CN108262046A - doped hexaaluminate oxide catalyst, preparation method and application thereof - Google Patents
doped hexaaluminate oxide catalyst, preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 61
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 26
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 229910002651 NO3 Inorganic materials 0.000 claims description 14
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 238000009938 salting Methods 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 238000002407 reforming Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005352 clarification Methods 0.000 claims description 4
- 238000006057 reforming reaction Methods 0.000 abstract description 17
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 13
- 239000013078 crystal Substances 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 8
- 229910052759 nickel Inorganic materials 0.000 abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 abstract description 7
- 150000002910 rare earth metals Chemical class 0.000 abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 abstract description 6
- 150000003624 transition metals Chemical class 0.000 abstract description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Inorganic materials [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 8
- LBVWQMVSUSYKGQ-UHFFFAOYSA-J zirconium(4+) tetranitrite Chemical compound [Zr+4].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O LBVWQMVSUSYKGQ-UHFFFAOYSA-J 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910020793 Co0.5Ni0.5 Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000005431 greenhouse gas Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- -1 rare earth ion Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/76—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J1/00—Production of fuel gases by carburetting air or other gases without pyrolysis
- C10J1/20—Carburetting gases other than air
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention provides a doped hexaaluminate oxide catalyst, a preparation method and application thereof. Doped hexaaluminate oxide catalysts having the general formula Re0.8ZrxMANi1‑ AAl11O19‑Wherein Re is L a or Sr, M is Co, Fe, Mn or Cu, x is more than or equal to 0 and less than or equal to 0.2, and A is more than or equal to 0 and less than or equal to 1, because M, Ni, Zr and rare earth metal L a and the like are introduced into hexaaluminate crystal lattices, the content of each element is controlled to ensure thatThe advantages of the transition metal, the rare earth element and the hexaaluminate are fully exerted, the catalytic performance and the stability of the hexaaluminate oxide catalyst in the reforming reaction of methane and carbon dioxide are improved, the temperature of the reforming reaction can be reduced, and the energy consumption and the equipment requirement are further reduced; meanwhile, the catalyst can be prepared by a solution method and a high-temperature roasting method which are commonly used in the prior art, so that the preparation process is simplified, the cost is reduced, and the catalyst is suitable for industrial popularization and application.
Description
Technical field
The present invention relates to synthesis gas preparation field, in particular to a kind of doped hexa-aluminate oxide catalyst, its
Preparation method and applications.
Background technology
People begin to the preparing synthetic gas by reforming reaction of research methane and carbon dioxide in the 1920s, in recent years people
It pays close attention to very much due to global warming phenomenon caused by greenhouse gases, methane and carbon dioxide is all greenhouse gases, therefore, how to be utilized
And reduce the attention that both greenhouse gases increasingly obtain people.This side of methane and carbon dioxide catalytic reforming preparing synthetic gas
Method is to utilize and convert one of most promising technology of carbon containing greenhouse gases.Methane and carbon dioxide reforms obtained synthesis
Gas has higher purity, and the ratio of hydrogen and carbon monoxide in synthesis gas than the synthesis gas obtained by methane vapor reforming
Example is relatively low, is 1:1, be highly suitable as F- T synthesis long chain hydrocarbons, ammonia synthesis, carbonylation, methanol-fueled CLC and other
The unstrpped gas of oxygenatedchemicals.In addition, methane and carbon dioxide reforming reaction can be as the medium of chemical energy deposit, it can be with
The transport of energy is carried out, which is a strong endothermic reaction, and back reaction can release the energy of 247kJ/mol.Therefore, should
Reaction is good energy storage and Transmission system.Energy needed for positive reaction can be obtained from mineral combustion, solar energy or nuclear energy
, these energy will be stored in product (CO and H in the form of chemical energy2Gaseous mixture) in.Therefore, methane and carbon dioxide is urged
Change reforming reaction all has huge potentiality in terms of economic benefit and environmental benefit.
During reforming reaction, common noble metal catalyst activity is very high, and very stable, but but due to your gold
Belong to it is expensive and be unfavorable for practical application in industry.And abundance, economy are easily promoted and have fine catalytic activity
The non-noble metal-based catalysts such as Co, Ni are the emphasis of people's research, but since high temperature sintering ability is limited, it is difficult to reach practical and answer
It is required that.Hexa-aluminate catalyzer is in methane and carbon dioxide reforming reaction, and high high-temp stability is good, carbon accumulation resisting ability
By force, dispersion degree is high, is the hot spot of current people's research.
There are two types of Magnetoplumbate-type and β-alumina for the crystal structure of hexa-aluminate, belong to hexagonal crystal system, by minute surface each other
Spinelle block accumulated along C uranium piles, each spinelle specular layer is separated by single layer oxide, and big sun is dispersed on minute surface
Ion, such as alkali metal, alkaline-earth metal, rare earth ion.Stratiform spinelle matrix is by Al3+And O2+Composition, stratiform spinelle
Block mixes suitable transition metal ions part substitution in octahedral interstices or tetrahedron gap in hexa-aluminate crystal
Al3+When, the high degree of dispersion in the skeleton of hexa-aluminate, and the success that can reach active metal is inlayed and skeleton structure is constant
Purpose.Since the structure of hexa-aluminate is stratiform, and the spinelle unit of axis direction is separated, therefore inhibit by minute surface
Crystal along the axis direction vertical with minute surface growth so that hexa-aluminate have anisotropy, the growth of crystal axially
Also it is suppressed.Therefore, hexa-aluminate has excellent thermal stability and stronger anti-caking power.Hexa-aluminate is compound simultaneously
Oxide catalyst raw material is easy to get, and cost is less than noble metal catalyst, and synthesis technology is simple.
Publication No. CN104383927B patent applications disclose urging for a kind of methane and CO 2 reformation preparing synthetic gas
Activated carbon using activated carbon as carrier, using cobalt nickel as active component, with additive modifications such as zirconiums, is passed through ammonia by the preparation method of agent
Water impregnates, and microwave radiation is modified, and is fabricated to electrode, and Co-Ni-Zr-K-Mg is loaded to carrier surface system by Electro Sorb method
Obtain catalyst.Preparation process is cumbersome, and reaction temperature is 850 DEG C, is unfavorable for commercial Application；Turn of methane and carbon dioxide simultaneously
Rate is relatively low.
Invention content
It is a primary object of the present invention to provide a kind of doped hexa-aluminate oxide catalyst, preparation method and its answer
With to solve the problems, such as that methane is low with the catalytic efficiency of CO 2 reformation catalyst in the prior art.
To achieve these goals, according to an aspect of the invention, there is provided a kind of doped hexa-aluminate oxide is urged
Agent, the general formula of catalyst is Re0.8ZrxMANi1-AAl11O19-δ, wherein, Re is La or Sr, M Co, Fe, Mn or Cu, 0≤x≤
0.2,0≤A≤1.
Further, in above-mentioned general formula, 0≤x≤0.1.
Further, in above-mentioned general formula, 0.5≤A≤1.
Further, the grain size of above-mentioned catalyst is 20~60 mesh.
According to the another aspect of the application, a kind of preparation method of catalyst is provided, the general formula of catalyst is
Re0.8ZrxMANi1-AAl11O19-δ, wherein, Re is La or Sr, M Co, Fe, Mn or Cu, 0≤x≤0.2,0≤A≤1, preparation side
Method includes：Molar ratio according to each element in general formula prepares the salt of Re elements, Zr elements, M element, Ni elements and Al elements respectively
Solution；It is mixed after each salting liquid is mixed with the aqueous isopropanol of polyethylene glycol, forms mixed system；To the mixture after clarification
System carries out water bath processing to gel, obtains jello；And gel is dried successively, is roasted, obtain catalyst.
Further, above-mentioned salting liquid is nitrate solution.
Further, in above-mentioned general formula, 0≤x≤0.1.
Further, the temperature of above-mentioned water bath processing is 70~90 DEG C；It is preferred that drying is dried at a temperature of using 120~160 DEG C
It is dry to implement.
Further, above-mentioned roasting includes carrying out low-temperature bake successively and high-temperature roasting, the calcination temperature of low-temperature bake are
350~500 DEG C, roasting time is 2~4h；The calcination temperature of high-temperature roasting is 1150~1300 DEG C, and roasting time is 5~7h.
Further, after above-mentioned roasting, preparation method, which is further included, presses successively roasting obtained calcining matter
Piece and the process being granulated, the granulation mesh number of granulation is 20~60 mesh.
According to another aspect of the present invention, provide a kind of reforming method of methane and carbon dioxide, including make methane and
The process that carbon dioxide is reacted under the catalytic action of catalyst, the catalyst are any of the above-described kind of catalyst.
Further, the condition of above-mentioned reaction includes：GHSV=6000~10000h-1,CH4:CO2=1:1, reaction temperature
It is 750~800 DEG C.
It applies the technical scheme of the present invention, since M, Ni, Zr and rare-earth metal La etc. are introduced into hexa-aluminate lattice, leads to
The advantages of crossing the content of control each element, making transition metal, rare earth element and hexa-aluminate is not fully exerted, and improves six aluminium
Catalytic performance and stability of the hydrochlorate oxide catalyst in methane and carbon dioxide reforming reaction, can reduce reforming reaction
Temperature, thereby reduce energy consumption and equipment requirement；Above-mentioned catalyst uses solwution method commonly used in the prior art and height simultaneously
Warm roasting method can be prepared, therefore simplify preparation process, cost be reduced, suitable for industrial application.
Description of the drawings
The accompanying drawings which form a part of this application are used to provide further understanding of the present invention, and of the invention shows
Meaning property embodiment and its explanation do not constitute improper limitations of the present invention for explaining the present invention.In the accompanying drawings：
Fig. 1 shows the XRD spectra of 4 catalyst according to an embodiment of the invention；
Fig. 2 shows the SEM figures of according to an embodiment of the invention 4 catalyst, amplification factors 15000；And
Fig. 3 shows the SEM figures of 4 catalyst according to an embodiment of the invention, amplification factor 65000.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the application can phase
Mutually combination.The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with the embodiments.
It is in the prior art Co-Ni-Zr-K-Mg of the auxiliary agent using activated carbon as carrier using zirconium as background technology is analyzed
Catalyst needs to be modified using microwave radiation, and be fabricated to electrode, and will load to carrier surface by Electro Sorb method is made catalysis
Agent, preparation process is cumbersome, and reaction temperature is 850 DEG C, is unfavorable for commercial Application.In order to solve this problem, this application provides
A kind of doped hexa-aluminate oxide catalyst, preparation method and its application.
In a kind of typical embodiment of the application, a kind of doped hexa-aluminate oxide catalyst is provided, this is urged
The general formula of agent is Re0.8ZrxMANi1-AAl11O19-δ, wherein, Re be La or Sr, M Co, Fe, Mn or Cu, 0≤x≤0.2,0≤
A≤1.(19- δ are the common representation method in this field or 19+ δ expressions can also be used, and wherein δ can change, as long as chemistry can
Receiving).
Since M, Ni, Zr and rare-earth metal La etc. are introduced into hexa-aluminate lattice, by controlling the content of each element, make
The advantages of transition metal, rare earth element and hexa-aluminate, is not fully exerted, and improves hexa-aluminate oxide catalyst in first
Catalytic performance and stability in alkane and CO 2 reforming reaction, can reduce the temperature of reforming reaction, thereby reduce energy
Consumption and equipment requirement；Above-mentioned catalyst can be prepared into using solwution method commonly used in the prior art and high-temperature roasting method simultaneously
It arrives, therefore simplifies preparation process, cost is reduced, suitable for industrial application.
In order to further improve the stability of catalyst, in preferably above-mentioned general formula, 0≤x≤0.1.More preferable above-mentioned general formula
In, 0.5≤A≤1.
The catalyst of the application application when preferably with graininess application, it is excellent to increase its contact area with reactant
Choose state catalyst grain size be 20~60 mesh.
In another typical embodiment of the application, a kind of preparation method of catalyst is provided, the catalyst
General formula is Re0.8ZrxMANi1-AAl11O19-δ, wherein, Re is La or Sr, M Co, Fe, Mn or Cu, 0≤x≤0.2,0≤A≤1,
The preparation method includes：Molar ratio according to each element in general formula prepares Re elements, Zr elements, M element, Ni elements and Al respectively
The salting liquid of element；It is mixed after each salting liquid is mixed with the aqueous isopropanol of polyethylene glycol, forms mixed system；After clarification
Mixed system carry out water bath processing to gel, obtain jello；And gel is dried successively, is roasted, it is urged
Agent.
The aqueous isopropanol of above-mentioned polyethylene glycol is as dispersant, by the salting liquid of each element and the isopropanol of polyethylene glycol
Solution mixes, and then can obtain jello using conventional heating water bath processing；Common hexa-aluminate is being formed to jello
Roasting is dried under the drying of oxide, roasting condition, you can the application catalyst, preparation process is simple, condition
It is easily achieved, therefore is conducive to popularization and application in the industry.M, Ni, Zr and rare-earth metal La are introduced six by above-mentioned preparation method
In aluminate lattice, by controlling the content of each element, making transition metal, rare earth element and hexa-aluminate the advantages of obtains fully
It plays, improves catalytic performance and stability of the hexa-aluminate oxide catalyst in methane and carbon dioxide reforming reaction,
The temperature of reforming reaction can be reduced, thereby reduces energy consumption and equipment requirement
Above-mentioned salting liquid uses oxygen-containing salting liquid commonly used in the prior art, in order to be further simplified operation, preferably
Above-mentioned salting liquid is nitrate solution.
In order to further improve the stability of catalyst, each salting liquid preferably is prepared according to below general formula, general formula is
La0.8ZrxCo0.5Ni0.5Al11O19-δ, wherein, 0≤x≤0.1.
In addition, speed is formed in order to accelerate jello, and ensure each component mutually dissolves in state, at preferably above-mentioned water-bath
The temperature of reason is 70~90 DEG C.
Drying process in above-mentioned preparation method is primarily to remove the moisture in each salting liquid, in order to avoid dried
Excessive variation occurs for each group isloation state in jello in journey, and preferably above-mentioned drying is dried at a temperature of using 120~160 DEG C to be implemented.
Roasting process in above-mentioned preparation method mainly forms crystal structure.Its roasting condition can refer to the prior art
Roasting condition during middle formation hexa-aluminate oxide.In a kind of preferred embodiment of the application, above-mentioned roasting is included successively
Low-temperature bake and high-temperature roasting are carried out, the calcination temperature of low-temperature bake is 350~500 DEG C, and roasting time is 2~4h；High temperature roasts
The calcination temperature of burning is 1150~1300 DEG C, and roasting time is 5~7h.Above-mentioned low-temperature bake is at the beginning of primarily to remove dispersant
Step forms spinel crystal phase, and high-temperature roasting is primarily to form hexa-aluminate crystal structure.
In the application another kind preferred embodiment, after firing, above-mentioned preparation method is further included to roasting gained
To calcining matter carry out tabletting and the process being granulated successively, the granulation mesh number of granulation is 20~60 mesh.
In the application in another typical embodiment, a kind of reforming method of methane and carbon dioxide is provided, is wrapped
The process that methane and carbon dioxide is made to be reacted under the catalytic action of catalyst is included, which is any of the above-described kind of catalysis
Agent.
It is each by controlling since M, Ni, Zr and rare-earth metal La are introduced into hexa-aluminate lattice by the catalyst of the application
The content of element, the advantages of making transition metal, rare earth element and hexa-aluminate, are not fully exerted, and improve hexa-aluminate oxidation
Catalytic performance and stability of the object catalyst in methane and carbon dioxide reforming reaction can reduce the temperature of reforming reaction,
Thereby reduce energy consumption and equipment requirement.
In order to balance the relationship of energy consumption and reaction-ure conversion-age, the condition of preferably above-mentioned reaction includes：GHSV=6000~
10000h-1,CH4:CO2=1:1, reaction temperature is 750~800 DEG C.
Above-mentioned reaction condition is substantially reduced relative to 850 DEG C commonly used in the prior art, therefore, it is possible to further reduce
Energy consumption and the requirement to equipment；Meanwhile the catalyst of the application and catalyst commonly used in the prior art, equally in above-mentioned condition
Under carry out catalysis reaction so that the conversion ratio of methane and carbon dioxide is improved significantly.
Below with reference to embodiment and comparative example, the advantageous effect of the application is further illustrated.
Embodiment 1
Zr parts replace the hexa-aluminate catalyzer La of La0.8ZrxCo0.5Ni0.5Al11O19-δ, using high-temperature roasting nitrate
It is prepared by method.La (NO3)3·6H2O、Zr(NO3)4·5H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2O and Al (NO3)3·
9H2O is with molar ratio 0.8：0：0.5:0.5:11, with water dissolution is distilled, are configured to mixed solution.Mixed solution is slowly dropped into again
In the aqueous isopropanol of 50mL heat containing 3g PEG 20000s, mixed system is formed, the mixed system after clarification is put into
80 DEG C of water-baths, which are steamed to gel, obtains jello, and jello then is put into 150 DEG C of baking oven dries, after shape of claying into power, by powder
End 400 DEG C of roasting 2h in low temperature Muffle furnace place into 1250 DEG C of roasting 5h in high temperature Muffle furnace, are down to room temperature, tabletting is made
Grain takes granularity as catalyst of the particle of 20~60 mesh as embodiment 1.
Embodiment 2
The present embodiment is unlike specific embodiment 1：La(NO3)3·6H2O、Zr(NO3)4·5H2O、Co(NO3)2·
6H2O、Ni(NO3)2·6H2O and Al (NO3)3·9H2O is with molar ratio 0.8:0.02:0.5:0.5:11.
Embodiment 3
The present embodiment is as different from Example 1：La(NO3)3·6H2O、Zr(NO3)4·5H2O、Co(NO3)2·6H2O、
Ni(NO3)2·6H2O and Al (NO3)3·9H2O is with molar ratio 0.8:0.04:0.5:0.5:11.
Embodiment 4
The present embodiment and La (NO unlike specific embodiment 13)3·6H2O、Zr(NO3)4·5H2O、Co(NO3)2·
6H2O、Ni(NO3)2·6H2O and Al (NO3)3·9H2O is with molar ratio 0.8:0.06:0.5:0.5:11.Its XRD testing result is shown in
Fig. 1 shows that gained crystal structure is Magnetoplumbate-type hexa-aluminate, belongs to hexagonal crystal system.Meanwhile SEM testing results see Fig. 2 and
3。
Embodiment 5
The present embodiment is unlike specific embodiment 1：La(NO3)3·6H2O、Zr(NO3)4·5H2O、Co(NO3)2·
6H2O、Ni(NO3)2·6H2O and Al (NO3)3·9H2O is with molar ratio 0.8:0.08:0.5:0.5:11.
Embodiment 6
The present embodiment is unlike specific embodiment 1：La(NO3)3·6H2O、Zr(NO3)4·5H2O、Co(NO3)2·
6H2O、Ni(NO3)2·6H2O and Al (NO3)3·9H2O is with molar ratio 0.8:0.1:0.5:0.5:11.
Embodiment 7
The present embodiment is unlike specific embodiment 1：Re is Sr, Sr (NO3)2·4H2O、Zr(NO3)4·5H2O、Co
(NO3)2·6H2O、Ni(NO3)2·6H2O and Al (NO3)3·9H2O is with molar ratio 0.8:0.06:0:1:11.
Embodiment 8
The present embodiment is unlike specific embodiment 1：La(NO3)3·6H2O、Zr(NO3)4·5H2O、Co(NO3)2·
6H2O、Ni(NO3)2·6H2O and Al (NO3)3·9H2O is with molar ratio 0.8:0.06：0:1:11.
Comparative example 1
The catalyst as a comparison case 2 prepared using the method for embodiment 5 in the patent application of Publication No. 10438392B
Catalyst.
Inventor uses H2-O2The dispersion degree of the catalyst active center of pulse titration detection embodiment 1 to 8, detection knot
Fruit is shown in Table 1.
Table 1
Catalytic performance test：
The catalyst of embodiment 1 to 8 and comparative example 1 is subjected to catalytic performance test under the following conditions：
Methane reforming with carbon dioxide carries out in fixed-bed quartz reactor, Catalyst packing 0.3g, methane dioxy
The air inlet ratio for changing carbon is 1:1, volume space velocity 9000h-1, reaction temperature is 800 DEG C, and nitrogen is first passed through in temperature-rise period, waits liter
Unstripped gas is passed through during temperature to reaction temperature again to be reacted.The conversion ratio of methane and carbon dioxide is shown in Table 2 on this condition, product
The selectivity of hydrogen and carbon monoxide is shown in Table 2 in gas, successive reaction 48h catalyst performance stabiliseds.
Table 2
Data in table 1 and 2 can be seen that under the conditions of 800 DEG C, and the hexa-aluminate that Zr substitutions part La is modified is urged
Agent La0.8ZrxCo0.5Ni0.5Al11O19-δ(x=0~0.1), as x=0.06, catalyst activity is best, activated centre dispersion
Highest is spent, is 28.5%, while the initial conversion highest of methane and carbon dioxide, respectively reaches 94.26% and 97.83%,
After reaction 48 hours, catalyst La0.8Zr0.06Co0.5Ni0.5Al11O19-δMore than the conversion ratio of upper methane is still maintained at
92.36%, titanium dioxide charcoal percent conversion is then maintained at more than 96.90%, in synthesizing gas by reforming methane with co 2 reaction
There is very outstanding catalysis reaction stability.
Reaction temperature is 850 DEG C in embodiment 5 in the patent application of Publication No. 10438392B, methane and carbon dioxide
Conversion ratio for 89.1% and 87.0%, with the raising of reaction temperature, catalytic activity increases, and this patent is relatively
Under the conditions of low reaction temperature, higher catalytic performance is maintained.
It can be seen from the above description that the above embodiments of the present invention realize following technique effect：
Since M, Ni, Zr and rare-earth metal La etc. are introduced into hexa-aluminate lattice, by controlling the content of each element, make
The advantages of transition metal, rare earth element and hexa-aluminate, is not fully exerted, and improves hexa-aluminate oxide catalyst in first
Catalytic performance and stability in alkane and CO 2 reforming reaction, can reduce the temperature of reforming reaction, thereby reduce energy
Consumption and equipment requirement；Above-mentioned catalyst can be prepared into using solwution method commonly used in the prior art and high-temperature roasting method simultaneously
It arrives, therefore simplifies preparation process, cost is reduced, suitable for industrial application.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, that is made any repaiies
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (11)
1. a kind of doped hexa-aluminate oxide catalyst, which is characterized in that the general formula of the catalyst is Re0.8ZrxMANi1- AAl11O19-δ, wherein, Re is La or Sr, M Co, Fe, Mn or Cu, 0≤x≤0.2,0≤A≤1.
2. catalyst according to claim 1, which is characterized in that in the general formula, 0≤x≤0.1.
3. catalyst according to claim 1, which is characterized in that in the general formula, 0.5≤A≤1.
4. catalyst according to claim 1, which is characterized in that the grain size of the catalyst is 20~60 mesh.
5. a kind of preparation method of catalyst, which is characterized in that the general formula of the catalyst is Re0.8ZrxMANi1-AAl11O19-δ,
Wherein, Re is La or Sr, M Co, Fe, Mn or Cu, 0≤x≤0.2,0≤A≤1, and the preparation method includes：
Molar ratio according to each element in the general formula prepares Re elements, Zr elements, M element, Ni elements and Al elements respectively
Salting liquid；
It is mixed after each salting liquid is mixed with the aqueous isopropanol of polyethylene glycol, forms mixed system；
Water bath processing is carried out to the mixed system after clarification to gel, obtains jello；And
The gel is dried successively, is roasted, obtains the catalyst.
6. preparation method according to claim 5, which is characterized in that the salting liquid is nitrate solution.
7. preparation method according to claim 5, which is characterized in that in the general formula, 0≤x≤0.1.
8. preparation method according to claim 5, which is characterized in that the temperature of the water bath processing is 70~90 DEG C；It is excellent
It selects described dry using drying implementation at a temperature of 120~160 DEG C.
9. preparation method according to claim 5, which is characterized in that the roasting includes carrying out low-temperature bake and height successively
Temperature roasting, the calcination temperature of the low-temperature bake is 350~500 DEG C, and roasting time is 2~4h；The roasting of the high-temperature roasting
Temperature is 1150~1300 DEG C, and roasting time is 5~7h；It is preferred that after the roasting, the preparation method is further included to roasting
It burns obtained calcining matter and carries out tabletting and the process being granulated successively, the granulation mesh number of the granulation is 20~60 mesh.
10. a kind of reforming method of methane and carbon dioxide, including making methane and carbon dioxide under the catalytic action of catalyst
The process reacted, which is characterized in that the catalyst is catalyst any one of Claims 1-4.
11. reforming method according to claim 10, which is characterized in that the condition of the reaction includes：GHSV=6000
~10000h-1,CH4:CO2=1:1, reaction temperature is 750~800 DEG C.
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