CN106824252B - Nickel-based mesoporous carbon dioxide methanation catalyst and preparation method thereof - Google Patents
Nickel-based mesoporous carbon dioxide methanation catalyst and preparation method thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Natural products O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 52
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 34
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 34
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 5
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims 1
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 238000010981 drying operation Methods 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- 239000011148 porous material Substances 0.000 abstract description 9
- 239000004480 active ingredient Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000029936 alkylation Effects 0.000 abstract 1
- 238000005804 alkylation reaction Methods 0.000 abstract 1
- 239000010453 quartz Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 238000001354 calcination Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- WITQLILIVJASEQ-UHFFFAOYSA-N cerium nickel Chemical compound [Ni].[Ce] WITQLILIVJASEQ-UHFFFAOYSA-N 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- LLOSCSXUNHLNGM-UHFFFAOYSA-N 1-(4-aminophenyl)-3-(dimethylamino)propan-1-one Chemical compound CN(C)CCC(=O)C1=CC=C(N)C=C1 LLOSCSXUNHLNGM-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 229920000428 triblock copolymer Polymers 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 238000005516 engineering process Methods 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
- 238000002372 labelling Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
- B01J29/0356—Iron group metals or copper
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Abstract
The invention provides a nickel-based mesoporous carbon dioxideAn alkylation catalyst and a preparation method thereof, and a nickel-based mesoporous carbon dioxide methanation catalyst is prepared by adopting a vacuum roasting mode for the first time. The beneficial effects are that: the nickel-based mesoporous carbon dioxide methanation catalyst is prepared by a vacuum roasting method, the obtained catalyst has a highly ordered mesoporous structure, and an active ingredient Ni is highly dispersed into a pore channel of an SBA-16 carrier in a nanoparticle form; catalysis of carbon dioxide methanation reaction (CO) using the catalyst prepared as described above2+4H2=CH4+2H2O), the conversion rate of carbon dioxide is high, and the selectivity to methane is strong; the preparation method has the advantages of simple steps, wide raw material sources and high economic value.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a nickel-based mesoporous carbon dioxide methanation catalyst and a preparation method thereof.
Background
Currently, energy and environmental issues have become a concern worldwide. One is the greenhouse effect caused by the emission of a large amount of greenhouse gases from fossil energy, thereby causing global warming and generating comprehensive negative effects on the aspects of ecology, economy and society. With the change of global climate, global greenhouse effect of all countries in the world is concerned more and more. Large amount of CO emitted from fossil fuel combustion2Is the main cause of global climate change, and the contribution rate of the climate change to global warming exceeds 60 percent. And secondly, unsafe factors of clean energy such as nuclear power energy bring unprecedented challenges to the production and survival of human beings.
How to effectively reduce CO discharged by industry2It is particularly important to convert it into usable resources, among which the carbon dioxide methanation reaction (CO)2+4H2=CH4+2H2O) is considered to be one of the most promising reactions. The methanation reaction is an exothermic reaction, so the methanation reaction has higher reaction equilibrium conversion rate at low temperature and is beneficial to CH4And (4) generating. The Ni-based catalyst can be used for methanation reaction. At present, in the prior art, the Ni-based catalyst mainly has low-temperature activity when being used for methanation reaction, and reverse water gas side reaction (CO) is easy to occur2+H2=CO+H2O), poor reaction selectivity. The problem to be solved by the methanation catalyst of carbon dioxide at present is how to improve the activity and selectivity of the catalyst.
In the prior art, for example, a Chinese patent with an authorization publication number of CN102416324B discloses a carbon dioxide methanation catalyst, a preparation method and application thereof, wherein the catalyst is prepared by mixing a metal nickel compound with biomass power plant ash through high-temperature roasting, and the weight percentage of the metal nickel component is 2-20%. The preparation method comprises the following steps: 1) preparing a metallic nickel compound into an aqueous solution with the mass concentration of 5-30%; 2) roasting the biomass power plant ash at the temperature of 300-400 ℃ for 20-40 min; 3) converting the raw material amount according to the weight percentage of the nickel component in the catalyst, mixing the aqueous solution of the metal nickel compound prepared in the step 1) with the biomass power plant ash roasted in the step 2, stirring and turning for 5-10 h, and uniformly soaking; 4) drying the impregnated biomass power plant ash at the temperature of 110-150 ℃ for 0.5-1.5 h; 5) and roasting the dried biomass power plant ash at the temperature of 400-500 ℃ for 3-6 h. The method changes waste into valuable, and the power plant ash waste is utilized to prepare the carbon dioxide methanation catalyst, but the catalytic activity and the selectivity of the catalyst prepared by the method are required to be improved.
Disclosure of Invention
The invention aims to provide a nickel-based mesoporous carbon dioxide methanation catalyst which has a highly ordered mesoporous structure, small active particles, high dispersity, high catalytic activity, strong methane selectivity and high carbon dioxide conversion rate and a preparation method thereof.
Aiming at the problems mentioned in the background technology, the invention adopts the technical scheme that:
a nickel-based mesoporous carbon dioxide methanation catalyst and a preparation method thereof comprise the following specific steps:
10%Ni-10%CeO2preparation of SBA-16 catalyst: weighing 0.6-0.8 part of Ni (NO)3)2·6H2O, 0.3-0.5 part of Ce (NO)3)3·6H2O, 0.5-0.7 part of deionized water and 0.9-1.2 parts of acetone, and adding 1-2 parts of SBA-16 after mixing to fully wet the mixture; putting the mixture into an electrothermal blowing dry box at the temperature of 55-65 ℃ for drying for 0.8-1.2 h; and drying, putting into a quartz tube, vacuumizing by using a vacuum pump, putting into a tube type resistance furnace, heating to 400-600 ℃, and roasting for 3-5 hours. Cooling to room temperature to obtain vacuum-calcined 10% Ni-10% CeO2The catalyst is/SBA-16. Synthesis ofThe finished product still has a highly ordered mesoporous structure of SBA-16, and the active ingredient Ni is highly dispersed into the pore canal of the SBA-16 carrier in the form of nano particles; catalysis of carbon dioxide methanation reaction (CO) using the catalyst prepared as described above2+4H2=CH4+2H2O), high conversion of carbon dioxide, and strong selectivity to methane.
Compared with the prior art, the invention has the advantages that: the synthesized finished product still has a highly ordered mesoporous structure of SBA-16, and the active ingredient Ni is highly dispersed into the pore channel of the SBA-16 carrier in the form of nano particles; catalysis of carbon dioxide methanation reaction (CO) using the catalyst prepared as described above2+4H2=CH4+2H2O), the conversion rate of carbon dioxide is high, and the selectivity to methane is strong; the preparation method has the advantages of simple steps, wide raw material sources and high economic value.
Drawings
FIG. 1 is a graph comparing carbon dioxide conversion for catalysts calcined under vacuum and air atmosphere;
FIG. 2 is a plot of methane selectivity versus a catalyst calcined under vacuum and air;
FIG. 3 is an XRD spectrum of a catalyst calcined at 600 ℃ under vacuum and air atmosphere.
Description of the labeling: curve 1 is 10% Ni-10% CeO2SBA-16-V, curve 2 from 10% Ni to 10% CeO2SBA-16-Air, curve 3 from 10% Ni to 10% CeO2SBA-16-V, curve 4 from 10% Ni to 10% CeO2SBA-16-Air, curve 5 from 10% Ni to 10% CeO2SBA-16-Air, curve 6 from 10% Ni to 10% CeO2/SBA-16-V。
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The technical solution of the present invention is further illustrated by the following figures and examples:
example 1:
a nickel-based mesoporous carbon dioxide methanation catalyst and a preparation method thereof comprise the following specific steps:
1) preparation of SBA-16 vector: weighing 10-15 parts of F127 (triblock copolymer), 25-35 parts of n-butyl alcohol, 400-600 parts of distilled water and a constant-temperature magnetic stirrer at the temperature of 43-47 ℃ for stirring for 0.8-1.2 h until the materials are uniformly mixed. Adding 15-20 parts of 35-40% hydrochloric acid, slowly dropwise adding 40-60 parts of TEOS (tetraethyl orthosilicate), and stirring at the constant temperature of 43-47 ℃ for 20-25 hours. Transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction at 105-120 ℃ for 20-25 h, cooling to room temperature, carrying out suction filtration, and washing for 2-5 times. And transferring the white powder to a watch glass, drying at 75-90 ℃ for 10-15 h, putting into a muffle furnace, setting the heating speed at 1-1.5 ℃/min, raising the temperature from room to 550-600 ℃, and calcining for 3-5 h to obtain the target product SBA-16 carrier. The carrier has high pore volume, high specific surface area and narrow pore channel distribution, can allow the active particles of the catalyst to enter pores, ensures high dispersion degree of metal loaded on the carrier, and has adjustable pore diameter and wall thickness and good thermal stability; the anti-sintering property of the catalytic active component is increased, so that the service life of the catalyst at high temperature is prolonged;
2）10%Ni-10%CeO2preparation of SBA-16 catalyst: weighing 0.6-0.8 part of Ni (NO)3)2·6H2O, 0.3-0.5 part of Ce (NO)3)3·6H2O, 0.5-0.7 part of deionized water and 0.9-1.2 parts of acetone are mixed, and then 1-2 parts of SBA-16 are added to fully wet the mixture, and because data is nonlinear, the active ingredient Ni is highly dispersed into the pore channel of the SBA-16 carrier in the form of nanoparticles according to the proportion; the Ni content is low, the activity is high, the anti-sintering property is strong, the stability is high, the conversion rate of carbon dioxide is high, and the generation amount of a side reaction product methane is small; putting the mixture into an electrothermal blowing dry box at the temperature of 55-65 ℃ for drying for 0.8-1.2 h; and drying, putting into a quartz tube, vacuumizing by using a vacuum pump, putting into a tube type resistance furnace, heating to 400-600 ℃, and roasting for 3-5 hours. Cooling to room temperature to obtain vacuum-calcined 10% Ni-10% CeO2The catalyst is/SBA-16. The synthesized finished product still has a highly ordered mesoporous structure of SBA-16, and the active ingredient Ni is highly dispersed into the pore channel of the SBA-16 carrier in the form of nano particles; catalysis of carbon dioxide methanation reaction (CO) using the catalyst prepared as described above2+4H2=CH4+2H2O), high conversion of carbon dioxide, and strong selectivity to methane.
Example 2:
a nickel-based mesoporous carbon dioxide methanation catalyst and a preparation method thereof are disclosed, wherein the optimization steps are as follows:
1) preparation of SBA-16 vector: 10.0g of F127 (triblock copolymer), 30.0g of n-butanol and 475ml of distilled water were weighed out and stirred with a constant temperature magnetic stirrer at 45 ℃ for 1 hour until uniform mixing was achieved. 17.5ml of 37% strength hydrochloric acid are added, 47.3g of TEOS (tetraethyl orthosilicate) are slowly added dropwise and the mixture is stirred at a constant temperature of 45 ℃ for 24 hours. Transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction at 110 ℃ for 24h, cooling to room temperature, carrying out suction filtration, washing with deionized water for 3 times, and then washing with 5% ethanol for 3 times to obtain white powder. And transferring the white powder to a watch glass, drying at 80 ℃ for 12h, putting into a muffle furnace, setting the heating speed at 1 ℃/min, heating to 600 ℃ from room temperature, and calcining for 4h to obtain the target product SBA-16 carrier.
2）10%Ni-10%CeO2Preparation of SBA-16 catalyst: weighing 0.6192gNi (NO)3)2·6H2O、0.3156gCe(NO3)3·6H2O, 0.57ml deionized water and 0.91ml acetone, and adding 1.0g SBA-16 after mixing to fully wet; drying in an electrothermal blowing dry box at 60 deg.C for 1 hr; drying, loading into quartz tube, vacuumizing, placing into tube-type resistance furnace, heating to 600 deg.C, and calcining for 4 hr. Cooling to room temperature to obtain 10% Ni-10% CeO vacuum roasted at 600 deg.C2Catalyst SBA-16 (noted as 10% Ni-10% CeO)2/SBA-16-V）。
The vacuum roasting is changed into the roasting in the air, and the experiment is repeated to obtain 10 percent of Ni to 10 percent of CeO2Catalyst SBA-16 (noted as 10% Ni-10% CeO)2SBA-16-Air). As can be seen from FIG. 1, the catalyst obtained by vacuum calcination has a higher conversion rate of carbon dioxide; as can be seen from FIG. 2, the catalyst obtained by vacuum calcination has higher selectivity to methane; fig. 3 shows that the diffraction peak intensity of the vacuum-calcined catalyst is weaker, and the half-peak width is larger, which indicates that the nickel-cerium particles in the vacuum-calcined catalyst are smaller, the dispersion degree of the nickel-cerium particles is higher, and the catalytic effect is better.
Example 3:
a nickel-based mesoporous carbon dioxide methanation catalyst and a preparation method thereof are disclosed, and further optimization steps are as follows:
1) preparation of SBA-16 vector: 10.0g of F127 (triblock copolymer), 30.0g of n-butanol and 475ml of distilled water were weighed out and stirred with a constant temperature magnetic stirrer at 45 ℃ for 1 hour until uniform mixing was achieved. 17.5ml of 37% strength hydrochloric acid are added, 47.3g of TEOS (tetraethyl orthosilicate) are slowly added dropwise and the mixture is stirred at a constant temperature of 45 ℃ for 24 hours. Transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction at 110 ℃ for 24h, cooling to room temperature, carrying out suction filtration, washing with deionized water for 3 times, and then washing with 5% ethanol for 3 times to obtain white powder. And transferring the white powder to a watch glass, drying at 80 ℃ for 12h, putting into a muffle furnace, setting the heating speed at 1 ℃/min, heating to 600 ℃ from room temperature, and calcining for 4h to obtain the target product SBA-16 carrier.
2）10%Ni-10%CeO2Preparation of SBA-16 catalyst: weighing 0.6192gNi (NO)3)2·6H2O、0.3156gCe(NO3)3·6H2O, 0.57ml of deionized water, 0.91ml of acetone, n-propylamine and β -4-aminobenzoyl ethyldimethylamine (the proportion of acetone, n-propylamine to β -4-aminobenzoyl ethyldimethylamine is 2: 1: 1), wherein n-propylamine and β -4-aminobenzoyl ethyldimethylamine obviously promote high dispersion of nickel and cerium, smaller nickel and cerium particles and higher dispersion degree of nickel and cerium particles and better catalytic effect, after mixing, adding 1.0g of SBA-16 to fully wet the nickel and cerium particles, putting the mixture into an electrothermal blowing drying box at 60 ℃, drying for 1h, putting the dried mixture into a quartz tube, vacuumizing the quartz tube by using a vacuum pump, putting the quartz tube into a tubular resistance furnace, heating the quartz tube to 600 ℃, roasting the quartz tube for 4h, cooling the quartz tube to room temperature, and obtaining vacuum roasting 10% of Ni and 10% of CeO at 600 ℃2Catalyst SBA-16 (noted as 10% Ni-10% CeO)2/SBA-16-V）。
The vacuum roasting is changed into the roasting in the air, and the experiment is repeated to obtain 10 percent of Ni to 10 percent of CeO2Catalyst SBA-16 (noted as 10% Ni-10% CeO)2SBA-16-Air). As can be seen from FIG. 1, the catalyst obtained by vacuum calcination has a higher conversion rate of carbon dioxide; as can be seen from FIG. 2, the catalyst obtained by vacuum calcination has higher selectivity to methane; as can be seen from FIG. 3, the diffraction peak intensity of the vacuum-calcined catalyst is weaker, and the half-peak width is larger, which shows that the nickel-cerium particles in the vacuum-calcined catalyst are smaller,the dispersion degree of the nickel-cerium particles is higher, and the catalytic effect is better.
And (3) testing the performance of the catalyst:
50mg of the catalyst was charged into a quartz tube reactor. Introducing 10ml/min of H2And N of 40ml/min2The temperature is increased from 25 ℃ to 450 ℃ at the heating rate of 10 ℃/min, and the reduction is carried out for 40 min. After reduction, the temperature is reduced to 200 ℃, and the gas is switched to be H of 40ml/min250ml/min of N2And CO at 10ml/min2The reaction was started. The reaction temperature is 200-450 ℃, 50 ℃ per step, and each step is carried out for 80 min. And (3) analyzing the composition of the tail gas and the feed gas after the reaction by adopting a Tianmei GC-7900 type gas chromatograph, wherein the detector is a thermal conductivity detector. The test result shows that the 10 percent Ni-10 percent CeO prepared by vacuum roasting2The SBA-16-V has good performance, the carbon dioxide conversion rate at 400 ℃ reaches more than 60 percent, and the methane selectivity is higher than 98 percent.
Conventional operations in the operation steps of the present invention are well known to those skilled in the art and will not be described herein.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A nickel-based mesoporous carbon dioxide methanation catalyst is characterized in that: 10% Ni and 10% CeO2Dispersed in mesoporous SiO2In the vector SBA-16; the preparation steps of the catalyst are as follows: ni (NO)3)2·6H2O and Ce (NO)3)3·6H2Adding deionized water and acetone into O, stirring, adding an SBA-16 carrier, drying, heating to 400-600 ℃, vacuum roasting for 3-5 h, and cooling to obtain vacuum roasted 10% Ni-10% CeO2The catalyst is/SBA-16.
2. The preparation method of the nickel-based mesoporous carbon dioxide methanation catalyst as claimed in claim 1, characterized in that: said Ni (NO)3)2·6H2O:Ce(NO3)3·6H2O is deionized water, and the mass volume ratio of acetone is 1g, (0.4-0.6) g, (0.8-1.1) mL, (1.5-2.0) mL; said Ni (NO)3)2·6H2The mass ratio of the O to the SBA-16 is 1: 1.6-1: 2.0; the preparation steps of the catalyst are as follows: ni (NO)3)2·6H2O and Ce (NO)3)3·6H2Adding deionized water and acetone into O, stirring, adding SBA-16 carrier, drying, vacuum roasting, and cooling to obtain vacuum roasted 10% Ni-10% CeO2The catalyst is/SBA-16.
3. The preparation method of the nickel-based mesoporous carbon dioxide methanation catalyst according to claim 2, characterized by comprising the following steps: in the step, the stirring speed is 200-400 r/min.
4. The preparation method of the nickel-based mesoporous carbon dioxide methanation catalyst according to claim 2, characterized by comprising the following steps: the drying operation is drying for 0.8-1.2 h in an electrothermal blowing dry box at the temperature of 55-65 ℃.
5. The preparation method of the nickel-based mesoporous carbon dioxide methanation catalyst according to claim 2, characterized by comprising the following steps: the vacuum roasting temperature is 400-600 ℃, and the roasting time is 3-5 h.
6. The preparation method of the nickel-based mesoporous carbon dioxide methanation catalyst according to claim 2, characterized by comprising the following steps: the cooling operation is natural cooling to room temperature.
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| CN110339855A (en) * | 2018-04-03 | 2019-10-18 | 华东理工大学 | A kind of nickel-base catalyst and the preparation method and application thereof |
| CN111514897B (en) * | 2020-05-11 | 2021-03-19 | 泰州禾益新材料科技有限公司 | Application of high-dispersion carbon-doped mesoporous silicon nanotube nickel-based catalyst in carbon dioxide methanation reaction |
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