CN111359626A - RuNi bimetal supported carbon dioxide methanation catalyst and preparation method thereof - Google Patents
RuNi bimetal supported carbon dioxide methanation catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 29
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 29
- 239000000956 alloy Substances 0.000 claims abstract description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000011068 loading method Methods 0.000 claims abstract description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000002244 precipitate Substances 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 230000009467 reduction Effects 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 45
- 238000005406 washing Methods 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 5
- 229910019891 RuCl3 Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
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- 239000002082 metal nanoparticle Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- 229910001845 yogo sapphire 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
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B01J35/23—
-
- B01J35/399—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
Abstract
The invention relates to a RuNi bimetal supported carbon dioxide methanation catalyst, which consists of an active component RuNi alloy and a carrier TiO2Composition is carried out; the molar ratio of Ru to Ni in the active component RuNi alloy is 0.1: 1-10: 1; the active component RuNi alloy is arranged on the TiO carrier2The loading amount on the catalyst is 0.1-30 wt%. Meanwhile, the invention also discloses a preparation method of the catalyst. The catalyst prepared by the invention shows excellent catalytic performance when used for synthesizing methane by carbon dioxide hydrogenation, and is easy to realize commercialization.
Description
Technical Field
The invention relates to CO2The technical field of catalytic hydrogenation methanation, in particular to a RuNi bimetal supported carbon dioxide methanation catalyst and a preparation method thereof.
Background
Rich and cheap CO2The direct conversion into chemicals not only can greatly reduce the emission of greenhouse gases, but also can reduce the human survival ring caused by greenhouse effectEnvironmental impact, and can prepare chemicals with high added values, and can show good environmental benefit and economic benefit. CO 22The catalytic hydromethanation technology is one of the most effective technologies for realizing resource utilization at present.
CO2The methanation catalyst mainly uses group 8 metal (such as Ni, Ru, Rh, Pd, Pt and Co, etc.) as typical active component, and uses oxide (such as SiO)2、ZrO2、TiO2Or Al2O3Etc.) are carriers, which have very high catalytic activity. The noble metal is expensive, so the commercial popularization economy is low. Therefore, the research of the non-noble metal catalyst has important significance. Ni is a non-noble metal with the best hydrogenation activity, and people have carried out a great deal of research on selective hydrogenation of the nickel base in the past decades, and the existing research shows that two active centers exist on the Ni-based catalyst, one is a hydrogenolysis metal center, and the corresponding active center is bare nickel which is not in contact with a carrier, and the active sites are easy to generate side reaction and carbon deposition; and the other active site is a hydrogenation active site, corresponding to nickel in contact with the support, which is the active center of the main reaction. Numerous studies have demonstrated that metallic nickel can significantly improve catalytic performance by forming alloys or intermetallics with other metals or metalloids.
The development of RuNi bimetallic catalyst can effectively reduce the preparation cost of the catalyst and fully play the role of higher CO of Ni-based catalyst2Methanation activity and low cost. Although some special preparation methods, such as a bimetallic simple substance solid-phase melting method, can prepare RuNi intermetallic compounds, the method is far away from the preparation and application of actual catalysts and is difficult to be applied to the actual catalytic process; the most commonly used methods for the preparation of supported metal catalysts are precipitation deposition and impregnation deposition. However, in most cases it is difficult to obtain metal nanocatalysts with uniform particle size, high dispersion and good thermal stability, especially at high loadings. This is mainly due to the uneven distribution of the active precursor on the support and to the weaker interaction with the support; in addition, agglomeration of metal nanoparticles during the catalytic reaction further reduces goldThe degree of dispersion of the genus.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a RuNi bimetallic supported carbon dioxide methanation catalyst which has excellent catalytic performance and is easy to realize commercialization.
The invention aims to solve another technical problem of providing a preparation method of the RuNi bimetallic supported carbon dioxide methanation catalyst.
In order to solve the problems, the RuNi bimetal supported carbon dioxide methanation catalyst is characterized in that: the catalyst consists of an active component RuNi alloy and a carrier TiO2Composition is carried out; the molar ratio of Ru to Ni in the active component RuNi alloy is 0.1: 1-10: 1; the active component RuNi alloy is arranged on the TiO carrier2The loading amount on the catalyst is 0.1-30 wt%.
The preparation method of the RuNi bimetallic supported carbon dioxide methanation catalyst comprises the following steps:
⑴ RuCl with the concentration of 0.05-5 mol/L3An aqueous solution and Ni (NO) with a concentration of 0.05-5 mol/L3)2•6H2The molar ratio of the Ru to the Ni of the O aqueous solution is 0.1: 1-10: 1, and continuously stirring for 0.5-4 hours at room temperature to obtain a mixed solution;
⑵ adding TiO into the mixed solution2Stirring the powder for 0.5-4 h at room temperature, and adjusting the pH value to 8.5; then raising the temperature to 40 ℃, dropwise adding a precipitator, coprecipitating the two metal salts, and continuously stirring for 1-12 hours; heating to 80 ℃, stirring for 1-24 h, filtering, washing and drying to obtain a precipitate; the addition amount of the precipitant is determined according to the precipitation types of Ru and Ni and the type of the selected precipitant, and the addition amount of the precipitant is 1.1 times of the theoretical value;
⑶, heating the precipitate to a reduction temperature of 400-700 ℃ at a heating rate of 1-20 ℃/min, reducing the precipitate at the reduction temperature, and cooling the precipitate to room temperature in the reducing atmosphere to obtain the RuNi bimetallic supported catalyst with a loading of 0.1-30 wt%.
The precipitant in the step ⑵ is Na2CO3、NaOH、K2CO3And KOH.
The drying condition in the step ⑵ is that the vacuum is 60 ℃ or the non-vacuum is 120 ℃, and the drying time is 12-24 h.
The reducing atmosphere in step ⑶ refers to high purity hydrogen or standard hydrogen.
Compared with the prior art, the invention has the following advantages:
1. the element proportion of the RuNi alloy in the invention can be adjusted by the precursor RuCl3And Ni (NO)3)2•6H2The proportion of O element is regulated, and the active RuNi bimetallic alloy atoms are highly dispersed on the carrier to form alloy while the proportion of Ru and Ni elements is controllably regulated. X-ray diffraction patterns show that the active component RuNi is highly dispersed on the carrier and only shows weak characteristic peaks (see FIG. 1).
2. The invention is in RuCl3And Ni (NO)3)2•6H2The method facilitates the uniform dispersion of the catalyst active component on the carrier by directly adding the carrier to the mixed solution of O (see FIG. 2).
3. The catalyst prepared by the invention shows excellent catalytic performance when used for synthesizing methane by carbon dioxide hydrogenation, and is easy to realize commercialization.
Subjecting the catalyst obtained by the invention to CO2And (5) hydrogenation reduction test. And (3) testing conditions are as follows: reaction gas CO2/H2Wherein the volume fraction ratio of the gas is CO2:H2= 1:3, flow rate of reaction gas is 80 mL/min; at a temperature of 240 ℃ and a pressure of 3 MPa. The test results are shown in table 1.
TABLE 1 RuNi catalysis of CO2Activity test result of hydrogenation synthesis methane
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is an X-ray diffraction pattern of RuNi catalyst of the present invention. Wherein: a is an X-ray diffraction pattern of the RuNi catalyst prepared in example 1, and b is an X-ray diffraction pattern of the RuNi catalyst prepared in example 2.
FIG. 2 is a transmission electron micrograph of RuNi catalyst of the present invention. Wherein a is a transmission electron microscope photograph of the RuNi catalyst prepared in the embodiment 1 of the present invention, and b is a transmission electron microscope photograph of the RuNi catalyst prepared in the embodiment 2 of the present invention.
Detailed Description
Example 1A RuNi bimetallic supported carbon dioxide methanation catalyst is prepared from active component RuNi alloy and carrier TiO2And (4) forming. Wherein: the molar ratio of Ru to Ni in the active component RuNi alloy is 0.1: 1; active component RuNi alloy on carrier TiO2The loading on the catalyst was 0.1 wt%.
The preparation method comprises the following steps:
⑴ RuCl with concentration of 0.3 mol/L31mL of aqueous solution and 0.3 mol/L of Ni (NO)3)2•6H2Mixing 10 mL of O aqueous solution (the molar ratio of Ru to Ni is 0.1: 1), and continuously stirring for 1h at room temperature to obtain a mixed solution;
⑵ the mixed solution was added with 206.2 g TiO2Stirring the powder for 0.5 h at room temperature, and adjusting the pH value to 8.5 by using ammonia water; the temperature was then raised to 40 ℃ and 0.94 g Na was added dropwise2CO3After the two metal salts are coprecipitated, continuously stirring for 1 h; heating to 80 deg.C, stirring for 2 h, filtering, washing with deionized water until filtrate is neutral, and vacuum drying at 60 deg.C for 12 h to obtain precipitate;
⑶ putting the precipitate in reducing atmosphere, heating to 400 deg.C reducing temperature with a heating rate of 10 deg.C/min, reducing at the reducing temperature, and cooling to room temperature in reducing atmosphere to obtain RuNi bimetal supported catalyst with a loading of 0.1 wt%.
The characterization results of XRD and transmission electron microscopy of the RuNi bimetallic supported catalyst are shown in figure 1a and figure 2a, and the characteristic peak positions of Ru and Ni are not seen in the figure, which indicates that the dispersion degree of the Ru and Ni is higher.
Example 2A RuNi bimetallic supported carbon dioxide methanation catalyst is prepared from active component RuNi alloy and carrier TiO2And (4) forming. Wherein: the molar ratio of Ru to Ni in the active component RuNi alloy is 0.1: 1; active component RuNi alloy on carrier TiO2The loading on the catalyst was 15 wt%.
The preparation method comprises the following steps:
⑴ RuCl with concentration of 0.3 mol/L31mL of aqueous solution and 0.3 mol/L of Ni (NO)3)2•6H2Mixing 10 mL of O aqueous solution (the molar ratio of Ru to Ni is 0.1: 1), and continuously stirring for 1h at room temperature to obtain a mixed solution;
⑵ the mixed solution was added with 1.17 g of TiO2Stirring the powder for 0.5 h at room temperature, and adjusting the pH value to 8.5 by using ammonia water; the temperature was then raised to 40 ℃ and 0.94 g Na was added dropwise2CO3After the two metal salts are coprecipitated, continuously stirring for 1 h; heating to 80 deg.C, stirring for 2 h, filtering, washing with deionized water until filtrate is neutral, and vacuum drying at 60 deg.C for 12 h to obtain precipitate;
⑶ putting the precipitate in a reducing atmosphere, heating to 400 ℃ reduction temperature at a heating rate of 10 ℃/min, reducing at the reduction temperature, and cooling to room temperature in the reducing atmosphere to obtain the RuNi bimetallic supported catalyst with 15 wt% of loading capacity.
The XRD and transmission electron microscope characterization results of the RuNi bimetallic supported catalyst are shown in figure 1b and figure 2b, and the characteristic peak positions of Ru and Ni are not seen in the figures, which also indicates that the dispersion degree of the Ru and Ni is higher.
Example 3A RuNi bimetallic Supported carbon dioxide methanation catalyst consisting of an active component RuNi alloy and a support TiO2And (4) forming. Wherein: the molar ratio of Ru to Ni was 0.1: 1; active component RuNi alloy on carrier TiO2The loading on the catalyst was 30 wt%.
The preparation method comprises the following steps:
⑴ RuCl with concentration of 0.3 mol/L31mL of aqueous solution and 0.3 mol/L of Ni (NO)3)2•6H2Mixing 10 mL of O aqueous solution (the molar ratio of Ru to Ni is 0.1: 1), and continuously stirring for 1h at room temperature to obtain a mixed solution;
⑵ the mixed solution was added with 0.48 g of TiO2Stirring the powder for 0.5 h at room temperature, and adjusting the pH value to 8.5 by using ammonia water; the temperature was then raised to 40 ℃ and 0.94 g Na was added dropwise2CO3After the two metal salts are coprecipitated, continuously stirring for 1 h; heating to 80 deg.C, stirring for 2 h, filtering, washing with deionized water until filtrate is neutral, and drying at 120 deg.C for 12 h to obtain precipitate;
⑶ putting the precipitate in a reducing atmosphere, heating to 400 ℃ reduction temperature at a heating rate of 10 ℃/min, reducing at the reduction temperature, and cooling to room temperature in the reducing atmosphere to obtain the RuNi bimetallic supported catalyst with the load of 30 wt%.
Example 4A RuNi bimetallic Supported carbon dioxide methanation catalyst, consisting of an active component RuNi alloy and a support TiO2And (4) forming. Wherein: the molar ratio of Ru to Ni is 10: 1; active component RuNi alloy on carrier TiO2The loading on the catalyst was 15 wt%.
The preparation method comprises the following steps:
⑴ RuCl with concentration of 0.3 mol/L 310 mL of aqueous solution and 0.3 mol/L of Ni (NO)3)2•6H2Mixing 1mL of O aqueous solution (the molar ratio of Ru to Ni is 10: 1), and continuously stirring for 1h at room temperature to obtain a mixed solution;
⑵ the mixed solution was added with 1.82 g of TiO2Stirring the powder for 0.5 h at room temperature, and adjusting the pH value to 8.5 by using ammonia water; the temperature was then raised to 40 ℃ and 0.56 g Na was added dropwise2CO3After the two metal salts are coprecipitated, continuously stirring for 1 h; heating to 80 deg.C, stirring for 2 h, filtering, washing with deionized water until filtrate is neutral, and drying at 120 deg.C for 12 h to obtain precipitate;
⑶ putting the precipitate in pure hydrogen atmosphere, heating to 400 ℃ reduction temperature with a heating rate of 10 ℃/min, reducing at the reduction temperature, and cooling to room temperature in reducing atmosphere to obtain RuNi bimetallic supported catalyst with 15 wt% of loading.
Example 5A RuNi bimetallic Supported carbon dioxide methanation catalyst consisting of an active ingredient RuNi alloy and a support TiO2And (4) forming. Wherein: the molar ratio of Ru to Ni was 8: 1; active component RuNi alloy on carrier TiO2The loading on the catalyst was 20 wt%.
The preparation method comprises the following steps:
⑴ RuCl with a concentration of 0.05 mol/L38 mL of aqueous solution and 0.05 mol/L of Ni (NO)3)2•6H2Mixing 1mL of O aqueous solution (the molar ratio of Ru to Ni is 8: 1), and continuously stirring for 0.5 h at room temperature to obtain a mixed solution;
⑵ the mixed solution was added with 0.17 g of TiO2Stirring the powder for 0.5 h at room temperature, and adjusting the pH value to 8.5 by using ammonia water; the temperature was then raised to 40 ℃ and 0.09 g K was added dropwise2CO3After the two metal salts are coprecipitated, stirring is continued for 5 hours; heating to 80 deg.C, stirring for 1h, filtering, washing with deionized water until filtrate is neutral, and drying at 60 deg.C for 24h to obtain precipitate;
⑶ putting the precipitate in pure hydrogen atmosphere, heating to 600 deg.C reduction temperature with a heating rate of 15 deg.C/min, reducing at the reduction temperature, and cooling to room temperature in reducing atmosphere to obtain RuNi bimetal supported catalyst with a loading of 20 wt%.
Example 6A RuNi bimetallic Supported carbon dioxide methanation catalyst consisting of an active component RuNi alloy and a support TiO2And (4) forming. Wherein: the molar ratio of Ru to Ni is 10: 1; active component RuNi alloy on carrier TiO2The loading on the catalyst was 15 wt%.
The preparation method comprises the following steps:
⑴ will be 5 mol/LRuCl 310 mL of aqueous solution and 5 mol/L of Ni (NO)3)2•6H2Mixing 1mL of O aqueous solution (the molar ratio of Ru to Ni is 10: 1), and continuously stirring for 4h at room temperature to obtain a mixed solution;
⑵ the mixed solution was added with 30.3 g of TiO2Stirring the powder for 0.5 h at room temperature, and adjusting the pH value to 8.5 by using ammonia water; then raising the temperature to 40 ℃, dropwise adding 10 g of NaOH, and continuously stirring for 12 hours after the two metal salts are coprecipitated; heating to 80 deg.C, stirring for 24 hr, filtering, washing with deionized water until filtrate is neutral, and drying at 120 deg.C for 14 hr to obtain precipitate;
⑶ putting the precipitate in pure hydrogen atmosphere, heating to 700 deg.C reduction temperature with 20 deg.C/min heating rate program, reducing at the reduction temperature, cooling to room temperature in reducing atmosphere to obtain RuNi bimetal supported catalyst with 15 wt% loading.
Example 7A RuNi bimetallic Supported carbon dioxide methanation catalyst, consisting of an active component RuNi alloy and a support TiO2And (4) forming. Wherein: the molar ratio of Ru to Ni is 10: 1; active component RuNi alloy on carrier TiO2The loading on the catalyst was 15 wt%.
The preparation method comprises the following steps:
⑴ RuCl with concentration of 0.3 mol/L 310 mL of aqueous solution and 0.3 mol/L of Ni (NO)3)2•6H2Mixing 1mL of O aqueous solution (the molar ratio of Ru to Ni is 10: 1), and continuously stirring for 1h at room temperature to obtain a mixed solution;
⑵ the mixed solution was added with 1.82 g of TiO2Stirring the powder for 0.5 h at room temperature, and adjusting the pH value to 8.5 by using ammonia water; then raising the temperature to 40 ℃, dropwise adding 0.54 g of KOH, and continuously stirring for 1h after the two metal salts are coprecipitated; heating to 80 deg.C, stirring for 2 h, filtering, washing with deionized water until filtrate is neutral, and drying at 120 deg.C for 12 h to obtain precipitate;
⑶ putting the precipitate in pure hydrogen atmosphere, heating to 400 ℃ reduction temperature with a heating rate of 10 ℃/min, reducing at the reduction temperature, and cooling to room temperature in reducing atmosphere to obtain RuNi bimetallic supported catalyst with 15 wt% of loading.
In examples 1 to 7, the reducing atmosphere refers to high purity hydrogen or standard hydrogen.
The carrier being TiO2Other metal or non-metal oxide supports may be used instead. The amount thereof was determined by calculation based on the amounts of Ru and Ni loaded.
The addition amount of the precipitant is determined according to the precipitation types of Ru and Ni and the type of the selected precipitant, and the addition amount of the precipitant is 1.1 times of the theoretical value. Theoretical value calculation method: with RuCl3For example, if Na is taken2CO3As a precipitant, RuCO is precipitated31mol of RuCl3Complete precipitation requires 1mol of Na2CO3The corresponding mass was 106 g.
Claims (5)
1. A RuNi bimetal load type carbon dioxide methanation catalyst is characterized in that: the catalyst consists of an active component RuNi alloy and a carrier TiO2Composition is carried out; the molar ratio of Ru to Ni in the active component RuNi alloy is 0.1: 1-10: 1; the active component RuNi alloy is arranged on the TiO carrier2The loading amount on the catalyst is 0.1-30 wt%.
2. The preparation method of RuNi bimetallic supported carbon dioxide methanation catalyst as claimed in claim 1, comprising the following steps:
⑴ RuCl with the concentration of 0.05-5 mol/L3An aqueous solution and Ni (NO) with a concentration of 0.05-5 mol/L3)2•6H2The molar ratio of the Ru to the Ni of the O aqueous solution is 0.1: 1-10: 1, and continuously stirring for 0.5-4 hours at room temperature to obtain a mixed solution;
⑵ adding TiO into the mixed solution2Stirring the powder for 0.5-4 h at room temperature, and adjusting the pH value to 8.5; then raising the temperature to 40 ℃, dropwise adding a precipitator, coprecipitating the two metal salts, and continuously stirring for 1-12 hours; heating to 80 deg.C, stirring for 1-24 hr, filtering, washingWashing and drying to obtain a precipitate; the addition amount of the precipitant is determined according to the precipitation types of Ru and Ni and the type of the selected precipitant, and the addition amount of the precipitant is 1.1 times of the theoretical value;
⑶, heating the precipitate to a reduction temperature of 400-700 ℃ at a heating rate of 10-20 ℃/min, reducing the precipitate at the reduction temperature, and cooling the precipitate to room temperature in the reducing atmosphere to obtain the RuNi bimetallic supported catalyst with a load of 0.1-30 wt%.
3. The method for preparing RuNi bimetallic supported carbon dioxide methanation catalyst as claimed in claim 2, wherein the precipitant in the step ⑵ is Na2CO3、NaOH、K2CO3And KOH.
4. The preparation method of RuNi bimetallic supported carbon dioxide methanation catalyst as claimed in claim 2, wherein the drying condition in the step ⑵ is vacuum of 60 ℃ or non-vacuum of 120 ℃ for 12-24 h.
5. The method for preparing RuNi bimetallic supported carbon dioxide methanation catalyst as claimed in claim 2, wherein the reducing atmosphere in the step ⑶ is high purity hydrogen or standard hydrogen.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115180593A (en) * | 2022-06-17 | 2022-10-14 | 北京化工大学 | Method for preparing high-added-value product by reforming light-driven co-thermal coupling hydrocarbons from carbonate refining |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1107078A (en) * | 1994-07-07 | 1995-08-23 | 南开大学 | Catalyst used for carbon dioxide hydrogenation reaction |
| CN102259003A (en) * | 2011-05-31 | 2011-11-30 | 武汉科林精细化工有限公司 | Coke-oven gas methanation catalyst and preparation method thereof |
| CN102489302A (en) * | 2011-11-22 | 2012-06-13 | 北京化工大学 | Titanium dioxide supported nickel catalyst preparation method and its application |
| CN104148065A (en) * | 2013-05-14 | 2014-11-19 | 中国科学院大连化学物理研究所 | Catalyst used for methanation of carbon dioxide, preparation method therefor and applications thereof |
| WO2016087976A1 (en) * | 2014-12-01 | 2016-06-09 | Sabic Global Technologies B.V. | Synthesis of trimetallic nanoparticles by homogeneous deposition precipitation, and application of the supported catalyst for carbon dioxide reforming of methane |
| CN108525676A (en) * | 2018-05-09 | 2018-09-14 | 南通龙翔新材料科技股份有限公司 | A kind of Ru-Ni/Ce-Zr composite oxide catalysts and preparation method thereof |
| CN109806874A (en) * | 2019-03-20 | 2019-05-28 | 福州大学 | A kind of preparation method and application of carbon dioxide methanation nickel-based multimetallic catalyst |
| CN110711582A (en) * | 2019-09-18 | 2020-01-21 | 郑州大学 | Catalyst, preparation method and application thereof |
-
2020
- 2020-05-07 CN CN202010375980.9A patent/CN111359626A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1107078A (en) * | 1994-07-07 | 1995-08-23 | 南开大学 | Catalyst used for carbon dioxide hydrogenation reaction |
| CN102259003A (en) * | 2011-05-31 | 2011-11-30 | 武汉科林精细化工有限公司 | Coke-oven gas methanation catalyst and preparation method thereof |
| CN102489302A (en) * | 2011-11-22 | 2012-06-13 | 北京化工大学 | Titanium dioxide supported nickel catalyst preparation method and its application |
| CN104148065A (en) * | 2013-05-14 | 2014-11-19 | 中国科学院大连化学物理研究所 | Catalyst used for methanation of carbon dioxide, preparation method therefor and applications thereof |
| WO2016087976A1 (en) * | 2014-12-01 | 2016-06-09 | Sabic Global Technologies B.V. | Synthesis of trimetallic nanoparticles by homogeneous deposition precipitation, and application of the supported catalyst for carbon dioxide reforming of methane |
| CN108525676A (en) * | 2018-05-09 | 2018-09-14 | 南通龙翔新材料科技股份有限公司 | A kind of Ru-Ni/Ce-Zr composite oxide catalysts and preparation method thereof |
| CN109806874A (en) * | 2019-03-20 | 2019-05-28 | 福州大学 | A kind of preparation method and application of carbon dioxide methanation nickel-based multimetallic catalyst |
| CN110711582A (en) * | 2019-09-18 | 2020-01-21 | 郑州大学 | Catalyst, preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| FELIX LANGE ET AL.: ""Heterogeneously-Catalyzed Hydrogenation of Carbon"", 《ENERGY TECHNOLOGY》 * |
| WENLONG ZHEN ET AL.: ""Enhancing Catalytic Activity and Stability for CO2 Methanation on Ni-Ru/γ-Al2O3 via Modulating Impregnation Sequence and Controlling Surface Active Species"", 《RSC ADVANCES》 * |
| 季明瑞等: "适用于二氧化碳甲烷化反应的Ni基催化剂", 《石油化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115180593A (en) * | 2022-06-17 | 2022-10-14 | 北京化工大学 | Method for preparing high-added-value product by reforming light-driven co-thermal coupling hydrocarbons from carbonate refining |
| CN115180593B (en) * | 2022-06-17 | 2024-01-19 | 北京化工大学 | Method for preparing high-added-value product by reforming light-driven carbonate refining co-thermal coupling hydrocarbon |
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