CN110639523A - Sulfur poisoning resistant Ni-based methanation catalyst and preparation method and application thereof - Google Patents
Sulfur poisoning resistant Ni-based methanation catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 title abstract description 13
- 239000011593 sulfur Substances 0.000 title abstract description 13
- 231100000572 poisoning Toxicity 0.000 title abstract description 10
- 230000000607 poisoning effect Effects 0.000 title abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 34
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 10
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 53
- 239000007789 gas Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000012018 catalyst precursor Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
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Abstract
The invention discloses a sulfur poisoning resistant Ni-based methanation catalyst and a preparation method and application thereof. The Ni-based methanation catalyst takes metal Ni particles as active components and SiO2Is a carrier, wherein the mass percentage of the metal Ni particles is 8-12%; the SiO2The specific surface area of the carrier is not less than 650m2g‑1Pore diameter is not less than 20nm, and pore volume is not less than 4cm3g‑1Wherein the proportion of the internal surface area is not less than 90 percent; the particle size of the metal Ni particles is 6-9nm, and the Ni particles are distributed in the carrier pore canal. The invention provides an application of the catalyst in synthesis gas methanation. The Ni-based methanation catalyst of the inventionCompared with the traditional catalyst which loads Ni active centers on the outer surface of a carrier, the catalyst has better sulfur poisoning resistance, so that the catalyst has longer service life.
Description
(I) technical field
The invention relates to a Ni-based methanation catalyst, a preparation method thereof and application thereof in methanation of synthesis gas (CO + 3H)2-CH4+H2O).
(II) background of the invention
With increasing emphasis on environmental and atmospheric pollution problems, the demand for clean energy is increasing. As an energy source with low pollution and high efficiency, the market demand of natural gas is rapidly rising in recent years. Because of the energy structure characteristics of rich coal, flat oil and little gas in China, the coal or biomass is used as the raw material to obtain the synthesis gas (CO + H) firstly through the gasification process2) Then obtaining CH by a catalytic reaction process4Is one of the important ways to obtain the clean energy. According to a large number of reports in literature, metals such as Ru, Rh, Fe, Co, Ni and the like have certain methanation reaction activity. In comparison, the metal Ni-based catalyst is a methanation catalyst with the potential of industrial application at present due to higher activity and low price. However, small amounts of sulfur-containing impurities (e.g., H) are inevitably present in the coal-to-synthesis gas2S) causing sulfur poisoning of the Ni-based methanation catalyst and resulting deactivation. The property of Ni active center can be changed by adding various alkali metal and noble metal additives, which is the main method commonly used for improving the sulfur poisoning resistance of Ni-based catalyst at present.
Disclosure of the invention
The invention aims to provide a Ni-based methanation catalyst with sulfur-tolerant toxicity performance, a preparation method thereof and application thereof in synthesis gas methanation.
In order to solve the technical problems, the invention adopts the following technical scheme:
in one aspect, the invention provides a Ni-based methanation catalyst, which takes metal Ni particles as active components and SiO2Is a carrier, wherein the mass percentage of the metal Ni particles is 8-12%; the SiO2The specific surface area of the carrier is not less than 650m2g-1Pore diameter is not less than 20nm, and pore volume is not less than 4cm3g-1Wherein the proportion of the internal surface area is not less than 90 percent; the particle size of the metal Ni particles is 6-9nm, and the Ni particles are distributed in the carrier pore canal.
Further, the mass percentage content of the metal Ni particles is 10%.
On the other hand, the invention provides a preparation method of the Ni-based methanation catalyst, which comprises the following steps:
1) dissolving a certain amount of nickel-containing inorganic salt in a certain volume of ethanol to obtain a solution A;
2) dropwise adding the solution A to SiO according to the loading requirement2On solid particles;
3) removing the solvent from the sample obtained in the step 2), and then roasting the obtained solid particles in the air at 400-600 ℃ for 3-6h to obtain a catalyst precursor loaded with NiO precursor particles, wherein the particle size of the NiO precursor particles is 6-8 nm;
4) reducing and activating the catalyst precursor obtained in the step 3) in an atmosphere containing hydrogen at the activation temperature of 400-500 ℃ for 4-10h to obtain the Ni-based methanation catalyst.
Further, in the step 1), the nickel-containing inorganic salt is nickel nitrate hexahydrate; wherein the concentration of nickel nitrate is 0.03-0.05g cm-3。
Further, in the step 3), the temperature for removing the solvent is 50-100 ℃.
Further, in the step 3), the roasting is carried out in an air atmosphere at the temperature of 500 ℃ for 4 hours.
Further, in the step 4), the hydrogen content in the hydrogen-containing atmosphere is 5-100% by volume, and if there are other gases besides hydrogen, the other gases may be N2Or Ar.
Further, in the step 4), the activation temperature is 480 ℃ and the activation time is 5 h.
In a third aspect, the present invention provides the use of the Ni-based methanation catalyst in syngas (CO + H)2) Application in methanation.
Compared with the prior art, the invention has the following advantages:
(1) the particle size of metal Ni particles in the Ni-based methanation catalyst prepared by the invention is 6-9nm, and the Ni particles are distributed in the pore canal of the carrier. During the methanation reaction, the diffusion speed of sulfur-containing gas molecules is lower than that of H2And CO molecules, so that Ni particles in poresThe sulfur molecule concentration on the surface is lower than that on the surface of Ni particle on the outer surface of the carrier, and the difference of gas molecule hole internal diffusion performance is used to reduce active center surface H2The concentration of S is increased, and the sulfur poisoning resistance of the Ni-based methanation catalyst is improved; therefore, compared with the traditional catalyst which loads Ni active centers on the outer surface of the carrier, the catalyst has longer service life.
(2) The preparation method and the used equipment of the catalyst are simple, and the aim of loading the Ni active center in the pore channel of the carrier is fulfilled.
(IV) description of the drawings
FIG. 1 is SiO that used in example 12Low temperature N of the A support2Physical adsorption-removal of attached figure.
FIG. 2 shows SiO used in comparative example 12Low temperature N of P support2Physical adsorption-removal of attached figure.
FIG. 3 is a graph showing the results of a sulfur poisoning resistance test in methanation reaction of the catalysts prepared in example 1 and comparative example 1.
(V) detailed description of the preferred embodiments
The technical solution of the present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited by the following examples. Also, various omissions, substitutions and changes in the form and details of the illustrated embodiments may be made without departing from the spirit of the inventions.
Example 1:
0.2745g of nickel nitrate hexahydrate is weighed and added to 7cm3A solution was formed in ethanol. The solution was then added dropwise to 0.5g SiO2-A vector (Nano technology). After drying at 65 ℃ for 12h, a solid sample was obtained. And roasting the dried solid sample at 500 ℃ in an air atmosphere for 4h to obtain a catalyst precursor. Finally, the prepared SiO is reacted in a hydrogen atmosphere2The supported Ni-based catalyst was reduced at 480 ℃ for 5h to obtain the final catalyst (Ni/SiO)2-a, metal Ni loading 10% wt.). FIG. 1 is SiO that used in example 12Low temperature N of the A support2Physical adsorption-removal of attached figure. From the figureCan be found in the sample in P/P0When approaching 1, N2The amount of adsorption suddenly increased greatly and no plateaus occurred. This indicates that the sample has predominantly a pore structure with larger pore diameters (table 1). At the same time, the sample had almost no outer surface. On the other hand, the catalyst prepared by the method described in example 1 had a NiO particle size smaller than the pore size of the catalyst (Table 1). In summary, the reduced Ni/SiO2The metallic Ni particles of the-A catalyst should be located in SiO2The mesoporous pore canal of the carrier.
Comparative example 1:
2.7459g of nickel nitrate hexahydrate and 2.9264g of polyethylene glycol were added to 150cm3Deionized Water and 50cm3In n-butanol solution, the mixture was refluxed at 120 ℃ for 2h, then 5g of SiO were added2P support (from Qingdao Baishahe catalyst works) (FIG. 2), and the solvent was removed at 120 ℃. The obtained sample was then calcined at 400 ℃ for 5 hours in an air atmosphere. Finally, reducing and activating the roasted sample for 5 hours at 480 ℃ in hydrogen atmosphere to obtain Ni/SiO2P catalyst (loading of metallic Ni 10% wt.). FIG. 2 shows SiO used in comparative example 12Low temperature N of P support2Physical adsorption-removal of attached figure. Compared with FIG. 1, the sample is in P/P0Near 1 time N2The adsorption amount did not increase greatly and a plateau region appeared.
Example 2: methanation reaction Performance test
From the catalysts prepared in example 1 and comparative example 1, the sulfur poisoning resistance of the catalysts in the methanation reaction was evaluated and tested by using a fixed bed reactor. The composition of the raw material gas for reaction is as follows: 23% of CO and N2:8％，H2S:20ppm，H2The balance; raw material gas flow rate: 60cm3min-1(ii) a Pressure: 1 MPa; reaction temperature: 420 ℃ is adopted. N in raw material gas2As an internal standard, the gas product was subjected to online qualitative and quantitative analysis by gas chromatography. From the experimental data (FIG. 3) it can be seen that the Ni/SiO prepared in example 12Catalyst in the presence of H2In the process of methanation reaction of CO of S molecules, the CO conversion rate can be kept at 100% within 15 h. According to the comparisonExample 1 Ni/SiO prepared2The CO conversion rate of the-P catalyst is rapidly reduced to about 19 percent in the same reaction condition and reaction time, and obvious deactivation phenomenon occurs. Therefore, the catalyst prepared by the method reported by the patent of the invention has better sulfur poisoning resistance in the CO methanation reaction.
TABLE 1 Ni/SiO2A and Ni/SiO2-characterization of the nature of the P catalyst:
Claims (9)
1. a Ni-base catalyst for methanation is prepared from Ni particles as active component and SiO2Is a carrier, wherein the mass percentage of the metal Ni particles is 8-12%; the SiO2The specific surface area of the carrier is not less than 650m2g-1Pore diameter is not less than 20nm, and pore volume is not less than 4cm3g-1Wherein the proportion of the internal surface area is not less than 90 percent; the particle size of the metal Ni particles is 6-9nm, and the Ni particles are distributed in the carrier pore canal.
2. The Ni-based methanation catalyst of claim 1, wherein: the mass percentage of the metal Ni particles is 10 percent.
3. A method of making the Ni-based methanation catalyst of claim 1, the method of making is:
1) dissolving a certain amount of nickel-containing inorganic salt in a certain volume of ethanol to obtain a solution A;
2) dropwise adding the solution A to SiO according to the loading requirement2On solid particles;
3) removing the solvent from the sample obtained in the step 2), and then roasting the obtained solid particles in the air at 400-600 ℃ for 3-6h to obtain a catalyst precursor loaded with NiO precursor particles, wherein the particle size of the NiO precursor particles is 6-8 nm;
4) reducing and activating the catalyst precursor obtained in the step 3) in an atmosphere containing hydrogen at the activation temperature of 400-500 ℃ for 4-10h to obtain the Ni-based methanation catalyst.
4. The method of claim 3, wherein: in the step 1), the nickel-containing inorganic salt is nickel nitrate hexahydrate; the concentration of the nickel nitrate in the solution A is 0.03-0.05g cm-3。
5. The method of claim 3, wherein: in the step 3), the temperature for removing the solvent is 50-100 ℃.
6. The method of claim 3, wherein: in the step 3), the roasting temperature is 500 ℃, and the roasting time is 4 hours.
7. The method of claim 3, wherein: in the step 4), the volume percentage of the hydrogen in the hydrogen-containing atmosphere is 5-100%, and if the hydrogen-containing atmosphere contains other gases besides hydrogen, the other gases are N2Or Ar.
8. The method of claim 3, wherein: in the step 4), the activation temperature is 480 ℃ and the activation time is 5 h.
9. Use of the Ni-based methanation catalyst of claim 1 in the methanation of synthesis gas.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4132672A (en) * | 1976-03-15 | 1979-01-02 | American Gas Association | Methanation catalyst |
| US4490480A (en) * | 1982-04-23 | 1984-12-25 | Internationale Octrooi Maatschappij "Octropa"B.V. | Nickel catalyst on alumina support |
| EP0974637A1 (en) * | 1998-07-22 | 2000-01-26 | Engelhard Corporation | Hydrogenation process |
| CN105170159A (en) * | 2015-04-17 | 2015-12-23 | 浙江工业大学 | Loaded Ni based catalyst and application thereof |
| CN105377422A (en) * | 2013-03-28 | 2016-03-02 | 新加坡科技研究局 | Methanation catalyst |
| CN107199047A (en) * | 2016-03-17 | 2017-09-26 | 华东理工大学 | A kind of Ni-based methanation catalyst being scattered in SBA-15 ducts and its preparation and application |
| CN107519911A (en) * | 2016-06-21 | 2017-12-29 | 华东理工大学 | It is a kind of to prepare nickel-base catalyst and its application in methanation reaction using organic molecule additive |
-
2018
- 2018-06-26 CN CN201810672429.3A patent/CN110639523A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4132672A (en) * | 1976-03-15 | 1979-01-02 | American Gas Association | Methanation catalyst |
| US4490480A (en) * | 1982-04-23 | 1984-12-25 | Internationale Octrooi Maatschappij "Octropa"B.V. | Nickel catalyst on alumina support |
| EP0974637A1 (en) * | 1998-07-22 | 2000-01-26 | Engelhard Corporation | Hydrogenation process |
| CN105377422A (en) * | 2013-03-28 | 2016-03-02 | 新加坡科技研究局 | Methanation catalyst |
| CN105170159A (en) * | 2015-04-17 | 2015-12-23 | 浙江工业大学 | Loaded Ni based catalyst and application thereof |
| CN107199047A (en) * | 2016-03-17 | 2017-09-26 | 华东理工大学 | A kind of Ni-based methanation catalyst being scattered in SBA-15 ducts and its preparation and application |
| CN107519911A (en) * | 2016-06-21 | 2017-12-29 | 华东理工大学 | It is a kind of to prepare nickel-base catalyst and its application in methanation reaction using organic molecule additive |
Non-Patent Citations (6)
| Title |
|---|
| CHANGKUN YUAN: "The SiO2 supported bimetallic Ni–Ru particles: A good sulfur-tolerant catalyst for methanation reaction", 《CHEMICAL ENGINEERING JOURNAL》 * |
| JING WANG ET.AL: "Deposition of carbon species on the surface of metal: As a poison or a promoter for the long-term stability of Ni/SiO2 methanation catalyst?", 《CHEMI CAL ENGIN EERING JOURNAL》 * |
| W.D. FITZHARRIS ET.AL: "Sulfur Deactivation of Nickel Methanation Catalysts", 《JOURNAL OF CATALYSIS》 * |
| 张蕾著: "《烟气脱硫脱硝技术及催化剂的研究进展》", 31 July 2016, 中国矿业大学出版社 * |
| 王晶，姚楠: "适用于合成气制甲烷的Ni基催化剂", 《化学进展》 * |
| 袁涌天等: "载体孔结构对镍基甲烷化催化剂催化活性的影响", 《天气化工（C1化学与化工）》 * |
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