CN113351211B - Cerium dioxide fibrous catalyst containing nickel particles and preparation method thereof - Google Patents
Cerium dioxide fibrous catalyst containing nickel particles 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 99
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 47
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 38
- 239000002245 particle Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 239000000835 fiber Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 23
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 18
- 239000002105 nanoparticle Substances 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 11
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011888 foil Substances 0.000 claims description 8
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002121 nanofiber Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 6
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005642 Oleic acid Substances 0.000 claims description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229940078494 nickel acetate Drugs 0.000 claims description 5
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- SRQNIPUSSAISTC-UHFFFAOYSA-N [Ni].CCCCCC Chemical compound [Ni].CCCCCC SRQNIPUSSAISTC-UHFFFAOYSA-N 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 150000000703 Cerium Chemical class 0.000 claims description 3
- 238000001523 electrospinning Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910021543 Nickel dioxide Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000012258 stirred mixture Substances 0.000 claims description 2
- 230000001404 mediated effect Effects 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000000197 pyrolysis Methods 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000012494 Quartz wool Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention discloses a cerium dioxide fibrous catalyst containing nickel particles and a preparation method thereof, belonging to the field of nano materials and chemical catalysis. The preparation method of the catalyst comprises the following steps: preparing nano nickel particles by an organic pyrolysis method, preparing fibrous cerium dioxide by an electrostatic spinning method, calcining at high temperature, impregnating, drying and the like to obtain the target catalyst. The content of active metal nickel of the catalyst is 1 to 20 percent, the content of cerium dioxide is 80 to 99 percent, and the specific surface area is 25 to 120m 2 Per g, the pore diameter is 5-50nm, the length of the fiber is 20nm-2 μm, and the diameter is 50-500nm. The invention prepares mesoporous fibrous Ni @ CeO by an electrostatic spinning method 2 The NF catalyst increases the porosity, increases the specific surface area, provides more reaction active centers and enhances the CO resistance of the carrier 2 The adsorption of (2) improves the conversion rate and reduces the optimal activation temperature. The catalyst has controllable appearance, high efficiency and stability, and is very suitable for CO 2 And (4) carrying out hydrogenation conversion reaction.
Description
Technical Field
The invention belongs to the field of nano materials and chemical catalysis, and particularly relates to a cerium dioxide fibrous catalyst containing nickel particles and a preparation method thereof.
Background
Slowing down or solving the problem of global warming is a major challenge for human sustainable development, carbon dioxide is a major greenhouse gas, and is a valuable research item for capturing, storing and utilizing the carbon dioxide. The conversion of the chemical can not only reduce the concentration of the chemical in the atmosphere, but also create economic benefits for the high-value chemical.
CO 2 A stable pi-shaped key is embedded in the structure, which is required toHigh temperature, high pressure or catalyst conditions. At present for CO 2 The catalyst for methanation reaction is mainly a supported catalyst, and the carrier is metal oxide, such as Al 2 O 3 、ZrO 2 、CeO 2 The active metals are classified into noble metals (Pd, pt, ru) and transition metals (Fe, co, ni). Noble metals have good catalytic effect on the reaction, but the manufacturing cost is too high, and the noble metals are still difficult to apply in practical production, such as patent CN 111514889A, and noble metal ruthenium is used as an active metal. And the reaction is an exothermic reaction and is limited by thermodynamic high temperature, so that the development of cheap and low-temperature high-efficiency catalysts is the key of the large-scale production of the reaction. The catalyst is also added with a catalytic promoter, such as patent CN 111229228A, but the reaction is carried out under high pressure, and the actual operation is very difficult. The morphology of the catalyst is also one of the important factors influencing the reaction, and patent CN 106824252B utilizes the channel effect of the mesoporous carrier to improve the dispersion degree of the active metal, but the activity of the catalyst at low temperature is very poor, and the optimal activity can be reached at 400 ℃.
Disclosure of Invention
The invention aims to provide a cerium dioxide fibrous catalyst containing nickel particles and a preparation method thereof.
Aiming at the problems mentioned in the background technology, the invention adopts the technical scheme that:
a mesoporous cerium dioxide fibrous catalyst containing nickel particles comprises active components of nickel and cerium dioxide;
wherein the nickel is nanoparticles with the size of 4-6nm, the content of the nickel in the catalyst is 1% -20%, the cerium dioxide is in the shape of mesoporous nanofiber, the content of the cerium dioxide in the catalyst is 80% -99%, and the specific surface area of the cerium dioxide is 25-120m 2 The diameter of the fiber is 50-500nm, the pore diameter is 5-50nm, the fiber length is 20nm-2 μm.
Furthermore, the nickel nanoparticles are prepared from a nickel salt precursor by using a high-temperature pyrolysis method; wherein the salt precursor of nickel comprises nickel nitrate, nickel acetate and nickel acetylacetonate.
The high-temperature pyrolysis method for preparing nickel nanoparticles comprises the following steps:
1) Dissolving a nickel salt precursor into a mixed solution of oleylamine and oleic acid;
2) Heating the fully dissolved mixture to 100 ℃, preserving heat for 1-3h, wherein the process needs to be carried out in an oxygen-free and water-free state, polyvinylpyrrolidone with the molar mass of 2-10 times of nickel is added in the process, the temperature is continuously preserved and stirred for 1h, then the temperature is reduced to room temperature, and the oxygen-free and water-free state still needs to be maintained in the cooling process;
3) And adding absolute ethyl alcohol into the stirred mixture, washing, centrifuging, drying to obtain nickel nano particles with uniform size, and dissolving the nickel nano particles in n-hexane.
Further, the mesoporous nano-fiber-shaped cerium dioxide is prepared from a cerium salt precursor by an electrostatic spinning method; wherein, the salt precursor of cerium comprises cerium nitrate and cerium acetate.
The preparation method of mesoporous nano fiber-shaped cerium dioxide by an electrospinning method comprises the following steps:
1) Adding a salt precursor of cerium into N-N dimethylformamide, and carrying out ultrasonic stirring for 10min to completely dissolve the salt precursor of cerium to obtain a uniform light yellow transparent solution;
2) Adding polyacrylonitrile and the nickel-n-hexane solution prepared by the method into the light yellow transparent solution obtained in the step 1), and continuously stirring for 12 hours at the temperature of 60 ℃ to deepen the color of the light yellow transparent solution;
3) Putting the solution with the darkened color obtained in the step 2) into an injector, setting the voltage to be 16kV, collecting the solution by adopting an electrostatic spinning machine roller aluminum foil, and carrying out vacuum drying on the collected product for 12 hours at the temperature of 60 ℃ to obtain the cerium dioxide containing the nickel particles and in the shape of the mesoporous nanofiber.
Further, the weight ratio of polyacrylonitrile to cerium salt precursor is 3:1.
a preparation method of a mesoporous cerium dioxide fibrous catalyst containing nickel particles comprises the following steps:
the cerium dioxide containing the nickel particles and having the mesoporous nanofiber shape, which is prepared by the method, is placed in a tubular furnace, pretreated for 2 hours at 200 ℃ in an inert atmosphere, and finally calcined for 2-4 hours at 500 ℃ in the air, so that the fibrous catalyst containing the nickel particles and having the mesoporous cerium dioxide shape is obtained.
Further, the nickel particle-containing mesoporous cerium dioxide fibrous catalyst is applied to methanation of carbon dioxide, and the application conditions are as follows: normal pressure, 225-425 ℃ of reaction temperature and 12000-36000h of reaction space velocity -1 Molar ratio of H 2 ：CO 2 ＝4：1。
Compared with the prior art, the invention has the beneficial effects that:
CO 2 the mesoporous fibrous Ni @ CeO is prepared by combining an organic pyrolysis method with an electrostatic spinning method 2 The NF catalyst increases the porosity, increases the specific surface area, provides more reaction active centers and enhances the CO resistance of the carrier 2 The adsorption of (2) improves the conversion rate and reduces the optimal activation temperature. The catalyst prepared by the method has controllable shape, high efficiency and stability, and is very suitable for CO 2 And (4) carrying out hydrogenation conversion reaction.
Drawings
FIG. 1 is a TEM image of nickel nanoparticles prepared in example 1 of the present invention.
Fig. 2 is an SEM image of the mesoporous ceria fibrous catalyst containing nickel particles prepared in example 1 of the present invention.
Fig. 3 is a physical adsorption and pore size distribution diagram of the nickel particle-containing mesoporous ceria fibrous catalyst prepared in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to specific examples, but the present invention is not limited to the following examples. The process is conventional unless otherwise specified, and the starting materials are commercially available from the open literature.
Example 1
(1) Taking a clean 250mL three-neck flask, introducing argon gas atmosphere, carrying out an experiment under the condition of ensuring an oxygen-free state, weighing 8.50g of nickel nitrate solid by using an electronic balance, adding about 15mL of oleylamine and 15mL of oleic acid, heating to 100 ℃, keeping the temperature for 2 hours, adding 17.0g of polyvinylpyrrolidone (PVP), keeping the temperature and stirring for reaction for 1 hour, cooling to room temperature, stopping introducing argon gas, washing and centrifuging for three times by using absolute ethyl alcohol to obtain nickel nanoparticles with uniform size (FIG. 1 is a TEM image of the nickel nanoparticles prepared in the embodiment, as shown in the figure, the size of the nickel nanoparticles is 5nm and the size is uniform), dissolving the nickel nanoparticles in 10mL of n-hexane, and sealing and storing;
(2) Weighing 2g of cerium nitrate, dissolving the cerium nitrate in 30mL of N-N Dimethylformamide (DMF) solution, performing ultrasonic treatment and stirring for 10 minutes to fully dissolve the cerium nitrate, then adding 6g of Polyacrylonitrile (PAN) and 1mL of nickel-N-hexane solution obtained in the step (1), and stirring overnight at the sealed condition of 60 ℃;
(3) Adding the uniformly stirred solution into an injector, starting an electrostatic spinning machine, setting the voltage to be 16kv, and collecting roller aluminum foils;
(4) The collected aluminum foil is dried at 60 ℃ for 12 hours in a vacuum environment, heated to 200 ℃ at 2 ℃/min in an argon atmosphere in a tube furnace, kept for two hours, and then heated to 500 ℃ at 5 ℃/min in an air atmosphere in a muffle furnace, and calcined for 3 hours to obtain a product catalyst (fig. 2 is an SEM image of a fibrous catalyst of mesoporous cerium dioxide containing nickel particles prepared in the embodiment, and as shown in the figure, the fibrous structure is obvious, and the diameter is uniform).
Fig. 3 is a physical adsorption and pore size distribution diagram, an adsorption/desorption curve and a hysteresis loop of the nickel-particle-containing mesoporous ceria fibrous catalyst prepared in this example, which show that the mesoporous of the material exists, and the pore size of the pore size analysis surface material is concentrated at 5-20nm, which is a typical mesoporous structure material.
Weighing 0.1g of catalyst, placing in the middle of a quartz tube with inner diameter of 4mm, outer diameter of 8mm and length of 32cm, plugging two sides with quartz wool, and evaluating with a fixed bed device to obtain a reaction gas molar ratio H 2 :CO 2 =4:1, space velocity of 12000h -1 Gas chromatography with TCD detector on-line separationThe product was isolated.
Example 2
(1) Taking a clean 250mL three-neck flask, introducing argon gas atmosphere, carrying out an experiment under the condition of ensuring an anaerobic state, weighing 8.50g of nickel acetylacetonate solid by using an electronic balance, adding about 10mL of oleylamine and 20mL of oleic acid, heating to 100 ℃, continuing to preserve heat for 2 hours, adding 17.0g of PVP, continuing to preserve heat and carrying out stirring reaction for 1 hour, stopping introducing argon gas after cooling to room temperature, washing with absolute ethyl alcohol and centrifuging for three times to obtain nickel nanoparticles with uniform size, dissolving the nickel nanoparticles in 10mL of n-hexane, and carrying out sealed storage;
(2) Weighing 2g of cerium acetate, dissolving the cerium acetate in 30mL of DMF solution, performing ultrasonic treatment and stirring for 10 minutes to fully dissolve the cerium acetate, then adding 6g of PAN and 1mL of nickel-n-hexane solution obtained in the step (1), and stirring overnight at the sealed condition of 60 ℃;
(3) Adding the uniformly stirred solution into an injector, starting an electrostatic spinning machine, setting the voltage to be 16kv, and collecting roller aluminum foils;
(4) Drying the collected aluminum foil at 60 ℃ for 12 hours in a vacuum environment, heating to 200 ℃ at 2 ℃/min in an argon atmosphere in a tube furnace, keeping for two hours, then heating to 500 ℃ at 5 ℃/min in the air, and calcining for 3 hours to obtain the product catalyst.
Weighing 0.1g of catalyst, placing in the middle of a quartz tube with inner diameter of 4mm, outer diameter of 8mm and length of 32cm, plugging two sides with quartz wool, adopting a fixed bed evaluation device, and determining the molar ratio H of reaction gas 2 :CO 2 =4:1, space velocity of 12000h -1 The gas chromatograph is equipped with a TCD detector to analyze the product on-line.
Example 3
(1) Taking a clean 250mL three-neck flask, introducing argon gas atmosphere, carrying out an experiment under an anaerobic state, weighing 8.50g of nickel acetate solid by using an electronic balance, adding about 20mL of oleylamine and 10mL of oleic acid, heating to 100 ℃, keeping the temperature for 2 hours, adding 17.0g of PVP, keeping the temperature and stirring for reaction for 1 hour, stopping introducing the argon gas after the temperature is reduced to room temperature, washing and centrifuging for three times by using absolute ethyl alcohol to obtain nickel nanoparticles with uniform size, dissolving the nickel nanoparticles in 10mL of n-hexane, and carrying out sealed storage;
(2) Weighing 2g of cerium acetate, dissolving the cerium acetate in 30mL of DMF solution, performing ultrasonic treatment and stirring for 10 minutes to fully dissolve the cerium acetate, then adding 6g of PAN and 1mL of nickel-n-hexane solution obtained in the step (1), and stirring overnight at the sealed condition of 60 ℃;
(3) Adding the uniformly stirred solution into an injector, starting an electrostatic spinning machine, setting the voltage to be 16kv, and collecting roller aluminum foils;
(4) Drying the collected aluminum foil at 60 ℃ for 12 hours in a vacuum environment, heating to 200 ℃ at 2 ℃/min in an argon atmosphere in a tube furnace, keeping for two hours, then heating to 500 ℃ at 5 ℃/min in the air, and calcining for 3 hours to obtain the product catalyst.
Weighing 0.1g of catalyst, placing in the middle of a quartz tube with inner diameter of 4mm, outer diameter of 8mm and length of 32cm, plugging two sides with quartz wool, adopting a fixed bed evaluation device, and determining the molar ratio H of reaction gas 2 :CO 2 =4:1, space velocity of 12000h -1 The gas chromatograph is equipped with a TCD detector to analyze the product on-line.
Examples 4 to 9
Catalysts were prepared according to the parameters as designed in Table 1, except for the parameters as designed, and by the same procedure as in example 1.
Table 1: examples 4-9 design parameters
| Examples | Nickel source | Oleic acid/mL | oleylamine/mL | Cerium source | Space velocity/h -1 |
| 4 | |
10 | 20 | Cerium acetate | 24000 |
| 5 | |
20 | 10 | Cerium nitrate | 24000 |
| 6 | |
15 | 15 | Cerium nitrate | 24000 |
| 7 | |
20 | 10 | Cerium nitrate | 36000 |
| 8 | |
15 | 15 | Cerium nitrate | 36000 |
| 9 | |
10 | 20 | Cerium acetate | 36000 |
The activity of the catalysts prepared in examples 4 to 9 was examined and analyzed, and the results of the examination and analysis in examples 1 to 3 were combined to obtain Table 2.
Table 2: catalyst activity detection analysis results
As shown in Table 2, the mesoporous fibrous catalyst prepared by the invention enhances the effect of the carrier on CO 2 The optimum active temperature is reduced and the CO is increased 2 Conversion of (2) is very suitable for CO 2 And (4) carrying out hydrogenation conversion reaction.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solutions of the present application and not to limit them; although the present application has been described in detail with reference to preferred embodiments, those of ordinary skill in the art will understand that: modifications to the embodiments of the present application or equivalent replacements of some technical features may still be made, which should all be covered by the scope of the technical solution claimed in the present application.
Claims (7)
1. A mesoporous cerium dioxide fibrous catalyst containing nickel particles is characterized in that,
the active components of the catalyst are nickel and cerium dioxide; wherein, the nickel is nanoparticles with the size of 4-6nm, the content of the nickel in the catalyst is 1% -20%, the cerium dioxide is in the shape of mesoporous nanofiber, the content of the cerium dioxide in the catalyst is 80% -99%, and the specific surface area of the cerium dioxide is 25-120m 2 Per g, aperture of 5-50nm, fiber lengthThe degree is 20nm-2 μm, the diameter is 50-500 nm;
the nickel nanoparticles are prepared from a nickel salt precursor by the following method:
1) Dissolving a nickel salt precursor into a mixed solution of oleylamine and oleic acid;
2) Heating the fully dissolved mixture to 100 ℃, preserving the heat by 1-3h, wherein the process is carried out in an oxygen-free and water-free state, adding polyvinylpyrrolidone with the mass of 2-10 times of that of nickel in the process, continuously preserving the heat, stirring 1h, cooling to room temperature, and keeping the oxygen-free and water-free state in the cooling process;
3) And adding absolute ethyl alcohol into the stirred mixture, washing, centrifuging, drying to obtain nickel nano particles with uniform size, and dissolving the nickel nano particles in n-hexane.
2. The fibrous catalyst of mesoporous ceria containing nickel particles according to claim 1, wherein the salt precursor of nickel comprises nickel nitrate, nickel acetate, nickel acetylacetonate.
3. The fibrous catalyst of mesoporous ceria containing nickel particles according to claim 1, wherein the ceria in the form of mesoporous nanofibers is prepared from a salt precursor of cerium by an electrospinning method;
wherein, the salt precursor of cerium comprises cerium nitrate and cerium acetate.
4. The method of preparing catalyst-mediated, porous nanofiber-shaped ceria according to claim 3, wherein the electrospinning method comprises the steps of:
1) Adding a salt precursor of cerium into N-N dimethylformamide, and completely dissolving by ultrasonic stirring for 10min to obtain a uniform light yellow transparent solution;
2) Adding polyacrylonitrile and the nickel-n-hexane solution prepared in the claim 1) into the light yellow transparent solution obtained in the step 1), and continuously stirring the mixture at the temperature of 60 ℃ for 12h, so that the light yellow transparent solution is darkened;
3) And (3) filling the solution with the darkened color obtained in the step 2) into an injector, setting the voltage to be 16kV, collecting the solution by adopting an electrostatic spinning machine roller aluminum foil, and performing vacuum drying on the collected product at 60 ℃ to obtain the cerium dioxide in the shape of the mesoporous nanofiber containing the nickel particles, wherein the vacuum drying is 12 h.
5. The method for preparing cerium dioxide in the shape of mesoporous nanofibers according to claim 4, wherein the polyacrylonitrile and the cerium salt precursor are added in a weight ratio of 3:1.
6. a method for preparing a fibrous catalyst of mesoporous ceria containing nickel particles, comprising:
placing the nickel particle-containing mesoporous nano fiber-shaped cerium dioxide prepared by the method of claim 4 in a tubular furnace, pretreating 2h at 200 ℃ in an inert atmosphere, and finally calcining 2-4h in a muffle furnace at 500 ℃ to obtain the nickel particle-containing mesoporous cerium dioxide fibrous catalyst.
7. The application of the nickel-particle-containing mesoporous cerium dioxide fibrous catalyst in methanation of carbon dioxide according to claim 1, wherein the application conditions are as follows: normal pressure, reaction temperature of 225-425 deg.c and reaction space velocity of 12000-36000h -1 Molar ratio of H 2 ：CO 2 =4：1。
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