CN110756213A - Aluminum nitride-based catalyst, preparation method and application - Google Patents
Aluminum nitride-based catalyst, preparation method and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 61
- 239000002184 metal Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000011258 core-shell material Substances 0.000 claims abstract description 17
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 28
- 239000012266 salt solution Substances 0.000 claims description 27
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 16
- 239000011261 inert gas Substances 0.000 claims description 15
- 229910017083 AlN Inorganic materials 0.000 claims description 14
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 11
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 claims description 11
- 238000006057 reforming reaction Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 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 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 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 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940071536 silver acetate Drugs 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052799 carbon Inorganic materials 0.000 abstract description 17
- 230000008021 deposition Effects 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000919 ceramic Substances 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 238000007654 immersion Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000002923 metal particle Substances 0.000 description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OWQNOTOYTSUHNE-UHFFFAOYSA-N carbon dioxide methane Chemical compound C.C(=O)=O.C OWQNOTOYTSUHNE-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J33/00—Protection of catalysts, e.g. by coating
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- 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
- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
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- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
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- 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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Abstract
The invention belongs to the field of catalyst preparation, and particularly relates to an aluminum nitride-based catalyst which has a core-shell structure and comprises an inner core and a shell, wherein the inner core is made of aluminum nitride, the shell is made of aluminum oxide, and an active metal component is arranged between the inner core and the shell. The invention also comprises a preparation method and application of the aluminum nitride-based catalyst. The invention has simple process and no pollution, and can be produced and used in large scale. The invention adopts novel aluminum nitride ceramic as a carrier, and the supported catalyst has high mechanical strength, high heat conductivity and high carbon deposit resistance. The active metal on the surface is coated by forming an alumina film to obtain a core-shell structure, so that the confinement effect of the active metal is realized, and the stability of the active metal and the carbon deposition resistance of the catalyst are improved.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to an aluminum nitride-based catalyst, a preparation method and application thereof.
Background
The AlN ceramic has excellent heat conductivity, high temperature resistance and corrosion resistance, not only meets the requirement of a large-scale methane-carbon dioxide reforming catalyst, but also can well improve the heat transfer of a catalyst bed, thereby inhibiting the problems of large migration and aggregation of metal particles caused by local non-uniformity in the heat transfer process, catalyst fracture caused by cold spots and the like.
At present, the carrier used in the methane-carbon dioxide reaction process is mostly low thermal conductivity carrier such as alumina and silica. Since the methane-carbon dioxide reaction is a strongly endothermic reaction, these low thermal conductivity supported catalysts tend to form "cold spots" in industrial applications leading to severe consequences such as catalyst cracking and reactor plugging. Moreover, the traditional industrial catalyst is difficult to completely solve the problems that metal particles are not grown and carbon deposition occurs in the catalytic reaction. This has also been a constraint on the large scale application of methane-carbon dioxide reforming processes. The improvement of the anti-sintering and carbon deposition performances of the catalyst is always the main research direction of the catalyst preparation process. At present, the performance of the catalyst preparation method used for improving the sintering resistance and the carbon deposition resistance in the laboratory research stage mainly adopts the methods of bimetallic alloying, addition of an auxiliary agent, physical limitation and the like. While bimetallic alloying and addition of additives only slow down the rate of sintering and carbon deposition. Although the effect of physical confinement can achieve complete sintering and carbon deposition resistance, the preparation method mainly comprises the technical means of hydrothermal synthesis, atomic layer deposition, ammonia evaporation induction method, microemulsion and the like, which are complex and seriously polluted, and the problems that metal is not completely coated and the like can be caused, so that the method is difficult to be used in large scale in industry.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, it is an object of the present invention to provide a simple, aluminum nitride-based catalyst with an environmentally friendly core-shell structure suitable for the reforming reaction of methane and carbon dioxide, which solves the problems of conventional Al2O3The problems of active metal sintering of the base catalyst and carbon deposition of the catalyst bring serious consequences to the reforming reaction of methane and carbon dioxide, and the method is suitable for industrial production of the aluminum nitride-based catalyst.
In order to achieve the above and other related objects, the present invention provides an aluminum nitride-based catalyst having a core-shell structure, including a core and a shell, wherein the core is aluminum nitride, the shell is aluminum oxide, and an active metal component is disposed between the core and the shell.
In some embodiments of the invention, the active metal component is selected from the group consisting of nickel, cobalt, platinum, iron, rhodium, palladium, silver, gold, and combinations of one or more thereof.
In some embodiments of the invention, the active metal component is selected from the group consisting of nickel, cobalt, platinum, and combinations of one or more thereof.
In some embodiments of the invention, the active metal component comprises 0.3 to 10% of the total mass of the catalyst.
In another aspect, the present invention provides a method for preparing the aluminum nitride-based catalyst according to the first aspect of the present invention, comprising the steps of:
1) roasting aluminum nitride powder under inert gas to obtain an aluminum nitride carrier;
2) providing a metal salt solution of an active metal component, and dropwise adding the metal salt solution to the aluminum nitride carrier in the step 1) to obtain a precursor A;
3) roasting the precursor A in the step 2) under inert gas;
4) preparing the precursor B from the roasted product in the step 3) in air with the relative humidity of 10-90%;
5) reducing the precursor B in the step 4) to obtain the aluminum nitride-based catalyst.
In some embodiments of the present invention, the aluminum nitride powder of step 1) contains less than 20% oxygen.
In some embodiments of the invention, the temperature of the calcination in the step 1) is 1300-1800 ℃, and the calcination time is 3-6 h.
In some embodiments of the invention, step 2) is performed by an equal volume impregnation method; the concentration of the active metal component in the soluble salt solution is 0.5 mol/L-3 mol/L.
In some embodiments of the present invention, the metal salt solution of the active metal component in step 2) is selected from one or more of nickel nitrate, nickel acetate, cobalt nitrate, cobalt acetate, ferric nitrate, chloroplatinic acid, ammonium chlororhodate, ammonium tetrachloropalladate, silver acetate, and chloroauric acid.
In some embodiments of the invention, the temperature of the roasting in the step 3) is 400-1000 ℃, and the roasting time is 3-6 h.
In some embodiments of the invention, the calcined product in the step 4) is placed in an environment with a temperature of 10-55 ℃; the standing time is 1 day to 1 year.
In some embodiments of the invention, the temperature of the reduction reaction of the precursor B in the step 5) is 400-850 ℃, and the reaction time is 1-5 hours.
In another aspect, the present invention provides the use of the aluminum nitride based catalyst of the present invention in methane-carbon dioxide reforming reactions.
The invention also provides a methane-carbon dioxide reforming reaction, which comprises the step of operating methane and carbon dioxide for 100-600 hours at the reaction temperature of 650-900 ℃ and the pressure of 1-5bar under the catalytic action of the aluminum nitride-based catalyst.
In some embodiments of the invention, the molar ratio of methane to carbon dioxide is from 0.7:1 to 1: 2.
Drawings
FIG. 1 shows the results obtained in example 2 of the present inventionNi @ Al with core-shell structure2O3Transmission electron microscopy images of/AlN catalyst.
FIG. 2 shows Ni @ Al of a core-shell structure obtained in example 2 of the present invention2O3Particle size distribution of Ni particle size variation before and after AlN catalyst reaction.
FIG. 3 shows Ni @ Al of a core-shell structure obtained in example 2 of the present invention2O3/AlN catalyst reactivity.
FIG. 4 shows Ni @ Al of a core-shell structure obtained in example 2 of the present invention2O3Carbon deposition amount of AlN catalyst.
Detailed Description
The aluminum nitride-based catalyst of the present invention, and the preparation method and application thereof are described in detail below.
The invention provides an aluminum nitride-based catalyst, which has a core-shell structure and comprises an inner core and a shell layer, wherein the inner core is made of aluminum nitride, the shell layer is made of aluminum oxide, and an active metal component is arranged between the inner core and the shell layer. The aluminum nitride as a carrier has high thermal conductivity and high mechanical property, the active metal component is attached to the aluminum nitride, and meanwhile, the aluminum oxide of the shell layer can completely wrap the active metal component on the surface to play a role in anchoring metal particles, so that the stability of the metal particles is enhanced, and the carbon deposition resistance of the catalyst is improved.
In the aluminum nitride-based catalyst provided by the invention, the active metal component is selected from one or more of nickel, cobalt, platinum, iron, rhodium, palladium, silver and gold. Preferably, the active metal component is selected from one or more of nickel, cobalt, platinum in combination. Further, the active metal component accounts for 0.3-10%, 0.3-5%, 5-10%, 0.3-1%, 1-3%, 3-5%, 5-7%, or 7-10% of the total mass of the catalyst. Within the above-mentioned loading range, the active metal component can be well supported on the aluminum nitride support.
A second aspect of the present invention provides a method for preparing the aluminum nitride-based catalyst according to the first aspect of the present invention, comprising the steps of:
1) roasting aluminum nitride powder under inert gas to obtain an aluminum nitride carrier;
2) providing a metal salt solution of an active metal component, and dropwise adding the metal salt solution into the aluminum nitride carrier in the step 1) to obtain a precursor A;
3) roasting the precursor A in the step 2) under inert gas;
4) and (3) preparing the precursor B from the roasted product in the step 3) in air with the relative humidity of 10-90%.
5) Reducing the precursor B in the step 4) to obtain the aluminum nitride-based catalyst.
In the preparation method of the aluminum nitride-based catalyst provided by the invention, in the step 1), the aluminum nitride powder is roasted under inert gas to obtain the aluminum nitride carrier. The aluminum nitride support may be an aluminum nitride ceramic. Specifically, the aluminum nitride powder contains less than 20% of oxygen, and the inert gas in the step 1) is selected from a fifth main group element, preferably, the inert gas is selected from N2And one or more of He and Ar. Under the general condition, the aluminum nitride powder is heated to 1300-1800 ℃ at the speed of 3-10 ℃/min under the inert gas atmosphere and is roasted at the constant temperature for 3-6 h to obtain the aluminum nitride carrier. In some embodiments, the temperature increase rate can also be 3-5 ℃/min, 5-7 ℃/min, or 7-10 ℃/min; the temperature during roasting can also be 1300-1500 ℃, 1500-1600 ℃, or 1600-1800 ℃; the roasting reaction time can also be 3-6 h, 3-4 h, 4-5 h, or 5-6 h.
In the preparation method of the aluminum nitride-based catalyst, in the step 2), a metal salt solution of an active metal component is provided, and the metal salt solution is dropwise added to the aluminum nitride carrier in the step 1) to obtain a precursor A. Specifically, the metal salt solution of the metal component needs to be stirred for 3-5 hours in the preparation process, an isometric immersion method is adopted in the step 2), the metal salt solution of the metal component is slowly dripped into the aluminum nitride carrier, the mixture is fully stirred and then dried, and the drying temperature is 100-130 ℃, and preferably 120 ℃. Wherein the concentration of the active metal component in the soluble salt solution in the step 2) is 0.5-3 mol/L, 0.5-1 mol/L, 1-2 mol/L, or 2-3 mol/L. The metal salt solution of the active metal component is selected from one or more of nickel nitrate, nickel acetate, cobalt nitrate, cobalt acetate, ferric nitrate, chloroplatinic acid, ammonium chlororhodate, ammonium tetrachloropalladate, silver acetate and chloroauric acid, preferably, the metal salt solution of the active metal component is selected from one or more of nickel nitrate, nickel acetate, cobalt nitrate, cobalt acetate and chloroplatinic acid.
In the preparation method of the aluminum nitride-based catalyst, the precursor A in the step 2) is roasted in inert gas in the step 3). In particular, the inert gas in step 3) is selected from the group consisting of the elements of the fifth main group, preferably the inert gas is selected from the group consisting of N2And one or more of He and Ar. In general, in an inert gas atmosphere, the temperature is raised to 400-1000 ℃ at a rate of 5-10 ℃/min and the mixture is roasted for 3-6 h at a constant temperature. In some embodiments, for example, the temperature rise rate can be 5-7 deg.C/min, 7-9 deg.C/min, 9-10 deg.C/min, or 6-8 deg.C/min. The constant temperature during roasting can be controlled at 700-900 ℃, 400-700 ℃ or 900-1000 ℃. The roasting time can also be 3-4 h, 4-5 h, or 5-6 h.
In the preparation method of the aluminum nitride-based catalyst provided by the invention, in the step 4), the roasted product obtained in the step 3 is placed in the air with the relative humidity of 10-90% to prepare a precursor B. Specifically, the roasted product is placed in a certain humidity range at an ambient temperature of 10-55 ℃, 10-20 ℃, 20-30 ℃, 30-40 ℃ or 40-55 ℃ for 1 day-1 year, 1 day-1 month, 1 month-3 months, 3 months-6 months, 6 months-9 months or 9 months-1 year.
In the preparation method of the aluminum nitride-based catalyst, the precursor B in the step 4) is reduced at high temperature in the step 5) to obtain the aluminum nitride-based catalyst with the core-shell structure. Specifically, the reduction temperature is 400-850 ℃, 400-500 ℃, 500-600 ℃, 600-700 ℃, or 700-850 ℃. The reaction time is 1-5 h, 1-2 h, 2-3 h, 3-4 h, or 4-5 h.
In a third aspect, the present invention provides the use of an aluminium nitride based catalyst according to the first aspect of the invention in a carbon dioxide methane reforming reaction.
The fourth aspect of the invention provides a carbon dioxide methane reforming reaction, which comprises mixing methane, carbon dioxide and the catalyst of the invention, and reacting at the reaction temperature of 650-900 ℃ and the pressure of 1-5 bar.
In the carbon dioxide-methane reforming reaction, the molar ratio of methane to carbon dioxide is 0.7: 1-1: 2. The reaction volume space velocity is 30000-120000 ml/g.h, 30000-50000 ml/g.h, 50000-80000 ml/g.h or 80000-120000 ml/g.h. The reaction temperature can also be 650-800 ℃ or 800-900 ℃. The pressure may also be 1-2bar, 2-3bar, 3-4bar, or 4-5 bar. The reaction time can be 100-600 h, 100-200 h, 1200-6300 h, 1300-6400 h, 1400-6500 h or 500-600 h.
The invention has the beneficial effects that:
(1) the invention has simple process and no pollution, and can be produced and used in large scale.
(2) The invention adopts novel aluminum nitride ceramic as a carrier, and the supported catalyst has high mechanical strength, high heat conductivity and high carbon deposit resistance.
(3) The active metal on the surface is coated by forming an alumina film to obtain a core-shell structure, so that the confinement effect of the active metal is realized, and the stability of the active metal and the carbon deposition resistance of the catalyst are improved.
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
It is to be understood that the processing equipment or apparatus not specifically identified in the following examples is conventional in the art.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
Example 1
Weighing 10g of active aluminum nitride fine powder, heating to 1500 ℃ at a speed of 10 ℃/min under a nitrogen atmosphere, and calcining for 3h to obtain a high-temperature treated aluminum nitride carrier; then 10g of nickel nitrate hexahydrate is weighed and 100ml of water is added to prepare a metal salt solution. Then slowly dripping the metal salt solution into the aluminum nitride carrier by adopting an isometric immersion method, fully stirring and drying at 120 ℃. N is a radical of2Under the atmosphere, the temperature is raised to 800 ℃ at the temperature raising speed of 5 ℃/min and is kept constant for 4 h. The prepared catalyst was exposed to air with a relative humidity of 90%, and the precursor B was obtained after standing at room temperature for 1 day. Reducing the precursor B at 800 ℃ for 4h to obtain the complete core-shell structure Ni @ Al2O3an/AlN catalyst.
The catalysts described above were tested for catalytic activity: 100mg of catalyst was placed in a fixed bed quartz tube reactor for catalyst performance testing, CH4And CO2The sampling quantity ratio is 1:1 (the flow rate is 50mL/min), the reaction temperature of the catalyst is 900 ℃, the reaction is carried out under normal pressure, and after the reaction for 100 hours, CH4And CO2The conversion rates are respectively kept at 92% and 95%, the catalyst activity is stable, no carbon deposition is formed, and the growth degree of Ni particles is low.
Example 2
Weighing 10g of active aluminum nitride fine powder, heating to 1500 ℃ at a speed of 10 ℃/min under a nitrogen atmosphere, and calcining for 3h to obtain a high-temperature treated aluminum nitride carrier; then 10g of nickel nitrate hexahydrate is weighed and 100ml of water is added to prepare a metal salt solution. Then using the equivalentThe product dipping method, slowly dropping the metal salt solution into the aluminum nitride carrier, fully stirring, and drying at 120 ℃. Heating to 800 ℃ at a heating rate of 5 ℃/min under Ar atmosphere, and keeping the temperature for 4 h. The prepared catalyst was exposed to air with a relative humidity of 65%, and the precursor B was obtained after standing at room temperature for 30 days. Reducing the precursor B at 800 ℃ for 4h to obtain the complete core-shell structure Ni @ Al2O3an/AlN catalyst. FIG. 1 shows that the Ni @ Al of the present embodiment2O3Transmission electron microscopy images of/AlN catalyst.
The catalysts described above were tested for catalytic activity: 100mg of catalyst was placed in a fixed bed quartz tube reactor for catalyst performance testing, CH4And CO2The sampling quantity ratio is 1:1 (the flow is 50mL/min), the reaction temperature of the catalyst is 800 ℃, the reaction pressure is 5bar, the activity is stable after 70h of reaction, and after 100h of reaction, as can be seen from figure 3, CH4And CO2The conversion rates were maintained at 74% and 78%, respectively, and the catalyst activity was stable, as can be seen from fig. 4, the catalyst of this example had no carbon deposit formation, and as can be seen from fig. 2, the Ni particle growth was low.
Example 3
Weighing 10g of active aluminum nitride fine powder, heating to 1500 ℃ at a speed of 10 ℃/min under a nitrogen atmosphere, and calcining for 3h to obtain a high-temperature treated aluminum nitride carrier; then 10g of nickel nitrate hexahydrate is weighed and 100ml of water is added to prepare a metal salt solution. Then slowly dripping the metal salt solution into the aluminum nitride carrier by adopting an isometric immersion method, fully stirring and drying at 120 ℃. Under the He atmosphere, the temperature is raised to 800 ℃ at the temperature raising speed of 5 ℃/min and is kept constant for 4 h. The prepared catalyst was exposed to humid air with a relative humidity of 10%, and the precursor B was obtained after standing at room temperature for 1 year. Reducing the precursor B at 800 ℃ for 4h to obtain the complete core-shell structure Ni @ Al2O3an/AlN catalyst.
The catalysts described above were tested for catalytic activity: 100mg of catalyst was placed in a fixed bed quartz tube reactor for catalyst performance testing, CH4And CO2The sampling quantity ratio is 1:1 (the flow rate is 50mL/min), the reaction temperature of the catalyst is 650 ℃, the reaction pressure is 5bar,after 100h of reaction, CH4And CO2The conversion rates are respectively kept at 45% and 49%, the catalyst activity is stable, no carbon deposition is formed, and the growth degree of Ni particles is low.
Example 4
Weighing 10g of active aluminum nitride fine powder, heating to 1500 ℃ at a speed of 10 ℃/min under a nitrogen atmosphere, and calcining for 3h to obtain a high-temperature treated aluminum nitride carrier; then 10g of cobalt nitrate hexahydrate and 100ml of water are weighed to prepare a metal salt solution. Then slowly dripping the metal salt solution into the aluminum nitride carrier by adopting an isometric immersion method, fully stirring and drying at 120 ℃. N is a radical of2Under the atmosphere, the temperature is raised to 800 ℃ at the temperature raising speed of 5 ℃/min and is kept constant for 4 h. The prepared catalyst was exposed to humid air with a relative humidity of 65%, and the precursor B was obtained after standing at room temperature for 30 days. Reducing the precursor B at 800 ℃ for 4h to obtain the complete core-shell structure Co @ Al2O3an/AlN catalyst.
The catalysts described above were tested for catalytic activity: 100mg of catalyst was placed in a fixed bed quartz tube reactor for catalyst performance testing, CH4And CO2The sampling quantity ratio is 1:1 (the flow rate is 50mL/min), the reaction temperature of the catalyst is 800 ℃, the reaction pressure is 3bar, and after the reaction for 100 hours, CH is added4And CO2The conversion rates are respectively kept at 65% and 66%, the catalyst activity is stable, no carbon deposition is formed, and the growth degree of Co particles is low.
Example 5
Weighing 10g of active aluminum nitride fine powder, heating to 1500 ℃ at a speed of 10 ℃/min under a nitrogen atmosphere, and calcining for 3h to obtain a high-temperature treated aluminum nitride carrier; then 2g of chloroplatinic acid is weighed and 100ml of water is added to prepare a metal salt solution. Then slowly dripping the metal salt solution into the aluminum nitride powder by adopting an isometric immersion method, fully stirring and drying at 120 ℃. Under the inert gas, the temperature is raised to 400 ℃ at the temperature raising speed of 5 ℃/min and is kept constant for 4 h. The prepared catalyst was exposed to humid air with a relative humidity of 65%, and the precursor B was obtained after standing at room temperature for 30 days. Reducing the precursor B at 800 ℃ for 4h to obtain the complete core-shell structure Pt @ Al2O3an/AlN catalyst.
The catalysts described above were tested for catalytic activity: 100mg of catalyst was placed in a fixed bed quartz tube reactor for catalyst performance testing, CH4And CO2The sampling quantity ratio is 1:1 (the flow rate is 100mL/min), the reaction temperature of the catalyst is 800 ℃, the reaction pressure is 5bar, and after the reaction for 100 hours, CH is added4And CO2The conversion rates are respectively kept at 68% and 69%, the catalyst activity is stable, no carbon deposition is formed, and the growth degree of Pt particles is low.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (15)
1. The aluminum nitride-based catalyst has a core-shell structure and comprises a core and a shell, wherein the core is made of aluminum nitride, the shell is made of aluminum oxide, and an active metal component is arranged between the core and the shell.
2. The aluminum nitride-based catalyst according to claim 1, wherein the active metal component is selected from the group consisting of nickel, cobalt, platinum, iron, rhodium, palladium, silver, gold, and combinations thereof.
3. The aluminum nitride-based catalyst according to claim 1, wherein the active metal component is selected from the group consisting of nickel, cobalt, platinum, and combinations thereof.
4. The aluminum nitride-based catalyst according to claim 1, wherein the active metal component is present in an amount of 0.3 to 10% by mass based on the total mass of the catalyst.
5. A process for the preparation of an aluminium nitride based catalyst according to any of claims 1 to 4, comprising the steps of:
1) roasting aluminum nitride powder under inert gas to obtain an aluminum nitride carrier;
2) providing a metal salt solution of an active metal component, and dropwise adding the metal salt solution to the aluminum nitride carrier in the step 1) to obtain a precursor A;
3) roasting the precursor A in the step 2) under inert gas;
4) preparing the precursor B from the roasted product in the step 3) in air with the relative humidity of 10-90%;
5) reducing the precursor B in the step 4) to obtain the aluminum nitride-based catalyst.
6. The method for producing an aluminum nitride-based catalyst according to claim 5, wherein the aluminum nitride powder in the step 1) contains less than 20% of oxygen.
7. The method for preparing the aluminum nitride-based catalyst according to claim 5, wherein the calcination temperature in the step 1) is 1300-1800 ℃ and the calcination time is 3-6 h.
8. The method for preparing an aluminum nitride-based catalyst according to claim 5, wherein the step 2) employs an equal volume impregnation method; the concentration of the active metal component in the soluble salt solution is 0.5 mol/L-3 mol/L.
9. The method for preparing an aluminum nitride-based catalyst according to claim 5, wherein the metal salt solution of the active metal component in step 2) is selected from one or more of nickel nitrate, nickel acetate, cobalt nitrate, cobalt acetate, ferric nitrate, chloroplatinic acid, ammonium chlororhodate, ammonium tetrachloropalladate, silver acetate, and chloroauric acid.
10. The method for preparing the aluminum nitride-based catalyst according to claim 5, wherein the calcination temperature in the step 3) is 400-1000 ℃ and the calcination time is 3-6 h.
11. The method for preparing the aluminum nitride-based catalyst according to claim 5, wherein the calcined product in the step 4) is placed in an environment with a temperature of 10-55 ℃ for 1 day-1 year.
12. The method for preparing the aluminum nitride-based catalyst according to claim 5, wherein the temperature of the reduction reaction of the precursor B in the step 5) is 400-850 ℃, and the reaction time is 1-5 h.
13. Use of an aluminium nitride based catalyst according to any one of claims 1 to 4 in methane-carbon dioxide reforming reactions.
14. A methane-carbon dioxide reforming reaction, which comprises the step of operating methane and carbon dioxide for 100-600 h at the reaction temperature of 650-900 ℃ and the pressure of 1-5bar under the catalysis of the aluminum nitride-based catalyst as claimed in any one of claims 1-4.
15. The methane-carbon dioxide reforming reaction according to claim 14, wherein the molar ratio of methane to carbon dioxide is 0.7:1 to 1: 2.
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