind of metal is embedded in the molecular sieve, and then the second Metal Supported in the molecular sieve that contains a kind of metal, but can make like this first metal that embeds in the molecular sieve that loss is arranged in the operating process such as filtration washing, can not guarantee that the metal of set load capacity embeds in the molecular sieve effectively.
Summary of the invention
The shortcoming that primary and foremost purpose of the present invention is to overcome prior art provides a kind of simple and convenient process for preparing of the Ni-based bimetallic catalyst take SBA-15 as carrier with not enough.
Another object of the present invention is to provide the Ni-based bimetallic catalyst take SBA-15 as carrier for preparing by above-mentioned preparation method.
A further object of the present invention is to provide the application of above-mentioned Ni-based bimetallic catalyst take SBA-15 as carrier.
Purpose of the present invention is achieved through the following technical solutions:
The preparation method of the Ni-based bimetallic catalyst take SBA-15 as carrier comprises the steps:
(1) adopt hydro-thermal method to prepare the SBA-15 mesopore molecular sieve.
(2) preparation of the Ni-based bimetallic catalyst take SBA-15 as carrier: with the nitrate water dissolving of nickel nitrate and rare earth metal, add the SBA-15 mesopore molecular sieve, dipping, dry in baking oven, gained pressed powder again roasting obtains Ni-based bimetallic catalyst take SBA-15 as carrier.
The method that hydro-thermal method described in the step (1) prepares mesoporous molecular sieve SBA-15 is preferably: with triblock copolymer surfactant P123(Aldrich, EO
20PO
70EO
20, M=5800) be dissolved in the hydrochloric acid solution, made it to dissolve fully in 3～5 hours 35～50 ℃ of lower stirrings; Add again ethyl orthosilicate (TEOS), 35～50 ℃ of lower stirrings 2～4 hours; Then after placing 24～60 hours in 50～60 ℃ water-bath, suction filtration dries naturally, and 500～550 ℃ of roastings obtained the SBA-15 mesopore molecular sieve in 3～6 hours in air atmosphere.Described hydrochloric acid solution is preferably 2molL
-1Hydrochloric acid solution; The mol ratio of described ethyl orthosilicate, P123 and hydrochloric acid is preferably 1:0.017:(5.85～8.0).
Rare earth metal described in the step (2) is preferably yttrium, cerium or lanthanum etc.
Dipping described in the step (2) is preferably 25～35 ℃ of dippings 20～40 minutes.
Drying described in the step (2) is preferably 95～110 ℃ of dryings 10～14 hours.
Roasting described in the step (2) is preferably 500～550 ℃ of roastings 3～5 hours.
The mol ratio of the nitrate of SBA-15, nickel nitrate and the rare earth metal described in the step (2) is preferably 1:(0.05～0.15): (0.02～0.06).
A kind of Ni-based bimetallic catalyst take SBA-15 as carrier is prepared by above-mentioned preparation method.
Described Ni-based bimetallic catalyst take SBA-15 as carrier is Ni-Y-SBA-15, Ni-Ce-SBA-15 or Ni-La-SBA-15 etc.
The pore volume of described Ni-based bimetallic catalyst take SBA-15 as carrier is 0.24～0.29cm
3/ g, specific area is 200～350m
2/ g, the aperture is 3.2～4.4nm.
In the described Ni-based bimetallic catalyst take SBA-15 as carrier, the mol ratio of Ni element and Si element is (0.04～0.15): 1, and thulium (Y, Ce or La) is (0.02～0.06) with the mol ratio of Si element: 1.
The above-mentioned application of Ni-based bimetallic catalyst in methane reforming reaction take SBA-15 as carrier.
The present invention has following advantage and effect with respect to prior art:
(1) preparation method provided by the invention adopts co-impregnation to introduce simultaneously two kinds of metals, and synthesis material is easy to get, and need not special vacuum equipment, and the hydrothermal temperature of synthetic SBA-15 is lower, and is simple to operate.The well-regulated hexagonal structure of product tool.
(2) hydrogen manufacturing has higher catalytic activity to the bimetallic catalyst of this method preparation to methane carbon dioxide reformation, and activity is higher than single-metal reforming catalyst Ni/SBA-15.
Description of drawings
Fig. 1 is the low-angle XRD spectra of the bimetallic catalyst Ni (0.10) for preparing-Ce (0.04)-SBA-15, Ni (0.15)-Y (0.03)-SBA-15 and Ni (0.10)-La (0.04)-SBA-15.
Fig. 2 is the N2 adsorption-desorption characterization result figure of SBA-15 and different bimetallic catalysts.
Fig. 3 is the SBA-15 mesopore molecular sieve (a) of preparation and the transmission electron microscope picture of Ni (0.10)-Ce (0.04)-SBA-15(b).
Fig. 4 is as a result figure of the catalytic performance of bimetallic catalyst in the methane carbon dioxide reformation hydrogen production reaction that prepare.
Fig. 5 is as a result figure of the catalytic performance of bimetallic catalyst in the methane carbon dioxide reformation hydrogen production reaction that prepare.
Fig. 6 is as a result figure of the catalytic performance of bimetallic catalyst in the methane carbon dioxide reformation hydrogen production reaction that prepare.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited to this.
In embodiment 1Ni (0.10)-Ce (0.04)-SBA-15(bracket numerical value be Ni and Ce respectively with the setting mol ratio of Si, set mol ratio refer to Ni in raw materials used and Ce respectively with the mol ratio of Si.）
(1) preparation of SBA-15 mesopore molecular sieve
With 2g triblock copolymer surfactant P123(Aldrich, EO
20PO
70EO
20, M=5800) being dissolved in 80mL concentration is 2molL
-1In the hydrochloric acid solution, made it to dissolve fully in 3 hours 40 ℃ of lower stirrings, in solution, add 4.2g ethyl orthosilicate (TEOS), stirred 2 hours 40 ℃ of lower continuation.Then static placement was taken out after 48 hours in 50 ℃ water-bath, and suction filtration dries naturally, and 500 ℃ of roastings obtained the SBA-15 mesopore molecular sieve in 4 hours in air atmosphere.Gained SBA-15 mesopore molecular sieve has regular two-dimentional hexagonal structure, and pore volume is 0.64cm
3/ g, specific area is 399m
2/ g, the aperture is 5.38nm.
The XRD of this SBA-15 mesopore molecular sieve is characterized on the D8ADVANCE X-ray diffractometer and carries out, and it the results are shown in Figure 1; Nitrogen-absorption representation carries out at Tristar II 3020 specific surfaces and pore size determination instrument, and it the results are shown in Figure 2; It is that the SBA-15 mesopore molecular sieve is scattered in the alcohol solvent that transmission electron microscope (TEM) characterizes, and ultrasonic processing placed on the copper mesh and observes after 1 hour, and instrument is JEM-2100HR, and it the results are shown in Figure 3.
(2) the following method of synthetic employing of Ni (0.10)-Ce (0.04)-SBA-15 catalyst: get 0.25g nitric acid nickel (NO
3)
26H
2O and 0.15g cerous nitrate Ce (NO
3)
36H
2O is dissolved in the 4mL distilled water altogether, add the above-mentioned SBA-15 mesopore molecular sieve of 0.50g, 32 ℃ flooded 30 minutes, drying is 12 hours in 110 ℃ baking oven, the roasting after 4 hours in 500 ℃ Muffle furnace of gained pressed powder obtains the Ni-based bimetallic catalyst Ni (0.10)-Ce (0.04)-SBA-15 take SBA-15 as carrier.The pore volume of gained Ni (0.10)-Ce (0.04)-SBA-15 is 0.25cm
3/ g, specific area is 346m
2/ g, the aperture is 3.5nm; After elementary analysis, the content of Ni and Ce is respectively 8.2wt% and 7.5wt%; The molar ratio of Ni and Si is 0.08, and the molar ratio of rare earth element ce and Si is 0.03.
With the Ni-SBA-15(Ni-SBA-15 preparation method of one-component and Ni-Ce-SBA-15 is similar and the content of nickel is identical, its TEM image is seen Fig. 3) compare, Ni-Ce-SBA-15 has good catalytic activity in methane reforming reaction, and it the results are shown in Figure 4.
In embodiment 2Ni (0.05)-Ce (0.02)-SBA-15(bracket numerical value be Ni and Ce respectively with the setting molar ratio of Si)
(1) preparation of SBA-15 mesopore molecular sieve
With 2g triblock copolymer surfactant P123(Aldrich, EO
20PO
70EO
20, M=5800) being dissolved in 60mL concentration is 2molL
-1In the hydrochloric acid solution, made it to dissolve fully in 4 hours 50 ℃ of lower stirrings, in solution, add 4.2g ethyl orthosilicate (TEOS), stirred 4 hours 35 ℃ of lower continuation.Then static placement was taken out after 24 hours in 60 ℃ water-bath, and suction filtration dries naturally, and 550 ℃ of roastings obtained the SBA-15 mesopore molecular sieve in 3 hours in air atmosphere.
(2) the following method of synthetic employing of Ni (0.05)-Ce (0.02)-SBA-15 catalyst: get 0.13g nitric acid nickel (NO
3)
26H
2O and 0.08g cerous nitrate Ce (NO
3)
36H
2O is dissolved in the 4mL distilled water altogether, add the above-mentioned SBA-15 mesopore molecular sieve of 0.50g, 25 ℃ of lower dippings 40 minutes, drying is 14 hours in 95 ℃ baking oven, the roasting after 3 hours in 550 ℃ Muffle furnace of gained pressed powder obtains the Ni-based bimetallic catalyst Ni (0.05)-Ce (0.02)-SBA-15 catalyst take SBA-15 as carrier.The pore volume of gained Ni (0.05)-Ce (0.02)-SBA-15 is 0.24cm
3/ g, specific area is 329m
2/ g, the aperture is 3.2nm; The content of Ni and Ce is respectively 4.0wt% and 3.9wt% after elementary analysis; The molar ratio of Ni and Si is 0.04, and the molar ratio of rare earth element ce and Si is 0.02.
In embodiment 3Ni (0.10)-Y (0.04)-SBA-15(bracket numerical value be Ni and Y respectively with the setting molar ratio of Si)
(1) preparation of SBA-15 mesopore molecular sieve
With 2g triblock copolymer surfactant P123(Aldrich, EO
20PO
70EO
20, M=5800) being dissolved in 70mL concentration is 2molL
-1In the hydrochloric acid solution, made it to dissolve fully in 5 hours 35 ℃ of lower stirrings, in solution, add 4.2g ethyl orthosilicate (TEOS), stirred 3 hours 50 ℃ of lower continuation.Then static placement was taken out after 60 hours in 50 ℃ water-bath, and suction filtration dries naturally, and 500 ℃ of roastings obtained the SBA-15 mesopore molecular sieve in 6 hours in air atmosphere.
(2) the following method of synthetic employing of Ni (0.10)-Y (0.04)-SBA-15: get 0.25g nitric acid nickel (NO
3)
26H
2O and 0.13g yttrium nitrate Y (NO
3)
36H
2O is dissolved in the 4mL distilled water altogether, add the above-mentioned SBA-15 mesopore molecular sieve of 0.50g, 35 ℃ of lower dippings 20 minutes, drying is 10 hours in 100 ℃ baking oven, the roasting after 5 hours in 520 ℃ Muffle furnace of gained pressed powder obtains SBA-15 and is the Ni-based bimetallic catalyst Ni (0.10) of carrier-Y (0.04)-SBA-15.The pore volume of gained Ni (0.10)-Y (0.04)-SBA-15 is 0.24cm
3/ g, specific area is 203m
2/ g, the aperture is 4.23nm; The content of Ni and Y is respectively 8.5wt% and 5.6wt%; The molar ratio of Ni and Si is 0.09, and the molar ratio of rare earth element y and Si is 0.04.
In embodiment 4Ni (0.05)-Y (0.06)-SBA-15(bracket numerical value be Ni and Y respectively with the setting molar ratio of Si)
(1) preparation of SBA-15 mesopore molecular sieve
With 2g triblock copolymer surfactant P123(Aldrich, EO
20PO
70EO
20, M=5800) being dissolved in 80mL concentration is 2molL
-1In the hydrochloric acid solution, made it to dissolve fully in 3 hours 50 ℃ of lower stirrings, in solution, add 4.2g ethyl orthosilicate (TEOS), stirred 4 hours 35 ℃ of lower continuation.Then static placement was taken out after 50 hours in 50 ℃ water-bath, and suction filtration dries naturally, and 500 ℃ of roastings obtained the SBA-15 mesopore molecular sieve in 3 hours in air atmosphere.
(2) the following method of synthetic employing of Ni (0.05)-Y (0.06)-SBA-15: get 0.13g nitric acid nickel (NO
3)
26H
2O and 0.20g yttrium nitrate Y (NO
3)
36H
2O is dissolved in the 4mL distilled water altogether, add the above-mentioned SBA-15 mesopore molecular sieve of 0.50g, 25 ℃ of lower dippings 30 minutes, drying is 11 hours in 95 ℃ baking oven, the roasting after 4 hours in 550 ℃ Muffle furnace of gained pressed powder obtains the Ni-based bimetallic catalyst Ni (0.05) of SBA-15 load-Y (0.06)-SBA-15.The pore volume of gained Ni (0.05)-Y (0.06)-SBA-15 is 0.27cm
3/ g, specific area is 219m
2/ g, the aperture is 4.04nm; The content of Ni and Y is respectively 4.1wt% and 8.1wt%; The molar ratio of Ni and Si is 0.04, and the molar ratio of rare earth element y and Si is 0.05.
In embodiment 5Ni (0.15)-Y (0.03)-SBA-15(bracket numerical value be Ni and Y respectively with the setting molar ratio of Si)
The synthetic method of SBA-15 molecular sieve is identical with embodiment 4 in the present embodiment.That different is nitric acid nickel (NO
3)
26H
2The consumption of O is 0.37g, yttrium nitrate Y (NO
3)
36H
2The consumption of O is 0.10g.The pore volume of preparation gained Ni (0.15)-Y (0.03)-SBA-15 is 0.26cm
3/ g, specific area is 230m
2/ g, the aperture is 4.09nm; The content of Ni and Y is respectively 12.9wt% and 4.0wt%; The molar ratio of Ni and Si is 0.13, and the molar ratio of rare earth element y and Si is 0.03.
In embodiment 6Ni (0.10)-La (0.04)-SBA-15(bracket numerical value be Ni and La respectively with the setting ratio of Si)
The synthetic method of SBA-15 molecular sieve is identical with embodiment 1 in the present embodiment.Different is with 0.14g lanthanum nitrate La (NO
3)
36H
2O replaces cerous nitrate.Preparation gained Ni-La-SBA-15 pore volume is 0.29cm
3/ g, specific area is 238m
2/ g, the aperture is 4.33nm; The content of Ni and La is respectively 9.4wt% and 7.9wt%; The molar ratio of Ni and Si is 0.10, and the ratio of rare-earth elements La and Si is 0.03.
In embodiment 7Ni (0.15)-La (0.06)-SBA-15(bracket numerical value be Ni and Y respectively with the ratio of Si)
The synthetic method of the SBA-15 molecular sieve of present embodiment is identical with embodiment 2.That different is nitric acid nickel (NO
3)
26H
2The consumption of O is 0.37g, lanthanum nitrate La (NO
3)
36H
2The consumption 0.20g of O.Preparation gained Ni-La-SBA-15 pore volume is 0.28cm
3/ g, specific area is 245m
2/ g, the aperture is 4.30nm; The content of Ni and La is respectively 13.8wt% and 10.9wt%; The molar ratio of Ni and Si is 0.14, and the ratio of rare-earth elements La and Si is 0.05.
Embodiment 8
The bimetallic catalyst that embodiment 1～7 is prepared and corresponding identical with above-mentioned corresponding embodiment content similar and nickel with the Ni-SBA-15(Ni-SBA-15 preparation method of one-component) carries out methane reforming reaction.
The condition of methane reforming reaction is as follows: the catalyst fines after the roasting through grinding, compressing tablet, pulverize, sieve after, get 60～80 purpose catalyst and carry out catalytic reaction, catalyst amount 0.1g.The reaction procatalyst was through 700 ℃ of hydrogen stream reduction 30 minutes.The condition of catalytic reaction: CH
4/ CO
2(mol ratio)=1/1, overall flow rate 62mLmin
-1, reaction temperature is 600～800 ℃, 50 ℃ of temperature intervals.Product detects online with Kechuang GC-9800 type gas chromatograph after cold-trap (mixture of ice and water) dewaters.
The result shows that bimetallic catalyst has good catalytic activity in methane reforming reaction shown in Fig. 4～6.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. the preparation method of the Ni-based bimetallic catalyst take SBA-15 as carrier is characterized in that comprising the steps:
(1) adopt hydro-thermal method to prepare the SBA-15 mesopore molecular sieve;
(2) preparation of the Ni-based bimetallic catalyst take SBA-15 as carrier: with the nitrate water dissolving of nickel nitrate and rare earth metal, add the SBA-15 mesopore molecular sieve, dipping, dry in baking oven, gained pressed powder again roasting obtains Ni-based bimetallic catalyst take SBA-15 as carrier.
2. the preparation method of the Ni-based bimetallic catalyst take SBA-15 as carrier according to claim 1, it is characterized in that the method that the hydro-thermal method described in the step (1) prepares the SBA-15 mesopore molecular sieve is: triblock copolymer surfactant P123 is dissolved in the hydrochloric acid solution, made it to dissolve fully in 3～5 hours 35～50 ℃ of lower stirrings; Add again ethyl orthosilicate, 35～50 ℃ of lower stirrings 2～4 hours; Then after placing 24～60 hours in 50～60 ℃ water-bath, suction filtration dries naturally, and 500～550 ℃ of roastings obtained the SBA-15 mesopore molecular sieve in 3～6 hours in air atmosphere.
3. the preparation method of the Ni-based bimetallic catalyst take SBA-15 as carrier according to claim 2 is characterized in that:
Described hydrochloric acid solution is 2molL
-1Hydrochloric acid solution;
The mol ratio of described ethyl orthosilicate, P123 and hydrochloric acid is 1:0.017:5.85～8.0.
4. the preparation method of the Ni-based bimetallic catalyst take SBA-15 as carrier according to claim 1 is characterized in that:
Rare earth metal described in the step (2) is yttrium, cerium or lanthanum;
Dipping described in the step (2) is 25～35 ℃ of dippings 20～40 minutes;
Drying described in the step (2) is 95～110 ℃ of dryings 10～14 hours;
Roasting described in the step (2) is 500～550 ℃ of roastings 3～5 hours;
The mol ratio of the nitrate of SBA-15, nickel nitrate and the rare earth metal described in the step (2) is 1:0.05～0.15:0.02～0.06.
5. Ni-based bimetallic catalyst take SBA-15 as carrier, it is characterized in that: each described preparation method prepares by claim 1～4.
6. the Ni-based bimetallic catalyst take SBA-15 as carrier according to claim 5, it is characterized in that: described Ni-based bimetallic catalyst take SBA-15 as carrier is Ni-Y-SBA-15, Ni-Ce-SBA-15 or Ni-La-SBA-15.
7. the Ni-based bimetallic catalyst take SBA-15 as carrier according to claim 5, it is characterized in that: the pore volume of described Ni-based bimetallic catalyst take SBA-15 as carrier is 0.24～0.29cm
3/ g, specific area is 200～350m
2/ g, the aperture is 3.2～4.4nm.
8. the Ni-based bimetallic catalyst take SBA-15 as carrier according to claim 5, it is characterized in that: in the described Ni-based bimetallic catalyst take SBA-15 as carrier, the mol ratio of Ni element and Si element is 0.04～0.15:1, and the mol ratio of thulium and Si element is 0.02～0.06:1.
9. each described Ni-based bimetallic catalyst application in methane reforming reaction take SBA-15 as carrier of claim 5～8.
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| CN110893347A (en) * | 2018-09-12 | 2020-03-20 | 华东理工大学 | Low-temperature high-activity nickel-based bimetallic methanation catalyst and preparation method and application thereof |
| CN111097494A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Multi-component composite catalyst and preparation method thereof |
| CN116371451B (en) * | 2023-04-14 | 2024-05-17 | 西安交通大学 | Cerium doped nickel-based catalyst suitable for methane dry reforming and preparation method thereof |
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| CN104001538A (en) * | 2014-06-12 | 2014-08-27 | 天津大学 | Nickel-loaded SBA-15 catalyst modified by cerium dioxide and preparation method and application of nickel-loaded SBA-15 catalyst modified by cerium dioxide |
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| CN107413373A (en) * | 2017-08-08 | 2017-12-01 | 太原理工大学 | A kind of high fast preparation method than table bimetallic silicide methanation catalyst |
| CN107413373B (en) * | 2017-08-08 | 2019-10-22 | 太原理工大学 | A kind of fast preparation method of high-specific surface area bimetallic silicide methanation catalyst |
| JP2019037905A (en) * | 2017-08-22 | 2019-03-14 | 国立研究開発法人物質・材料研究機構 | Catalytic substance for low temperature methane reforming |
| CN110339856A (en) * | 2018-04-03 | 2019-10-18 | 华东理工大学 | One kind is with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methanation catalyst and the preparation method and application thereof of carrier |
| CN110893347A (en) * | 2018-09-12 | 2020-03-20 | 华东理工大学 | Low-temperature high-activity nickel-based bimetallic methanation catalyst and preparation method and application thereof |
| CN111097494A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Multi-component composite catalyst and preparation method thereof |
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