CN118341490A - Nickel-cerium catalyst and preparation method and application thereof - Google Patents
Nickel-cerium catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- WITQLILIVJASEQ-UHFFFAOYSA-N cerium nickel Chemical compound [Ni].[Ce] WITQLILIVJASEQ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 16
- 238000001179 sorption measurement Methods 0.000 claims abstract description 11
- 230000003993 interaction Effects 0.000 claims abstract description 6
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 84
- 239000000243 solution Substances 0.000 claims description 26
- 229910052684 Cerium Inorganic materials 0.000 claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 239000012018 catalyst precursor Substances 0.000 claims description 18
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 35
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- 239000012086 standard solution Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 239000001569 carbon dioxide Substances 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Abstract
The invention relates to a nickel-cerium catalyst, which comprises three elements of Ni, ce and O, wherein the content of Ce is 15-20at%, the nickel-cerium catalyst comprises Ni and CeO 2 nano particles with the particle diameters of 5-10nm respectively, and the nickel-cerium interfaces are connected together through Ce [ O ] x -Ni interaction to improve the adsorption capacity of CO 2, wherein x is between 1.5 and 2. The invention also provides a preparation method and application of the nickel-cerium catalyst. According to the nickel-cerium catalyst disclosed by the invention, CO 2 can be adsorbed and methanated at medium and low temperature (150-350 ℃), high-efficiency CO 2 adsorption and conversion are realized, excellent catalytic stability is achieved, and the methanation performance of the nickel-cerium catalyst is improved.
Description
Technical Field
The invention relates to methanation of carbon dioxide (CO 2), in particular to a nickel-cerium catalyst, a preparation method and application thereof.
Background
With global industrialization upgrade, the demand for fossil fuels is continuously increased, so that the footprint of CO 2 is continuously increased, and the greenhouse effect is generated, so that the sustainable development of society is further inhibited. Therefore, achieving efficient catalytic conversion of CO 2 at medium and low temperatures is a promising technology. On one hand, the reduction of the conversion temperature of CO 2 can reduce the energy consumption, which is beneficial to environmental protection; on the other hand, the conversion efficiency of CO 2 is improved, and the emission of CO 2 in the atmosphere and industrial tail gas can be reduced.
From the thermodynamic point of view, the methanation reaction of CO 2 is a strongly exothermic reaction, which is advantageous for the reaction at low temperature and high pressure, while CO byproduct is produced at high temperature, so that the methanation reaction of CO 2 is advantageous for improving the yield of methane and the durability of the catalyst at relatively low temperature. However, from the reaction kinetics point of view, the kinetic barrier for the active hydrogenation to methane is high due to the high chemical stability of the CO 2 molecules. Therefore, it is needed to provide a technical solution capable of performing methanation reaction on CO 2 at low temperature.
Disclosure of Invention
In order to solve the problem of high kinetic barrier for converting CO 2 into methane by activated hydrogenation in the prior art, the invention provides a nickel-cerium catalyst, and a preparation method and application thereof.
The nickel-cerium catalyst comprises three elements of Ni, ce and O, wherein the content of Ce is 15-20 at%, the nickel-cerium catalyst comprises Ni and CeO 2 nano particles with the particle diameters of 5-10nm respectively, and the nickel-cerium interfaces are connected together through Ce [ O ] x -Ni interaction to improve the adsorption capacity of CO 2, wherein x is between 1.5 and 2.
Preferably, the Ni particle size of the nickel cerium catalyst is 10nm and the CeO 2 particle size is 5nm.
Preferably, the nickel cerium catalyst has a molar ratio of Ni to Ce of 5:1.
The preparation method of the nickel cerium catalyst comprises the following steps: s1, mixing a nickel-based solution, a cerium-based solution and oxalic acid, and evaporating to obtain a solid, wherein solute ions of the nickel-based solution comprise Ni 2+, and solute ions of the cerium-based solution comprise Ce 3+; s2, drying and grinding the solid, and calcining for 1-3 hours in an air atmosphere at 350-450 ℃ to prepare a catalyst precursor; s3, carrying out reduction treatment on the catalyst precursor for 20-40 min in a reducing atmosphere at 350-450 ℃ to obtain the nickel-cerium catalyst.
Preferably, the step S1 specifically includes: mixing a nickel-based solution and a cerium-based solution to prepare an active mixed solution; then mixing the active mixed solution with oxalic acid, and stirring and dispersing to prepare a loaded mixed solution; and evaporating the loaded mixed solution at 60-70 ℃ to obtain a solid.
Preferably, the molar ratio of Ni 2+ to Ce 3+ in the supported mixture is between 4.5:1-5.5: 1.
Preferably, the molar ratio of Ni 2+ to Ce 3+ in the supported mixture is 5:1.
Preferably, the reducing atmosphere comprises H 2 at a volume concentration and the balance inert gas.
The use of the above nickel cerium catalyst according to the invention, wherein CO 2 and H 2 are methanated by the cerium nickel catalyst at a temperature of 150-350 ℃.
Preferably, the methanation temperature is between 150-250 ℃. In a preferred embodiment, the methanation temperature is 200 ℃.
According to the nickel-cerium catalyst disclosed by the invention, CO 2 can be adsorbed and methanated at medium and low temperature (150-350 ℃), high-efficiency CO 2 adsorption and conversion are realized, excellent catalytic stability is achieved, and the methanation performance of the nickel-cerium catalyst is improved. Specifically, the invention constructs Ce [ O ] x-Ni interface by coprecipitation method, and combines Ni and CeO 2 nano particles tightly, the existence of the interface can obviously promote the adsorption capacity of CO 2, promote the adsorption and activation of CO 2, and simultaneously, the formation of the interface regulates the particle size of Ni particles, promotes the synergistic effect of Ni and CeO 2, and realizes 90% CO 2 conversion rate and 100% methane selectivity at low temperature (150-350 ℃).
Drawings
Fig. 1 is an X-ray diffraction (XRD) pattern of the catalysts prepared according to example 1 and comparative examples 1-3 of the present invention.
Fig. 2 is a High Resolution Transmission Electron Microscope (HRTEM) image of the nickel cerium catalyst prepared according to example 1 of the present invention.
Fig. 3 is a Temperature Programmed Desorption (TPD) diagram of CO 2 of the catalysts prepared according to example 1 and comparative examples 1-3 of the present invention.
FIG. 4 is a graph of the catalytic activity of the catalysts prepared according to example 1 and comparative examples 1-4 of the present invention, where the curve corresponding to the straight arrow represents the CO 2 conversion and the curve corresponding to the top curved arrow represents the CH 4 selectivity.
Fig. 5 is a graph of the stability of catalysts prepared according to example 1 and comparative example 3 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Unless otherwise defined, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. As used herein, the word "comprising" and the like means that elements or items preceding the word are included in the element or item listed after the word and equivalents thereof without precluding other elements or items.
The nickel-cerium catalyst comprises three elements of Ni, ce and O, wherein the content of Ce is 15-20 at%, the nickel-cerium catalyst comprises Ni and CeO 2 nano particles with the particle diameters of 5-10nm respectively, and the nickel-cerium interfaces are connected together through Ce [ O ] x -Ni interaction to improve the adsorption capacity of CO 2, wherein x is between 1.5 and 2. For example, the nickel-cerium interfaces are primarily joined together by Ce [ O ] 2 -Ni interactions. In a preferred embodiment, the nickel cerium catalyst has a Ni particle size of about 10nm and a CeO 2 particle size of about 5 nm. In particular, by regulating the proportion of Ni to Ce, the particle size of Ni of the nickel-cerium catalyst is optimized, namely the dispersity of Ni is regulated, and Ni and CeO 2 achieve good synergistic effect, so that the high-efficiency methanation reaction of carbon dioxide at a lower temperature is realized, and the catalyst has higher methane selectivity. In a preferred embodiment, the nickel cerium catalyst has a molar ratio of Ni to Ce of 5:1. in a preferred embodiment, the specific surface area of the nickel cerium catalyst is 100m 2/g.
The preparation method of the nickel-cerium catalyst comprises the steps of mixing a nickel-based solution, a cerium-based solution and oxalic acid, and evaporating to obtain a solid, wherein solute ions of the nickel-based solution comprise Ni 2+, and solute ions of the cerium-based solution comprise Ce 3+. Specifically, after mixing a nickel-based solution and a cerium-based solution, preparing an active mixed solution; then mixing the active mixed solution with oxalic acid, and stirring and dispersing to prepare a loaded mixed solution; and evaporating the loaded mixed solution at 60-70 ℃ to obtain a solid. In a preferred embodiment, the nickel-based solution is Ni (NO 3)2 solution and the cerium-based solution is Ce (NO 3)3 solution. Wherein the molar ratio of Ni 2+ to Ce 3+ in the supported mixture is between 4.5:1 and 5.5:1. In a preferred embodiment, the molar ratio of Ni 2+ to Ce 3+ in the supported mixture is 5:1.
The preparation method of the nickel cerium catalyst comprises the steps of drying and grinding solids, and calcining for 1-3 hours in an air atmosphere at 350-450 ℃ to prepare a catalyst precursor. In a preferred embodiment, the calcination temperature is 400℃and the calcination time is 2 hours.
The preparation method of the nickel-cerium catalyst comprises the steps of reducing the catalyst precursor for 20-40 min in a reducing atmosphere at 350-450 ℃ to prepare the nickel-cerium catalyst. Wherein the reducing atmosphere comprises hydrogen and inert gas. For example, the reducing atmosphere includes hydrogen and nitrogen. In a preferred embodiment, the reducing atmosphere comprises H 2% by volume and the balance inert gas. In a preferred embodiment, the reduction temperature is 400℃and the reduction time is 30 minutes.
Thus, ceO 2 and Ni are synthesized by adopting a coprecipitation method, the preparation process is simple, the process parameters are easy to control, and the requirements on preparation equipment are low.
The use of the cerium-nickel catalyst according to the invention in a methanation reaction of carbon dioxide, comprising methanation of CO 2 and H 2 by means of the cerium-nickel catalyst at a temperature of 150-350 ℃. In a preferred embodiment, the methanation temperature is 200 ℃. In a preferred embodiment, the nickel cerium catalyst precursor is filled into a fixed bed reaction tube, the reduction atmosphere is introduced to reduce for 30min at 400 ℃, the flow rate of the reduction gas is controlled to be 50mL/min, and after the temperature in the reaction tube is reduced to room temperature of 25 ℃, the volume ratio is introduced to be 4:1, controlling the flow rate of the mixed gas to be 70mL/min, and carrying out carbon dioxide methanation reaction at 150-250 ℃.
Thus, the cerium-nickel catalyst of the present invention can exhibit excellent low-temperature activity, methane selectivity and excellent stability in the methanation reaction of carbon dioxide.
Preparation example 1
Preparing a nickel standard solution: 5.8158g of Ni (NO 3)2·6H2 O was dissolved in absolute ethanol to a volume of 50mL to prepare a nickel standard solution, wherein the molar concentration of Ni 2+ in the nickel standard solution was 4mol/mL.
Preparing cerium standard solution: 7.8160g of Ce (NO 3)3·6H2 O is dissolved in absolute ethyl alcohol to 50mL to prepare a cerium standard solution, wherein the molar concentration of Ce 3+ in the cerium standard solution is 3.6 mol/mL).
Example 1
50.000ML of nickel standard solution and 11.111mL of cerium standard solution are mixed, the volume is fixed to 120.00mL by using absolute ethyl alcohol, and the mixture is mixed with 6.3035g of oxalic acid dihydrate and magnetically stirred at 25 ℃ for 6 hours to prepare a precursor mixed solution. In the precursor mixture, the molar ratio of Ni 2+ to Ce 3+ is 5:1.
And (3) drying the precursor mixed solution in an oven at 65 ℃ for 12 hours, grinding, placing the ground powder in a muffle furnace, heating to 400 ℃ at a heating rate of 2 ℃/min under an air atmosphere, and preserving heat and calcining for 2 hours to obtain the catalyst precursor.
And (3) treating the catalyst precursor for 30min in a reducing atmosphere at 400 ℃, and cooling to room temperature to obtain the nickel-cerium catalyst. Wherein the reducing atmosphere specifically comprises the following components in percentage by volume: 19 with nitrogen. Wherein, the specific surface area of the nickel cerium catalyst is 100m 2/g.
Comparative example 1
The difference from example 1 was that 50.000mL of a nickel standard solution and 2.778mL of a cerium standard solution were mixed, the volume was fixed to 120.00mL using absolute ethanol, and then the mixture was magnetically stirred with 6.3035g of oxalic acid dihydrate at 25℃for 6 hours to prepare a precursor mixture. In the precursor mixture, the molar ratio of Ni 2+ to Ce 3+ is 20:1.
Comparative example 2
The difference from example 1 was that 50.000mL of a nickel standard solution and 50.000mL of a cerium standard solution were mixed, the volume was fixed to 120.00mL using absolute ethanol, and then the mixture was magnetically stirred with 6.3035g of oxalic acid dihydrate at 25℃for 6 hours to prepare a precursor mixture. In the precursor mixture, the molar ratio of Ni 2+ to Ce 3+ was 1.1:1.
Comparative example 3
The difference from example 1 was that 50.000mL of a nickel standard solution was directly fixed to 120.00mL using absolute ethanol, and then the solution was magnetically stirred with 6.3035g of oxalic acid dihydrate at 25℃for 6 hours to prepare a precursor mixture. The amount of Ni in the catalyst produced was 100wt.%.
Comparative example 4
The difference from example 1 was that 2.778mL of cerium standard solution was directly fixed to 120.00mL using absolute ethanol, and then magnetically stirred with 6.3035g of oxalic acid dihydrate at 25℃for 6 hours to prepare a precursor mixture. The amount of CeO 2 in the catalyst produced was 100wt.%.
The catalyst precursors prepared in example 1 and comparative examples 1 to 3 were subjected to structural analysis using an X-ray diffractometer, and the scanning range was 10 to 90℃and the scanning speed was 2℃per minute, and the results are shown in FIG. 1. As can be seen from fig. 1, the catalyst precursor prepared according to comparative example 3 exhibited characteristic diffraction peaks of NiO, whereas with the addition of CeO 2, niO characteristic diffraction peaks were gradually weakened and diffraction peaks were widened, which suggests that the size of Ni nanoparticles was gradually regulated as the Ce content was increased, and that the average particle diameters of Ni in example 1 and comparative examples 1-3, calculated by the scherrer formula, were about 10nm,15nm,5nm and 30nm, respectively, and the particle diameters of CeO 2 were 5nm,15nm,10nm and 30nm, respectively. In addition, the particle size of CeO 2 in comparative example 4 was 20nm.
The nickel cerium catalyst prepared in example 1 was subjected to structural analysis using a cold field emission electron microscope, and the results thereof are shown in fig. 2. As can be seen from fig. 2, the nickel cerium catalyst prepared in example 1 exhibited distinct Ni (111) and CeO 2 (111) lattice fringes, 0.2nm and 0.31nm, respectively. In addition, the unique CeO 2 and Ni active interfaces can be seen from FIG. 2, which suggests that there is a strong interaction and synergy between Ni and CeO 2.
The catalyst precursors prepared in example 1 and comparative examples 1-3 were subjected to a CO 2 -TPD test with a catalyst amount of 0.1000g, the catalyst was saturated adsorbed in 5vol.% He gas, then desorbed at a programmed temperature of 5 ℃/min, and the change in CO 2 curve was recorded by mass spectrometry, the results of which are shown in FIG. 3. As can be seen from fig. 3, with the addition of CeO 2, the adsorption capacity of the catalyst for CO 2 can be significantly improved, comparative example 3 has substantially no adsorption capacity for CO 2, the desorption curve is approximately a straight line, and example 1 shows the strongest adsorption capacity for CO 2.
0.2100G of the catalyst precursor prepared in example 1 and comparative examples 1 to 3 were charged into a fixed bed straight reaction tube having a tube length of 50cm and a diameter of 2cm, respectively, in a volume ratio of 1:19 and nitrogen as reducing gas, treating the catalyst precursor for 30min at the reducing gas flow rate of 50mL/min and the temperature of 400 ℃, then cooling the inside of the reaction tube, and introducing the catalyst precursor into the reaction tube at the flow rate of 70mL/min at the volume ratio of 5 when the temperature is cooled to the room temperature of 25 ℃:20:75 CO 2、H2 and He, and carrying out carbon dioxide methanation reaction at 150-350 ℃. The reaction tail gas was analyzed on line based on gas chromatography, and the concentration of the reaction tail gas was detected by using a Thermal Conductivity Detector (TCD) after separation by a column chromatography using pure helium as a carrier gas, and the detection result is shown in fig. 4. As can be seen from fig. 4, the catalytic activity of the catalysts of example 1 and comparative examples 1-2 is significantly higher than that of comparative examples 3 and 4, which demonstrates that the synergy of Ni and CeO 2 in the catalysts can significantly improve the catalytic activity for methanation of carbon dioxide, and that the catalyst provided in example 1 has a molar ratio of Ni to Ce of 5:1, which has the highest activity in catalyzing methanation of carbon dioxide, the conversion rate of carbon dioxide reaches 85.6% at 200 ℃ and 90.4% at 250 ℃, which shows that Ni and CeO 2 have a synergistic effect, and the molar ratio of Ni to Ce is 5:1, can reach better catalytic effect.
0.2100G of the catalyst precursor prepared in example 1 were taken and introduced into a fixed bed straight reaction tube in a volume ratio of 1:19 and nitrogen as reducing gas, treating the catalyst precursor for 30min at the reducing gas flow rate of 50mL/min and the temperature of 400 ℃, then cooling the inside of the reaction tube, and introducing the catalyst precursor into the reaction tube at the flow rate of 70mL/min when the temperature is cooled to the room temperature of 25 ℃ with the volume ratio of 1:4, CO 2 and H 2, the reaction tube was warmed to 200 ℃ and timing started. On-line analysis is carried out on the reaction tail gas in the reaction period of 0-90h based on the flash chromatography, pure helium is used as carrier gas, the reaction tail gas is separated by a chromatographic column and then concentration detection is carried out by a Thermal Conductivity Detector (TCD), and the detection result is shown in figure 5. As can be seen from fig. 5, the catalyst provided in example 1 still has good catalytic performance after 90 hours of stability test, the CO 2 conversion rate is continuously maintained above 78%, and the CH 4 selectivity is also maintained above 99%. However, comparative example 3 showed a significant deactivation in a short time, and the CO 2 conversion and the CH 4 selectivity decreased rapidly.
While the embodiments of the present invention have been described in detail hereinabove, it will be apparent to those skilled in the art that various modifications and variations can be made to these embodiments. It is to be understood that such modifications and variations are within the scope and spirit of the present invention as set forth in the following claims. Moreover, the invention as described herein is capable of other embodiments and of being practiced or of being carried out in various ways.
Claims (10)
1. The nickel-cerium catalyst is characterized by comprising three elements of Ni, ce and O, wherein the content of Ce is 15-20 at%, the nickel-cerium catalyst comprises Ni and CeO 2 nano particles with the particle diameters of 5-10nm respectively, and the nickel-cerium interfaces are connected together through Ce [ O ] x -Ni interaction to improve the adsorption capacity of CO 2, wherein x is between 1.5 and 2.
2. The nickel-cerium catalyst according to claim 1, wherein the nickel-cerium catalyst has a particle diameter of Ni of 10nm and a particle diameter of ceo 2 of 5nm.
3. The nickel-cerium catalyst according to claim 1, characterized in that the molar ratio of Ni and Ce of the nickel-cerium catalyst is 5:1.
4. A method for preparing a nickel cerium catalyst according to any one of claims 1 to 3, comprising the steps of:
s1, mixing a nickel-based solution, a cerium-based solution and oxalic acid, and evaporating to obtain a solid, wherein solute ions of the nickel-based solution comprise Ni 2+, and solute ions of the cerium-based solution comprise Ce 3+;
S2, drying and grinding the solid, and calcining for 1-3 hours in an air atmosphere at 350-450 ℃ to prepare a catalyst precursor;
s3, carrying out reduction treatment on the catalyst precursor for 20-40 min in a reducing atmosphere at 350-450 ℃ to obtain the nickel-cerium catalyst.
5. The method according to claim 4, wherein the step S1 specifically comprises: mixing a nickel-based solution and a cerium-based solution to prepare an active mixed solution; then mixing the active mixed solution with oxalic acid, and stirring and dispersing to prepare a loaded mixed solution; and evaporating the loaded mixed solution at 60-70 ℃ to obtain a solid.
6. The method of claim 5, wherein the molar ratio of Ni 2+ to Ce 3+ in the supported mixture is between 4.5:1-5.5: 1.
7. The method according to claim 6, wherein the molar ratio of Ni 2+ to Ce 3+ in the supported mixture is 5:1.
8. The method according to claim 4, wherein the reducing atmosphere comprises H 2 at a volume concentration and the balance inert gas.
9. Use of a nickel cerium catalyst according to any of claims 1-3, characterized in that CO 2 and H 2 are methanated by the cerium nickel catalyst at a temperature of 150-350 ℃.
10. The process according to claim 9, wherein the methanation temperature is between 150 and 250 ℃.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118341490A true CN118341490A (en) | 2024-07-16 |
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