CN116371414B - High-temperature stable reduction-resistant cerium oxide-nickel ferrite composite catalyst and preparation method and application thereof - Google Patents
High-temperature stable reduction-resistant cerium oxide-nickel ferrite composite catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- DIHNQCDIYCAPLW-UHFFFAOYSA-N [O-2].[Ce+3].[Ni+2] Chemical compound [O-2].[Ce+3].[Ni+2] DIHNQCDIYCAPLW-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000009467 reduction Effects 0.000 title claims abstract description 12
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 claims abstract description 101
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 56
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 56
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 150000000703 Cerium Chemical class 0.000 claims abstract description 27
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 23
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 22
- 239000011258 core-shell material Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000006722 reduction reaction Methods 0.000 claims description 12
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 230000003197 catalytic effect Effects 0.000 abstract description 20
- 238000002156 mixing Methods 0.000 abstract description 10
- 230000001737 promoting effect Effects 0.000 abstract description 2
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 20
- 239000000126 substance Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 229910003264 NiFe2O4 Inorganic materials 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 238000010531 catalytic reduction reaction Methods 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- KPZSTOVTJYRDIO-UHFFFAOYSA-K trichlorocerium;heptahydrate Chemical compound O.O.O.O.O.O.O.Cl[Ce](Cl)Cl KPZSTOVTJYRDIO-UHFFFAOYSA-K 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- -1 iron metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
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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
- 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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- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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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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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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Abstract
The invention discloses a high-temperature stable reduction-resistant cerium oxide-nickel ferrite composite catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing and dispersing cerium salt and nickel ferrite in ethanol, igniting, and calcining the burnt product to obtain a cerium oxide-nickel ferrite composite catalyst; the cerium oxide-nickel ferrite composite catalyst has a core-shell structure, namely cerium oxide wraps nickel ferrite, wherein the mass ratio of cerium oxide in the shell to nickel ferrite in the core is 1:100-1:2.5. The cerium oxide-nickel ferrite composite catalyst prepared by the invention has higher carbon dioxide catalytic efficiency and thermal stability under high-temperature reducing atmosphere, thereby realizing the efficient conversion of carbon dioxide into high-added-value products and effectively promoting the emission reduction and economic utilization of carbon dioxide.
Description
Technical Field
The invention belongs to the technical field of nickel ferrite spinel application, and particularly relates to a high-temperature stable reduction-resistant cerium oxide-nickel ferrite composite catalyst, and a preparation method and application thereof.
Background
Nickel ferrite has excellent electrochemical performance, magnetic performance and catalytic performance due to its special crystal structure, and is widely applied to various fields. Current nickel ferrite samples are generally impure and contain nickel, iron metals and oxides, wherein nickel has better hydrogen activating capability, methane byproducts are easy to generate in the field of carbon dioxide hydrogenation reduction, and the selectivity of the products is reduced. In addition, nickel ferrite has poor stability under the condition of high temperature of reducing atmosphere (such as carbon monoxide, hydrogen and the like) and is easy to be converted into alloy and agglomerate to influence the normal running of the reduction reaction, so that the nickel ferrite catalyst needs to be modified, and the selectivity and stability of the nickel ferrite catalyst in the process of catalyzing and reducing carbon dioxide are improved.
Disclosure of Invention
The invention aims to: the invention provides a high-temperature stable reduction-resistant cerium oxide-nickel ferrite composite catalyst, and a preparation method and application thereof, so as to solve the problem of poor selectivity and stability in the existing nickel ferrite catalyst catalytic reduction process of carbon dioxide.
The invention comprises the following steps: in order to achieve the above object, the present invention provides a preparation method of a high-temperature stable reduction-resistant cerium oxide-nickel ferrite composite catalyst, the preparation method comprising:
dispersing cerium salt and nickel ferrite in ethanol and igniting, and calcining the burnt product to obtain a cerium oxide-nickel ferrite composite catalyst; the cerium oxide-nickel ferrite composite catalyst has a core-shell structure, namely cerium oxide wraps nickel ferrite, wherein the mass ratio of cerium oxide in the shell to nickel ferrite in the core is 1:100-1:2.5.
Typically, the cerium oxide-coated nickel ferrite is a brown solid.
In the invention, the ethanol is used as a dispersing agent of cerium salt and nickel ferrite, is used for dispersing the cerium salt and the nickel ferrite, is also an indispensable raw material for carrying out combustion reaction, can ensure that the raw material is fully combusted, and the combustion temperature can reach more than 1000 ℃, so that cerium element in the cerium salt forms cerium oxide on the surface of the nickel ferrite to form cerium oxide-coated nickel ferrite.
Nickel ferrite has a large number of oxygen vacancies on the surface and has good reducibility, and has high catalytic activity in the field of CO 2 catalytic reduction, but the nickel ferrite still has the defects of poor stability under high temperature conditions, easiness in generating CH 4 byproducts and the like, so that the nickel ferrite is difficult to apply on a large scale. Cerium oxide has good high-temperature stability for CO 2 catalytic reduction and high selectivity for CO, but the CO 2 conversion rate is low. The cerium oxide-nickel ferrite composite catalyst synthesized by wrapping the nickel ferrite with cerium oxide can form an interface protection effect with the nickel ferrite by utilizing the chemical property of cerium oxide and the reducible characteristic of cerium oxide, so that the inactivation rate of the nickel ferrite at high temperature is reduced, and the CO selectivity is improved. In addition, the high-temperature synthesis process is also beneficial to the high-temperature tolerance of the cerium oxide-nickel ferrite composite catalyst.
The purpose of defining the mass ratio of cerium oxide to nickel ferrite is to allow the cerium oxide to encapsulate the nickel ferrite to form a core-shell structure and a metal interface. When the mass ratio is too large, cerium oxide is easy to completely wrap nickel ferrite, so that a core substance cannot act on a reaction system, and the activity of a catalyst is low; when the mass ratio is too small, the catalytic interface between nickel ferrite and cerium oxide is easy to be small, the activity is low, and the deactivation of Wen Tuanju is easy to be carried out. Meanwhile, the molar ratio of cerium element to nickel ferrite can be obtained through the mass ratio of cerium oxide to nickel ferrite, and further the molar ratio of cerium salt to nickel ferrite required by the reaction can be obtained.
Optionally, the cerium salt is cerium nitrate. The reason for selecting cerium nitrate is that the cerium oxide coated nickel ferrite catalyst formed by using the precursor has the best catalytic performance.
Optionally, the calcining temperature is 500-800 ℃, the calcining time is 20-40 min, and the calcining atmosphere is an oxygen-containing environment.
The effect of defining the calcination temperature and time is to fully oxidize the cerium salt present on the nickel ferrite surface to form cerium oxide. When the calcination temperature is too high or the calcination time is too long, the cerium oxide is sintered and agglomerated at a high temperature, so that nickel ferrite cannot be well wrapped, a catalytic interface is affected, and the catalytic stability and the catalyst activity are low; when the calcining temperature is too low or the calcining time is too short, the cerium salt cannot be completely converted into cerium oxide, so that the cerium oxide cannot well wrap nickel ferrite, the molding of a catalytic interface is affected, and the catalytic stability and the catalytic activity are affected.
Alternatively, the oxygen-containing environment may be an air atmosphere.
Optionally, the mass to volume ratio of the cerium salt, the nickel ferrite and the ethanol is 0.013g:1g:10ml to 1.008g:1g:10ml.
The purpose of defining the mass to volume ratio is to ensure that the cerium salt and nickel ferrite are sufficiently dispersed in the ethanol. When the mass-volume ratio is too large, the addition amount of ethanol is relatively small, so that the nickel ferrite is poor in dispersion, and part of the nickel ferrite is not coated by cerium oxide; when the mass-to-volume ratio is too small, it is indicated that the addition amount of cerium salt or nickel ferrite is small, resulting in relatively long calcination time, so that cerium oxide is sintered and agglomerated, and the activity is affected.
In addition, the invention also comprises the cerium oxide-nickel ferrite composite catalyst prepared by the method and application thereof, and the cerium oxide-nickel ferrite composite catalyst is applied to carbon dioxide conversion reaction.
The beneficial effects are that: compared with the prior art, the high-temperature stable reduction-resistant cerium oxide-nickel ferrite composite catalyst and the preparation method and application thereof provided by the invention have the following advantages:
according to the invention, cerium salt, nickel ferrite and ethanol are mixed and stirred and then ignited, the obtained product is calcined to obtain the cerium oxide-nickel ferrite composite catalyst, the mass ratio of cerium oxide to nickel ferrite is limited, cerium salt can form cerium oxide to be coated on nickel ferrite particles, the cerium oxide-nickel ferrite composite catalyst is obtained, and the efficient and stable conversion of carbon dioxide is realized through the synergistic effect of nickel ferrite and cerium oxide.
The cerium oxide-nickel ferrite composite catalyst prepared by the invention has higher carbon dioxide catalytic efficiency and thermal stability under high-temperature reducing atmosphere, thereby realizing the efficient conversion of carbon dioxide into high-added-value products and effectively promoting the emission reduction and economic utilization of carbon dioxide.
Drawings
FIG. 1 is a flow chart of the preparation of a cerium oxide-nickel ferrite composite catalyst according to an embodiment of the present invention;
FIG. 2 is an XRD pattern of a cerium oxide-nickel ferrite composite catalyst according to an embodiment of the present invention;
FIG. 3 is an XRD pattern of a cerium oxide-nickel ferrite composite catalyst and nickel ferrite as it is in an embodiment of the present invention;
FIG. 4 is a graph showing the results of the stability test of the cerium oxide-nickel ferrite composite catalyst and nickel ferrite as they are in the examples of the present invention.
Detailed Description
In order to make the technical solution of the present invention clearer, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, 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.
As shown in fig. 1, the preparation method of the cerium oxide-nickel ferrite composite catalyst in the embodiment of the invention comprises the following steps:
Uniformly mixing cerium salt, nickel ferrite and ethanol, igniting, and calcining the burnt product to obtain a cerium oxide-nickel ferrite composite catalyst; the cerium oxide-nickel ferrite composite catalyst is of a core-shell structure, namely cerium oxide wraps nickel ferrite, wherein the mass ratio of cerium oxide in the shell to nickel ferrite in the core is 1:100-1:2.5.
The cerium oxide-nickel ferrite composite catalyst prepared by the method can be applied to carbon dioxide hydrogenation catalytic reaction, and can be particularly applied to: in the reverse water gas conversion, CO 2 hydrogenation high-efficiency conversion is realized.
Example 1:
Cerium salt is selected as cerium nitrate hexahydrate;
the mass volume ratio of the cerium nitrate hexahydrate, the nickel ferrite and the ethanol is 0.013g:1g:10ml;
Mixing cerium nitrate hexahydrate, nickel ferrite and ethanol, stirring for 10min to uniformity, igniting, calcining under air atmosphere at 600 ℃ for 30min, and grinding to obtain cerium oxide coated nickel ferrite, which is denoted as CeO 2-NiFe2O4 -N;
the obtained cerium oxide coated nickel ferrite is of a core-shell structure, wherein the mass ratio of the cerium oxide in the shell to the nickel ferrite in the core is 1:100.
Example 2:
Cerium salt is selected as cerium nitrate hexahydrate;
the mass volume ratio of the cerium nitrate hexahydrate, the nickel ferrite and the ethanol is 0.025g:1g:10ml;
Mixing cerium nitrate hexahydrate, nickel ferrite and ethanol, stirring for 10min to uniformity, igniting, calcining under air atmosphere at 600 ℃ for 30min, and grinding to obtain cerium oxide coated nickel ferrite, which is denoted as CeO 2-NiFe2O4 -N;
the obtained cerium oxide coated nickel ferrite is of a core-shell structure, wherein the mass ratio of the cerium oxide in the shell to the nickel ferrite in the core is 1:50.
Example 3:
Cerium salt is selected as cerium nitrate hexahydrate;
the mass volume ratio of cerium nitrate hexahydrate, nickel ferrite and ethanol is 0.126g:1g:10ml;
Mixing cerium nitrate hexahydrate, nickel ferrite and ethanol, stirring for 10min to uniformity, igniting, calcining under air atmosphere at 600 ℃ for 30min, and grinding to obtain cerium oxide coated nickel ferrite, which is denoted as CeO 2-NiFe2O4 -N;
the obtained cerium oxide coated nickel ferrite is of a core-shell structure, wherein the mass ratio of the cerium oxide in the shell to the nickel ferrite in the core is 1:20.
Example 4:
Cerium salt is selected as cerium nitrate hexahydrate;
the mass volume ratio of cerium nitrate hexahydrate, nickel ferrite and ethanol is 0.252g:1g:10ml;
Mixing cerium nitrate hexahydrate, nickel ferrite and ethanol, stirring for 10min to uniformity, igniting, calcining under air atmosphere at 600 ℃ for 30min, and grinding to obtain cerium oxide coated nickel ferrite, which is denoted as CeO 2-NiFe2O4 -N;
the obtained cerium oxide coated nickel ferrite is of a core-shell structure, wherein the mass ratio of the cerium oxide in the shell to the nickel ferrite in the core is 1:10.
Example 5:
Cerium salt is selected as cerium nitrate hexahydrate;
The mass volume ratio of cerium nitrate hexahydrate, nickel ferrite and ethanol is 0.504g:1g:10ml;
Mixing cerium nitrate hexahydrate, nickel ferrite and ethanol, stirring for 10min to uniformity, igniting, calcining under air atmosphere at 600 ℃ for 30min, and grinding to obtain cerium oxide coated nickel ferrite, which is denoted as CeO 2-NiFe2O4 -N;
the obtained cerium oxide coated nickel ferrite is of a core-shell structure, wherein the mass ratio of the cerium oxide of the shell to the nickel ferrite of the core is 1:5.
Example 6:
Cerium salt is selected as cerium nitrate hexahydrate;
The mass volume ratio of the cerium nitrate hexahydrate, the nickel ferrite and the ethanol is 1.008g:1g:10ml;
Mixing cerium nitrate hexahydrate, nickel ferrite and ethanol, stirring for 10min to uniformity, igniting, calcining under air atmosphere at 600 ℃ for 30min, and grinding to obtain cerium oxide coated nickel ferrite, which is denoted as CeO 2-NiFe2O4 -N;
the obtained cerium oxide coated nickel ferrite is of a core-shell structure, wherein the mass ratio of the cerium oxide of the shell to the nickel ferrite of the core is 1:2.5.
Comparative example 1:
cerium salt is selected as cerium chloride heptahydrate;
The mass volume ratio of the cerium chloride heptahydrate, the nickel ferrite and the ethanol is 0.866g:1g:10ml;
Mixing cerium chloride heptahydrate, nickel ferrite and ethanol, stirring for 10min to uniformity, igniting, calcining under air atmosphere at 600 ℃ for 30min, and grinding to obtain cerium oxide coated nickel ferrite, which is denoted as CeO 2-NiFe2O4 -Cl;
the obtained cerium oxide coated nickel ferrite is of a core-shell structure, wherein the mass ratio of the cerium oxide of the shell to the nickel ferrite of the core is 1:2.5.
Comparative example 2:
Selecting cerium salt as cerium acetate;
the mass volume ratio of the cerium acetate, the nickel ferrite and the ethanol is 0.738g:1g:10ml;
mixing cerium acetate, nickel ferrite and ethanol, stirring for 10min to uniformity, igniting, calcining under air atmosphere at 600 ℃ for 30min, and grinding to obtain cerium oxide coated nickel ferrite, which is denoted as CeO 2-NiFe2O4 -Ac;
The obtained cerium oxide coated nickel ferrite is of a core-shell structure, wherein the mass ratio of the cerium oxide in the shell to the nickel ferrite in the core is 1:5.
Comparative experiment 1:
The cerium oxide-nickel ferrite composite catalysts prepared in examples 1 to 6 and comparative examples 1 to 2 were subjected to catalytic activity detection, and the test method included: the prepared cerium oxide-nickel ferrite composite catalyst is subjected to carbon dioxide hydrogenation reduction reaction at the normal pressure of 500 ℃, and the specific steps are as follows:
0.05g of the cerium oxide-nickel ferrite composite catalyst is weighed, a catalytic experiment is carried out by adopting a U-shaped tube reaction heater in air flow with the volume ratio of H 2/CO2/Ar=4%: 1%:95% and the flow rate of 500ml/min, and the product is detected by a FID detector of gas chromatography, wherein the experimental result is shown in table 1.
The calculation formula is as follows: CO 2 conversion= (nCO 2 in-nCO2 out)/nCO2 in x 100%, where:
nCO 2 in represents the CO 2 content in the reaction gas,
NCO 2 out represents the CO 2 content in the product gas.
TABLE 1
| Experimental objects | CO 2 conversion (%) |
| Example 1 | 61.1 |
| Example 2 | 62.11 |
| Example 3 | 63.59 |
| Example 4 | 63.82 |
| Example 5 | 63.95 |
| Example 6 | 64.39 |
| Comparative example 1 | 37.28 |
| Comparative example 2 | 45.54 |
The CO 2 conversion rate reflects the activity degree of the cerium oxide-nickel ferrite composite catalyst on the catalytic hydrogenation of carbon dioxide to carbon monoxide, and the higher the conversion rate is, the better the catalytic activity of the cerium oxide-nickel ferrite composite catalyst is.
From the data of examples 1-6, it can be seen that:
Cerium nitrate hexahydrate is used as cerium salt, and ethanol is used as an organic solvent, so that the mass volume ratio of the cerium nitrate hexahydrate, nickel ferrite and ethanol is defined to be 1.008g:1g:5ml, the obtained cerium oxide-nickel ferrite composite catalyst has the highest conversion rate in the hydrogenation catalysis of carbon dioxide.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
(1) The cerium oxide-nickel ferrite composite catalyst obtained by using cerium salt as cerium nitrate is determined to have strong catalytic conversion capability in carbon dioxide catalytic hydrogenation.
(2) The cerium oxide-nickel ferrite composite catalyst provided by the embodiment of the invention has good surface quality and excellent catalytic effect, has better performance than the common carbon dioxide hydrogenation catalyst, and can be applied to carbon dioxide catalytic reduction in reverse water gas conversion, volatile organic compound waste gas catalytic treatment, solid oxide fuel cells and industrial carbon dioxide catalytic reduction to generate organic matters or carbon monoxide.
Comparative experiment 2:
The high temperature stability test was performed on example 5 and nickel ferrite, and the test method included: the cerium oxide-nickel ferrite composite catalyst and the nickel ferrite are respectively and continuously subjected to carbon dioxide hydrogenation reaction at the normal pressure of 700 ℃, and the specific steps are as follows:
0.05g of cerium oxide-nickel ferrite composite catalyst and nickel ferrite are respectively weighed, and H 2：CO2 is introduced into the mixture according to the volume ratio: ar=4%: 1%:95% gas, flow rate 500ml/min, and a catalytic experiment was performed using a U-tube reaction heater, and the product was detected by a FID detector of gas chromatography, and the experimental results are shown in FIG. 4.
As shown by experimental results, the cerium oxide-nickel ferrite composite catalyst has excellent high-temperature stability, and can continuously and efficiently reduce carbon dioxide into carbon monoxide.
FIG. 2 is an XRD pattern of the cerium oxide-nickel ferrite composite catalyst prepared in examples 1 to 6, the abscissa shows the characteristic peak position, and the ordinate shows the characteristic peak intensity. Wherein CeO 2 PDF#34-0394 represents a cerium oxide substance standard card, niFe 2O4 PDF#86-2267 represents a nickel ferrite substance standard card, fe 2O3 PDF#72-0469 represents an iron oxide substance standard card, and NiO PDF#71-1179 represents a nickel oxide substance standard card. As can be seen from the graph, the cerium oxide-nickel ferrite composite catalyst has clear CeO 2 peak and NiFe 2O4 peak, and as the coating amount of cerium oxide increases, the NiFe 2O4 peak gradually weakens and the CeO 2 peak gradually increases.
FIG. 3 is an XRD pattern of the cerium oxide-nickel ferrite composite catalyst and nickel ferrite obtained in example 6 and comparative examples 1 to 2, wherein the abscissa represents the characteristic peak position and the ordinate represents the characteristic peak intensity. Wherein CeO 2 PDF#34-0394 represents a cerium oxide substance standard card, niFe 2O4 PDF#86-2267 represents a nickel ferrite substance standard card, fe 2O3 PDF#72-0469 represents an iron oxide substance standard card, and NiO PDF#71-1179 represents a nickel oxide substance standard card. As can be seen from the graph, the example 6 and the comparative examples 1-2 have obvious CeO 2 peak and NiFe 2O4 peak, wherein the example 6 has smaller peak intensity and weaker crystallinity, which indicates that the prepared cerium oxide-nickel ferrite composite catalyst has more oxygen vacancies and further has higher reactivity.
FIG. 4 is a graph showing the results of the stability test of the cerium oxide-nickel ferrite composite catalyst prepared in example 5 with nickel ferrite as it is, the abscissa shows the test time, and the ordinate shows the conversion of CO 2 for a total of 50 hours. As can be seen from the figure, the catalytic conversion of the nickel ferrite into CO 2 in the high-temperature reducing atmosphere has three stages of rapid drop, rise and stabilization, the catalytic activity after stabilization is greatly reduced compared with that before reaction, and the cerium oxide-nickel ferrite composite catalyst prepared in the embodiment 5 has higher high-temperature reaction activity and better stability.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The foregoing is only a specific embodiment of the invention to enable those skilled in the art to understand or practice the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. A preparation method of a high-temperature stable reduction-resistant cerium oxide-nickel ferrite composite catalyst, which is characterized by comprising the following steps:
Dispersing cerium salt and nickel ferrite in ethanol and igniting, and calcining the burnt product to obtain a cerium oxide-nickel ferrite composite catalyst; the cerium oxide-nickel ferrite composite catalyst is of a core-shell structure, wherein the mass ratio of the cerium oxide in the shell to the nickel ferrite in the core is 1:100 to 1:2.5;
The calcination temperature is 500-800 ℃ and the calcination time is 20-40 min.
2. The method according to claim 1, wherein the cerium salt is cerium nitrate.
3. The method of claim 1, wherein the calcined atmosphere is an oxygen-containing environment.
4. The preparation method according to claim 1, wherein the mass-to-volume ratio of the cerium salt, the nickel ferrite and the ethanol is 0.013g:1g:10ml to 1.008g:1g:10ml.
5. A high temperature stable reduction resistant cerium oxide-nickel ferrite composite catalyst prepared by the preparation method of any one of claims 1-4.
6. The use of the cerium oxide-nickel ferrite composite catalyst according to claim 5, wherein the cerium oxide-nickel ferrite composite catalyst is used in a hydrogenation reduction reaction of carbon dioxide.
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