CN113368862A - Carbon dioxide methanation catalyst and preparation method and application thereof - Google Patents
Carbon dioxide methanation catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 23
- 239000001569 carbon dioxide Substances 0.000 title claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 34
- 239000007864 aqueous solution Substances 0.000 claims abstract description 30
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012495 reaction gas Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229910002090 carbon oxide Inorganic materials 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 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
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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Abstract
The invention relates to CO2Methanation catalyst, preparation method and application thereof, and gamma-Al serving as catalyst2O3As carrier, metal Ni as active component, Eu2O3As an auxiliary agent, the mass of metal Ni is 3-25% of the mass of the carrier, and Eu2O3The mass of (A) is 1-8% of the mass of the carrier; the preparation method comprises the following steps: mixing Ni (NO)3)2Aqueous solution, Eu (NO)3)2Aqueous solutionMixing and dropping to gamma-Al2O3Uniformly stirring the powder, drying and roasting to obtain the catalyst for catalyzing CO2And (4) hydrogenation synthesis of methane. Compared with the prior art, the invention provides CO2Catalyst for the reaction of synthesizing methane by hydrogenation, since Eu2O3The addition of the catalyst promotes the active component Ni and the carrier gamma-Al2O3The interaction of the catalyst is beneficial to the high dispersion of Ni, and the CO content of the catalyst is improved2Thereby increasing CO2Catalytic activity of methanation.
Description
Technical Field
The invention belongs to CO2The technical field of methane synthesis by hydrogenation, and relates to CO2A methanation catalyst, a preparation method and application thereof.
Background
CO2Is the most dominant greenhouse gas. With the rapid development of industrialization, fossil fuels are used in large quantities, thereby causing CO in the atmosphere2The concentration continues to rise, which in turn raises a number of environmental issues related to the greenhouse effect.
CO2Is also an important carbon source. Introducing CO2The organic chemicals or fuels such as methanol, ethanol, dimethyl ether, methane and the like are converted, so that the organic chemicals or fuels have good commercial value and development prospect. Methane is the major component of natural gas and can be transported using existing natural gas infrastructure and distribution networks, as compared to other stored fuels (methanol, ethanol, dimethyl ether, etc.). Thus, CO2Methanation the transition from fossil energy to synthetic energy can be achieved at lower cost (Vrijburg W L, Moioli E, Chen W, et al. ACS Catalysis,2019,9(9): 7823-.
CO2The key point of methanation is to prepare a catalyst with excellent performance. Ni catalyst to CO2Methanation has better catalytic activity, but the problems of sintering, agglomeration, carbon deposition and the like are easy to occur in the reaction, and the activity and the stability of the catalyst are reduced. Therefore, it is required to support Ni, an active component, on a carrier, to improve the activity and stability of the catalyst by improving the dispersion degree of the active component, and to reduce carbon deposition on the surface of the catalyst. Carrier bag widely used at presentIncluding gamma-Al2O3、CeO2、ZrO2、SiO2Etc. of which gamma-Al2O3Due to low price and relatively good performance, in CO2Widely used as a carrier for Ni-based catalysts in methanation processes, but Ni/gamma-Al2O3The catalytic activity of (a) is not sufficiently high.
Disclosure of Invention
The invention aims to provide CO2A methanation catalyst, a preparation method and application thereof. Eu in the invention2O3Modified Ni/gamma-Al2O3Application of catalyst to CO2The hydrogenation synthesis of methane reaction shows excellent catalytic performance.
The purpose of the invention can be realized by the following technical scheme:
CO (carbon monoxide)2Methanation catalyst based on gamma-Al2O3As carrier, metal Ni as active component, Eu2O3As an auxiliary agent, the mass of the metal Ni is 3-25% of the mass of the carrier, and the Eu is2O3The mass of (B) is 1-8% of the mass of the carrier.
Preferably, the mass of the metal Ni is 20% of that of the carrier, and the Eu is2O3The mass of (b) is 5% of the mass of the carrier.
CO (carbon monoxide)2The preparation method of the methanation catalyst comprises the following steps: mixing Ni (NO)3)2Aqueous solution, Eu (NO)3)2Mixing the aqueous solution and dropwise adding the aqueous solution to the gamma-Al2O3And (3) uniformly stirring the powder, and then drying and roasting the powder to obtain the catalyst. The catalyst is prepared by an isometric impregnation method.
Further, said Ni (NO)3)2The preparation process of the aqueous solution comprises the following steps: mixing Ni (NO)3)2·6H2Dissolving O in water to obtain Ni (NO)3)2An aqueous solution.
Further, said Eu (NO)3)2The preparation process of the aqueous solution comprises the following steps: eu is mixed2O3Dissolved in HNO3In the water solution, the water solution is added,obtaining Eu (NO)3)2An aqueous solution.
Further, the stirring is performed at room temperature.
Further, the drying temperature is 105-.
Further, the roasting process is as follows: heating from room temperature to 390-410 ℃ at the heating rate of 4-6 ℃/min, and roasting for 3-5 h.
CO (carbon monoxide)2Use of methanation catalyst for catalyzing CO2And (4) hydrogenation synthesis of methane.
Further, the application process specifically comprises: the catalyst is filled in a reaction tube, and H is firstly utilized2The catalyst is reduced by the reducing gas, and then the catalyst is introduced with CO at the temperature of 220-230 DEG C2And H2By reaction gas of (2) to CO2And carrying out methanation reaction to obtain methane.
Compared with the prior art, the invention provides CO2Catalyst for the reaction of synthesizing methane by hydrogenation, since Eu2O3The addition of the catalyst promotes the active component Ni and the carrier gamma-Al2O3The interaction of the catalyst is beneficial to the high dispersion of Ni, and the CO content of the catalyst is improved2Thereby increasing CO2Catalytic activity of methanation.
Drawings
FIG. 1 shows xEu-20Ni/γ -Al prepared in examples 1 to 4 and comparative example 22O3An XRD pattern of the catalyst, wherein (a) x ═ 1; (B) x is 3; (C) x is 5; (D) x is 8; (F) x is 0.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
The gases used in the following examples and comparative examples were obtained from Shanghai Wei Chuang Standard gas Co., Ltd, and the other reagents were obtained from Shanghai reagent Co., national drug group, all of which were analytically pure.
In each of the following examples and comparative examples, the catalytic reaction was carried out in a fixed bed reactor, and the product of the catalytic reaction, such as CH4、CO2And CO and the like are measured by an Agilent gas chromatograph.
The information on the model, specification, manufacturer, etc. of the equipment and analytical instrument used in each of the following examples and comparative examples is shown in Table 1.
TABLE 1 model, Specification, manufacturer of the instruments used
The invention provides CO2Methanation catalyst based on gamma-Al2O3As carrier, metal Ni as active component, Eu2O3As an auxiliary agent, the mass of metal Ni is 3-25% of the mass of the carrier, and Eu2O3The mass of (B) is 1-8% of the mass of the carrier.
Preferably, the mass of the metal Ni is 20% of the mass of the support, Eu2O3The mass of (b) is 5% of the mass of the carrier.
The invention also provides a preparation method of the catalyst, which comprises the following steps: mixing Ni (NO)3)2Aqueous solution, Eu (NO)3)2Mixing the aqueous solution and dropwise adding the aqueous solution to the gamma-Al2O3And (3) uniformly stirring the powder, drying and roasting to obtain the catalyst.
Wherein Ni (NO)3)2The preparation process of the aqueous solution comprises the following steps: mixing Ni (NO)3)2·6H2Dissolving O in water to obtain Ni (NO)3)2An aqueous solution. Eu (NO)3)2The preparation process of the aqueous solution comprises the following steps: eu is mixed2O3Dissolved in HNO3In aqueous solution to obtain Eu (NO)3)2An aqueous solution.
Stirring was carried out at room temperature. The drying temperature is 105-115 ℃, and the drying time is 6-12 h. The roasting process is as follows: heating from room temperature to 390-410 ℃ at the heating rate of 4-6 ℃/min, and roasting for 3-5 h.
The invention also provides the application of the catalyst, namely the catalyst is used for catalyzing CO2And (4) hydrogenation synthesis of methane.
The application process specifically comprises the following steps: the catalyst is filled in the reaction tube, and H is utilized2The catalyst is reduced by the reducing gas, and then the catalyst is introduced with CO at the temperature of 220-230 DEG C2And H2By reaction gas of (2) to CO2And carrying out methanation reaction to obtain methane.
Example 1:
eu (Eu)2O3Modified Ni/gamma-Al2O3Catalyst using gamma-Al2O3As carrier, metal Ni as active component, Eu2O3Is an auxiliary agent, wherein the content of Ni accounts for 20 percent of the mass of the carrier, and Eu2O3The content of (B) is 1% of the mass of the carrier.
The preparation method of the catalyst specifically comprises the following steps:
(1) weighing 1.982g Ni (NO)3)2·6H2O was placed in a crucible and dissolved by adding 2g of deionized water to form Ni (NO)3)2An aqueous solution; weighing 0.02g Eu2O3Placing in a crucible, adding 0.3g HNO with 69% concentration3Dissolving it to form Eu (NO)3)2An aqueous solution;
(2) mixing the Ni (NO) obtained in the step (1)3)2Aqueous solution, Eu (NO)3)2The aqueous solution was mixed and added dropwise to 2g of gamma-Al2O3Stirring the powder evenly at room temperature, transferring the powder into a drying oven, and drying the powder at 110 ℃ overnight;
(3) transferring the mixture obtained in the step (2) to a muffle furnace, and heating from room temperature to 400 ℃ at the heating rate of 5 ℃/min for roasting for 4h to obtain Eu2O3Modified Ni/gamma-Al2O3Catalyst A.
Example 2:
eu (Eu)2O3Modified Ni/gamma-Al2O3Catalyst using gamma-Al2O3As carrier, metal Ni as active component, Eu2O3Is an auxiliary agent, wherein the content of Ni accounts for 20 percent of the mass of the carrier, and Eu2O3The content of (B) is 3% of the mass of the carrier.
In the preparation method of the catalyst, only the Eu weighed in the step (1)2O3The mass becomes 0.06g, i.e., Eu2O3Is 3% of the carrier, and the other example 1 is the same as example 1, to obtain Eu2O3Modified Ni/gamma-Al2O3And (B) a catalyst.
Example 3:
eu (Eu)2O3Modified Ni/gamma-Al2O3Catalyst using gamma-Al2O3As carrier, metal Ni as active component, Eu2O3Is an auxiliary agent, wherein the content of Ni accounts for 20 percent of the mass of the carrier, and Eu2O3The content of (B) is 5% of the mass of the carrier.
In the preparation method of the catalyst, only the Eu weighed in the step (1)2O3The mass becomes 0.10g, i.e., Eu2O3Is 5% of the carrier, and is otherwise the same as in example 1, to obtain Eu2O3Modified Ni/gamma-Al2O3And (3) a catalyst C.
Example 4:
eu (Eu)2O3Modified Ni/gamma-Al2O3Catalyst using gamma-Al2O3As carrier, metal Ni as active component, Eu2O3Is an auxiliary agent, wherein the content of Ni accounts for 20 percent of the mass of the carrier, and Eu2O3The content of (B) is 8% of the mass of the carrier.
In the preparation method of the catalyst, only the Eu weighed in the step (1)2O3The mass becomes 0.16g, i.e., Eu2O3Is 8% of the carrier, and is otherwise the same as in example 1, to obtain Eu2O3Modified Ni/gamma-Al2O3And (3) a catalyst D.
Comparative example 1:
Ni/gamma-Al2O3Catalyst using gamma-Al2O3As a carrier, goldNi is used as an active component, wherein the content of Ni accounts for 3 percent of the mass of the carrier.
The preparation method of the catalyst specifically comprises the following steps:
(1) 0.297g of Ni (NO) was weighed3)2·6H2O was placed in a crucible and dissolved by adding 2.3g of deionized water to form Ni (NO)3)2An aqueous solution;
(2) mixing the Ni (NO) obtained in the step (1)3)2The aqueous solution was added dropwise to 2g of gamma-Al2O3Stirring the powder evenly at room temperature, transferring the powder to a drying oven, and drying the powder at 110 ℃ overnight;
(3) transferring the mixture obtained in the step (2) to a muffle furnace, heating the mixture from room temperature to 400 ℃ at the heating rate of 5 ℃/min, and roasting the mixture for 4 hours to obtain Ni/gamma-Al2O3Catalyst E.
Comparative example 2:
Ni/gamma-Al2O3Catalyst using gamma-Al2O3As a carrier, metal Ni is an active component, wherein the content of Ni accounts for 20 percent of the mass of the carrier.
In the preparation method of the catalyst, only Ni (NO) weighed in the step (1)3)2·6H2The mass of O was changed to 1.982g, that is, the Ni content was 20% by mass of the carrier, otherwise, Ni/γ -Al was prepared in the same manner as in comparative example 12O3Catalyst F.
Comparative example 3:
Ni/gamma-Al2O3Catalyst using gamma-Al2O3As a carrier, metal Ni is an active component, wherein the content of Ni accounts for 25 percent of the mass of the carrier.
In the preparation method of the catalyst, only Ni (NO) weighed in the step (1) is used3)2·6H2The mass of O was changed to 2.477g, that is, the Ni content was 25% by mass of the carrier, otherwise, Ni/γ -Al was obtained in the same manner as in comparative example 12O3Catalyst G.
FIG. 1 shows xEu-20Ni/γ -Al prepared in examples 1 to 4 and comparative example 22O3An XRD pattern of the catalyst, wherein (a) x ═ 1; (B) x is 3; (C) x is 5; (D) x is 8(ii) a (F) x is 0. As can be seen in FIG. 1, the catalyst samples tested all showed NiO and γ -Al2O3Characteristic diffraction peaks. Eu not shown in FIG. 12O3Characteristic diffraction peak of Eu, indicating Eu2O3Highly dispersed on the catalyst surface or present in an amorphous form. With Eu2O3The increase of the addition amount weakens the characteristic diffraction peak intensity of NiO, widens the peak shape, and shows that the average grain diameter of NiO is reduced, the dispersity is increased, and the improvement of the catalyst activity is facilitated.
The catalyst prepared by the method is applied to CO2And (4) hydrogenation synthesis of methane. The specific process is as follows:
0.15g each of the catalysts A, B, C, D and E, F, G obtained in examples 1 to 4 and comparative examples 1 to 3 was packed in a stainless reaction tube in a reducing gas (H) at a flow rate of 30ml/min2:N21:9), heating from room temperature to 500 ℃ at the heating rate of 5 ℃/min, continuously introducing reducing gas for reduction for 4h, cooling to 225 ℃, and switching the gas into reaction gas (CO)2:H21:4), the flow rate of the reaction gas is 60ml/min, and the space velocity is 24000ml · g-1·h-1And sampling and analyzing after the reaction is carried out for 4 hours. The catalyst activity test results are shown in table 2:
table 2 results of catalyst activity test
As can be seen from Table 2 above, the products obtained in examples 1, 2, 3 and 4 were used for CO2The catalytic effects of the catalysts A, B, C and D for the reaction of synthesizing methane by hydrogenation are obviously better than that of the catalyst F obtained in the comparative example 2. With Eu2O3Increase in content, CO of the resulting catalyst A, B, C, D2The conversion rate is gradually increased when Eu2O3Is added in an amount of 5 wt.%, and CO is present at 275 deg.C2The conversion rate of the catalyst already reaches 80 percent, and the yield of the methane also reaches more than 80 percent; CO at 325 deg.C2The conversion reached a maximum of 91.9%, the theoretical conversion being near thermodynamic equilibrium. Increase Eu continuously2O3Addition amount of (2), CO2The conversion rate did not increase significantly. In conclusion, the CO prepared by the invention2Catalysts for the hydrogenation of methane to CO2The hydrogenation synthesis of methane has high catalytic activity and selectivity, and has good development prospect.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The carbon dioxide methanation catalyst is characterized by comprising gamma-Al2O3As carrier, metal Ni as active component, Eu2O3As an auxiliary agent, the mass of the metal Ni is 3-25% of the mass of the carrier, and the Eu is2O3The mass of (B) is 1-8% of the mass of the carrier.
2. The carbon dioxide methanation catalyst according to claim 1, wherein the mass of the metal Ni is 20% of the mass of the carrier, and the Eu is2O3The mass of (b) is 5% of the mass of the carrier.
3. A method for preparing the carbon dioxide methanation catalyst according to claim 1 or 2, characterized in that the method comprises: mixing Ni (NO)3)2Aqueous solution, Eu (NO)3)2Mixing the aqueous solution and dropwise adding the aqueous solution to the gamma-Al2O3And (3) uniformly stirring the powder, and then drying and roasting the powder to obtain the catalyst.
4. A compound of claim 3The preparation method of the carbon oxide methanation catalyst is characterized in that the Ni (NO) is3)2The preparation process of the aqueous solution comprises the following steps: mixing Ni (NO)3)2·6H2Dissolving O in water to obtain Ni (NO)3)2An aqueous solution.
5. The method for preparing a carbon dioxide methanation catalyst according to claim 3, wherein the Eu (NO) is used3)2The preparation process of the aqueous solution comprises the following steps: eu is mixed2O3Dissolved in HNO3In aqueous solution to obtain Eu (NO)3)2An aqueous solution.
6. The method for preparing a carbon dioxide methanation catalyst according to claim 3, wherein the stirring is performed at room temperature.
7. The preparation method of the carbon dioxide methanation catalyst as claimed in claim 3, characterized in that the drying temperature is 105-115 ℃ and the drying time is 6-12 h.
8. The preparation method of the carbon dioxide methanation catalyst according to claim 3, characterized in that the roasting process is: heating from room temperature to 390-410 ℃ at the heating rate of 4-6 ℃/min, and roasting for 3-5 h.
9. Use of the carbon dioxide methanation catalyst according to claim 1 or 2, wherein the catalyst is used to catalyse CO2And (4) hydrogenation synthesis of methane.
10. The application of the carbon dioxide methanation catalyst according to claim 9, characterized in that the application process specifically comprises: the catalyst is filled in a reaction tube, and H is firstly utilized2The catalyst is reduced by the reducing gas, and then the catalyst is introduced with CO at the temperature of 220-230 DEG C2And H2By reaction gas of (2) to CO2Methanation reaction to obtainAn alkane.
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