CN108940287A - A kind of Ni bimetallic Nano capsule catalyst and its preparation and application - Google Patents
A kind of Ni bimetallic Nano capsule catalyst and its preparation and application Download PDFInfo
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- CN108940287A CN108940287A CN201810712246.XA CN201810712246A CN108940287A CN 108940287 A CN108940287 A CN 108940287A CN 201810712246 A CN201810712246 A CN 201810712246A CN 108940287 A CN108940287 A CN 108940287A
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- Prior art keywords
- catalyst
- capsule
- added
- shell
- nano capsule
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 239000002088 nanocapsule Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002775 capsule Substances 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000956 alloy Substances 0.000 claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 10
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- 238000006057 reforming reaction Methods 0.000 claims abstract description 7
- 210000003850 cellular structure Anatomy 0.000 claims abstract description 4
- 239000008187 granular material Substances 0.000 claims abstract description 4
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- FDCJDKXCCYFOCV-UHFFFAOYSA-N 1-hexadecoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC FDCJDKXCCYFOCV-UHFFFAOYSA-N 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 229910018054 Ni-Cu Inorganic materials 0.000 claims description 7
- 229910018481 Ni—Cu Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910017709 Ni Co Inorganic materials 0.000 claims description 6
- 229910003267 Ni-Co Inorganic materials 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- 229910003262 Ni‐Co Inorganic materials 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 6
- 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 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 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 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 239000013528 metallic particle Substances 0.000 abstract description 6
- 238000005245 sintering Methods 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 238000004873 anchoring Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 44
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 35
- 229910002092 carbon dioxide Inorganic materials 0.000 description 25
- 239000007789 gas Substances 0.000 description 18
- 239000001569 carbon dioxide Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 230000008859 change Effects 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000006004 Quartz sand Substances 0.000 description 7
- 238000001833 catalytic reforming Methods 0.000 description 7
- 238000005352 clarification Methods 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000000693 micelle Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 230000003019 stabilising effect Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 description 1
- UWIULCYKVGIOPW-UHFFFAOYSA-N Glycolone Natural products CCOC1=C(CC=CC)C(=O)N(C)c2c(O)cccc12 UWIULCYKVGIOPW-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002923 metal particle Substances 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
- 239000005445 natural material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010181 polygamy Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010902 straw Substances 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/396—
-
- B01J35/40—
-
- B01J35/50—
-
- B01J35/647—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
-
- 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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
-
- 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
Abstract
The invention discloses a kind of Ni bimetallic Nano capsule catalyst and its preparation and application, the catalyst to be made of capsule shell and metal inner core；Capsule shell is silica, and metal inner core is bimetallic ambrose alloy or nickel cobalt particle；Ambrose alloy or nickel cobalt total content are in 10~20wt%, ambrose alloy or nickel cobalt bimetal granule partial size in 1~4nm, capsule cavity (6.5~7.5) nm × (15~60) nm, 5.5 ± 3nm of capsule shell thickness in the Nano capsule catalyst；The Nano capsule catalyst has twin-stage cellular structure, wherein the hole of 3~4nm derives from capsule hollow body lumen from the duct that penetrates of shell, the hole of 12~15nm.The unique space confinement structure of the catalyst steric hindrance of shell cavity space appropriate, capsule structure (anchoring of the height nanosizing, metallic particles of metallic particles inside shell) and bimetallic synergistic effect under pyroreaction can the effectively sintering of inhibitory activity component and carbon distribution formation, the activity and stability having had in biogas reforming reaction.
Description
Technical field
The present invention relates to Nano capsule structure catalyst, specifically a kind of Ni bimetallic Nano capsule catalyst and
The application of preparation method and the catalyst in biogas reforming reaction.
Background technique
Biogas be mainly derived from agricultural crop straw, in forest tree castoff and industrial wastewater biomass anaerobic degradation,
Its main component is that methane (50%-70%) and carbon dioxide (30%-50%), the composition ratio of the two make it can be used as first
The natural material of alkane CO 2 reformation preparing synthetic gas, and then be applied to produce the fields such as hydrogen, fuel cell or synthetic oil.But
Methane is slightly more than carbon dioxide in usual biogas composition, and excessive methane readily facilitates the sintering of catalyst activity metal simultaneously
Serious carbon distribution is generated, it is higher to catalyst requirement.
Nickel-base catalyst is due to its excellent activity, content inexpensive and abundant, it is considered to be in industrial application preferably
Catalyst.However, the prerequisite of industrial catalyst is must to provide higher metal for most of pyroreactions
Content (>10wt%) and smaller nanocrystalline grain size (<5nm), but the fact is that, in most cases, Ni nano particle exists
It is invariably prone to be sintered in the case that tenor is high and forms carbon distribution.Therefore, high stability industry Ni base catalyst is designed
Significant challenge is that high activity Ni nano particle how to be made still to be able to be stabilized under high load amount and hot conditions.
In order to overcome the negative effect of Ni nanoparticles sinter and carbon distribution to catalyst activity and stability, on the one hand, can
To carry out bimetallic modified synergic to Ni nano particle, improve the electronic effect and geometric effect of catalyst, effective separate metal
The polygamy position active site of particle surface inhibits the formation in carbon distribution site；On the other hand, porous oxide can be coated on activity
It is modified that core-shell structure is formed on metal, and metal sintering and Carbon deposition are inhibited by cladding metallic site.If two methods are joined
It closes, is expected to greatly improve the reactivity of reforming catalyst and long period stability.For example, Chinese patent CN104998649A is public
A kind of SiO is opened2The preparation method of@NiCe catalyst with core-casing structure, methane carbon dioxide reformation catalytic efficiency are higher.So
And nuclear-shell structure type catalyst is since (Ni particle is typically larger than 10nm to limited active metal exposure, and particle is bigger, exposure
Active surface is fewer) and fine and close thickness of the shell cause the active site Ni to be insufficient for the quick diffusion of reactant and convert.This
Outside, the metallic particles being coated in shell chamber can move freely, and lead to metal-carrier interaction of difference, be not suitable for high first
The reforming reaction process of alkane concentration.
Summary of the invention
The purpose of the present invention is to provide a kind of Ni bimetallic Nano capsule catalyst, which should have space limit
Domain structure and bimetallic synergistic effect, while meeting higher tenor (> 10wt%) and lesser nanocrystalline grain size
(< 5nm), it can the sintering of effective inhibitory activity component and the formation of carbon distribution under pyroreaction.
To achieve the above object, technical solution provided by the invention is as follows:
A kind of Ni bimetallic Nano capsule catalyst, is made of capsule shell and metal inner core；The capsule shell
For silica, the metal inner core is bimetallic ambrose alloy or nickel cobalt particle；Ambrose alloy or nickel in the Nano capsule catalyst
Cobalt total content in 10~20wt%, ambrose alloy or nickel cobalt bimetal granule partial size in 1~4nm, capsule cavity (6.5~7.5) nm ×
(15~60) nm, 5.6 ± 3nm of capsule shell thickness；The Nano capsule catalyst has twin-stage cellular structure, wherein 3~
The hole of 4nm derives from capsule hollow body lumen from the duct that penetrates of shell, the hole of 12~15nm.
The catalyst has unique space confinement structure, and (metallic particles height nanosizing, metallic particles are anchored on shell
Shell chamber reaction compartment internal, appropriate, capsule structure have steric hindrance) and bimetallic synergistic effect, under pyroreaction
Can the effectively sintering of inhibitory activity component and carbon distribution formation, outstanding activity and steady is illustrated in biogas reforming reaction
It is qualitative.
The preparation method of Nano capsule catalyst of the present invention, comprising the following steps:
(1) 10~50g surfactant is weighed in container, and hexamethylene is added to 100mL, heats simultaneously at 40~60 DEG C
Stirring；
(2) the Ni-Co mixed salt solution or Ni-Cu mixed salt solution of 5~10mL, 1.5~2.0mol/L, Ni-Co is added
Or the molar ratio of Ni-Cu is 4~1:1,2~8mL hydrazine hydrate is added to after mixing in stirring；
(3) it after aging 0.5~for 24 hours, increases speed of agitator and the concentrated ammonia liquor of 15mL and the mixed solution of deionized water is simultaneously added,
It is slowly added to 7.5~15mL TEOS later；
(4) acetone demulsification is added after hydrolyzing 1~48h, and is centrifuged；
(5) by the sample of upper step dry 12 at 50~120 DEG C~for 24 hours, then in air atmosphere with 1~5 DEG C/min
Rate calcined at 500~800 DEG C.Ni-Cu (Co) total content is in 10~20wt.%, Ni-Cu (Co) in gained catalyst
Bimetal granule partial size is in 1~4nm, capsule cavity (6.5~7.5) nm × (15~60) nm, 5.5 ± 3nm of shell thickness.
Surfactant described in step (1) is polyoxyethylene (10) cetyl ether, the mono- 4- nonylplenyl ether of polyethylene glycol
One or both of.
Ni-Co mixed salt solution described in step (2) is mixed solution, nickel chloride and the chlorine of nickel nitrate and cobalt nitrate
Change the mixed solution of cobalt or the mixed solution of nickel acetylacetonate and acetylacetone cobalt；The Ni-Cu mixed salt solution is nitric acid
The mixing of the mixed solution of nickel and copper nitrate, the mixed solution of nickel chloride and copper chloride or nickel acetylacetonate and acetylacetone copper is molten
Liquid.
The effect of hydrazine hydrate is multiple in step (2), has the function of reducing agent, couplant and raw infusion.
Concentrated ammonia liquor content is 1~3mL in mixed solution in step (3).
The Nano capsule catalyst can be applied in biogas reforming reaction, react in piston flow fixed bed reaction
It being carried out in device, the condition of reforming reaction is preferred are as follows: pressure is normal pressure, 650~750 DEG C of reduction temperature, reaction temperature 700~850
DEG C, gas space velocity GHSV is 12~48Lg-1·h-1, biogas mole group is as CH4:CO2:N2=1.1~1.4:1:1~
5。
The special capsule structure of catalyst of the present invention is embodied in its unique preparation principle (see Fig. 1): 1) present invention uses
Micro- sol system, since grease stabilising system concentration range is very wide, micella particle is small, can by adjust preparation parameter make Ni
Partial size stability contorting is in 1~4nm；2), present invention introduces bimetallic auxiliary agent Cu, Co not but not destroy microemulsion system micella
Stability can reduce the reducing electrode potential of Ni precursor salt instead, promote the quick formation of metal inner core in micella；3) this hair
Micro- sol system of bright use can not only realize that the monodisperse of the opposite water phase of oil uniformly coats, moreover it is possible to realize in the opposite micella of oil
The cladding of spontaneous gas phase (from the decomposition of reduction coupling agent), during material self assembles coat, water phase nickel presoma is gone back
Former process reduction coupling agent N2H4A small amount of N can be generated2、NH3Or H2Equal bubbles, bubble can in slightly soluble glue micelle volume of the present invention
It is stabilized, and orderly expands original globular micelle to column to ullage under the promotion of the directed forces of natural buoyancy
Capsule, thus realize the growth course of orderly capsule clad structure.
Compared with prior art, the invention has the following advantages:
(1) the unique Nano capsule structure of catalyst prepared by the present invention can be used as a microreactor, for reaction
Gas provides enough spaces with reacting for active site, and monodispersed configuration state avoids catalyst in pyroreaction
Under interfere with each other；
(2) Cu or Co metal is introduced in catalyst prepared by the present invention to form alloy nanoparticle with Ni, separated
While Ni metallic site, the electronic effect and geometric effect of catalyst can be improved, reduce metallic particles partial size, catalysis is improved and live
Property and stability；
(3) catalyst activity tenor prepared by the present invention ensure that in 10~20wt%, average grain diameter < 4nm
Active site has biggish exposed surface area, and within the unit time, the conversion ratio of methane and carbon dioxide is higher, meanwhile, it is small
Active metal particles can effectively inhibit the generation of the carbon distribution in high-temperature reaction process；
(4) active metal can be strictly anchored on silica capsule construction interior by catalyst prepared by the present invention,
Migration and aggregation of the active metal in high-temperature reaction process are limited, ensure that active site will not be reduced.And by anchor
Fixed active metal is due to the physical action strong with carrier, so that not easily leading to the formation for the carbon coated for inactivating active site；
(5) capsule catalyst prepared by the present invention has unique twin-stage cellular structure (Fig. 2), wherein the hole of 3~4nm
From the duct that penetrates of shell, promote reaction gas diffusion, the hole of 12~15nm derives from capsule hollow body lumen, promotes reaction
Gas is reacted in capsule inner surface；
(6) micro- sol system that preparation method of the present invention uses can not only realize that the monodisperse of the opposite water phase of oil uniformly wraps
It covers, moreover it is possible to the cladding for realizing spontaneous gas phase in the opposite micella of oil, during material self assembles coat, the reduction of water phase nickel presoma
Process can generate a small amount of N2、NH3Or H2Equal bubbles, bubble can be stabilized in slightly soluble glue micelle volume of the present invention, and certainly
Orderly expand original globular micelle to column capsule to ullage under the promotion of the directed forces of body buoyancy, thus realizes have
The growth course of sequence capsule clad structure.
(7) preparation method grease stabilising system concentration range of the present invention is wide, Ni bimetallic mix salinity 1.5~
2.0mol/L still is able to realize the formation of monodisperse capsule structure, and preparation process is simple, and batch output is high.
Detailed description of the invention
Fig. 1 is Ni bimetallic Nano capsule catalyst preparation schematic diagram of the present invention.
Fig. 2 is the graph of pore diameter distribution of embodiment 2Ni bimetallic Nano capsule catalyst.
Fig. 3 is that the TEM of embodiment 3Ni bimetallic Nano capsule catalyst schemes.
Fig. 4 is the XRD diagram of embodiment 4Ni bimetallic Nano capsule catalyst.
Fig. 5 is the reaction evaluating figure of embodiment 3Ni bimetallic Nano capsule catalyst.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
And it does not limit the scope of the invention.
Embodiment 1: 10g polyoxyethylene (10) cetyl ether is weighed in conical flask, hexamethylene is added to 100mL, at 40 DEG C
Lower heating is simultaneously stirred.When the change clarification to be seen to solution, the nickel nitrate and copper nitrate mixed solution of 5mL 2.0mol/L is added
(Ni:Cu molar ratio is 1:1), 2mL hydrazine hydrate is added to after mixing in stirring.Then it after aging 0.5h, increases revolving speed and is added
The mixed solution of concentrated ammonia liquor (25wt.%) and 13mL deionized water of 2ml, are slowly added to 10mL TEOS, after hydrolyzing 1h later
Isopropanol demulsification is added, and is centrifuged.Finally by obtained sample at 110 DEG C dry 12h, then in air atmosphere with 1 DEG C/
The rate of min is calcined at 500 DEG C, obtains bimetal nano capsule catalyst 1.
By calcined 1 tabletting of catalyst, sieving, the catalyst of 20~40 mesh of 0.1g is taken, after mixing with quartz sand
It is packed into reaction tube, then leads to nitrogen and hydrogen mixture at 650 DEG C and restores 1h, be passed through methane and carbon dioxide and N later2Gas into
Row catalytic reforming reaction, CH4:CO2:N2=1.2:1:5, the total air speed of gas are 12Lg-1·h-1, reaction temperature is 700 DEG C, is used
Gas-chromatography analyzes its product.Within the reaction time of 200h, the conversion ratio of methane and carbon dioxide is stablized 71%
With 79%.
Embodiment 2: 20g polyoxyethylene (10) cetyl ether is weighed in conical flask, hexamethylene is added to 100mL, at 45 DEG C
Lower heating is simultaneously stirred.When the change clarification to be seen to solution, the nickel nitrate and cobalt nitrate mixed solution of 7mL 1.8mol/L is added
(Ni:Co molar ratio is 2:1), 3mL hydrazine hydrate is added to after mixing in stirring.Then it after aging 1.5h, increases revolving speed and is added
The concentrated ammonia liquor of 1.5ml and the mixed solution of 13.5mL deionized water, are slowly added to 12.5mL TEOS later, add after hydrolyzing 6h
Enter isopropanol demulsification, and is centrifuged.Finally by obtained sample at 80 DEG C it is dry for 24 hours, then in air atmosphere with 1.5 DEG C/
The rate of min is calcined at 600 DEG C, obtains bimetal nano capsule catalyst 2.
By calcined 2 tabletting of catalyst, sieving, the catalyst of 40~60 mesh of 0.1g is taken, after mixing with quartz sand
It is packed into reaction tube, then leads to nitrogen and hydrogen mixture at 680 DEG C and restores 1h, be passed through methane and carbon dioxide and N later2Gas into
Row catalytic reforming reaction, CH4:CO2:N2=1.3:1:2, the total air speed of gas are 24Lg-1·h-1, reaction temperature is 750 DEG C, is used
Gas-chromatography analyzes its product.Within the reaction time of 200h, the conversion ratio of methane and carbon dioxide is stablized 81%
With 88%.
Embodiment 3: 34g polyoxyethylene (10) cetyl ether is weighed in conical flask, hexamethylene is added to 100mL, at 50 DEG C
Lower heating is simultaneously stirred.When the change clarification to be seen to solution, the nickel nitrate and copper nitrate mixed solution of 5mL 1.5mol/L is added
(Ni:Cu molar ratio is 4:1), 4mL hydrazine hydrate is added to after mixing in stirring.Then it after aging 3h, increases revolving speed and 1ml is added
Concentrated ammonia liquor and 14mL deionized water mixed solution, be slowly added to 10mL TEOS later, isopropanol be added after hydrolyzing 12h
Demulsification, and be centrifuged.Obtained sample is finally dried to 12h at 100 DEG C, then in air atmosphere with the rate of 2 DEG C/min
It is calcined at 700 DEG C, obtains bimetal nano capsule catalyst 3.
By calcined 3 tabletting of catalyst, sieving, the catalyst of 20~40 mesh of 0.1g is taken, after mixing with quartz sand
It is packed into reaction tube, then leads to nitrogen and hydrogen mixture at 700 DEG C and restores 1h, be passed through methane and carbon dioxide and N later2Gas into
Row catalytic reforming reaction, CH4:CO2:N2=1.2:1:3, the total air speed of gas are 48Lg-1·h-1, reaction temperature is 800 DEG C, is used
Gas-chromatography analyzes its product.Within the reaction time of 600h, the conversion ratio of methane and carbon dioxide is stablized 90%
With 94%.
Embodiment 4: 40g polyoxyethylene (10) cetyl ether is weighed in conical flask, hexamethylene is added to 100mL, at 60 DEG C
Lower heating is simultaneously stirred.When the change clarification to be seen to solution, nickel acetylacetonate and the acetylacetone cobalt that 10mL 1.5mol/L is added are mixed
Solution (Ni:Co molar ratio is 3:1) is closed, 6mL hydrazine hydrate is added to after mixing in stirring.Then it after aging 6h, increases revolving speed and adds
Enter the concentrated ammonia liquor of 1ml and the mixed solution of 14mL deionized water, be slowly added to 15mL TEOS later, wait hydrolyze for 24 hours afterwards be added it is different
Propyl alcohol demulsification, and be centrifuged.Obtained sample is finally dried to 16h at 120 DEG C, then in air atmosphere with 3 DEG C/min's
Rate is calcined at 800 DEG C, obtains bimetal nano capsule catalyst 4.
By calcined 4 tabletting of catalyst, sieving, the catalyst of 40~60 mesh of 0.1g is taken, after mixing with quartz sand
It is packed into reaction tube, then leads to nitrogen and hydrogen mixture at 750 DEG C and restores 1h, be passed through methane and carbon dioxide and N later2Gas into
Row catalytic reforming reaction, CH4:CO2:N2=1.1:1:5, the total air speed of gas are 36Lg-1·h-1, reaction temperature is 850 DEG C, is used
Gas-chromatography analyzes its product.Within the reaction time of 400h, the conversion ratio of methane and carbon dioxide is stablized 97%
With 99%.
Embodiment 5: 50g polyoxyethylene (10) cetyl ether is weighed in conical flask, hexamethylene is added to 100mL, at 50 DEG C
Lower heating is simultaneously stirred.When the change clarification to be seen to solution, the nickel chloride and cobalt chloride mixed solution of 8mL 2.0mol/L is added
(Ni:Co molar ratio is 3:1), 8mL hydrazine hydrate is added to after mixing in stirring.Then it after aging 12h, increases revolving speed and is added
The concentrated ammonia liquor of 1.5ml and the mixed solution of 13.5mL deionized water, are slowly added to 15mL TEOS later, are added after hydrolyzing 48h
Isopropanol demulsification, and be centrifuged.Obtained sample is finally dried to 20h at 60 DEG C, then in air atmosphere with 4 DEG C/min's
Rate is calcined at 650 DEG C, obtains bimetal nano capsule catalyst 5.
By calcined 5 tabletting of catalyst, sieving, the catalyst of 20~40 mesh of 0.1g is taken, after mixing with quartz sand
It is packed into reaction tube, then leads to nitrogen and hydrogen mixture at 700 DEG C and restores 1h, be passed through methane and carbon dioxide and N later2Gas into
Row catalytic reforming reaction, CH4:CO2:N2=1.4:1:1, the total air speed of gas are 32Lg-1·h-1, reaction temperature is 800 DEG C, is used
Gas-chromatography analyzes its product.Within the reaction time of 200h, the conversion ratio of methane and carbon dioxide is stablized 91%
With 95%.
Embodiment 6: the mono- 4- nonylplenyl ether of 10g polyethylene glycol and 10g polyoxyethylene (10) cetyl ether are weighed in taper
Bottle is added hexamethylene to 100mL, heats and stir at 50 DEG C.When the change clarification to be seen to solution, 6mL 1.5mol/L is added
Nickel acetylacetonate and acetylacetone copper mixed solution (Ni:Cu molar ratio be 4:1), 5mL hydration is added to after mixing in stirring
Hydrazine.Then it after aging 18h, increases revolving speed and the concentrated ammonia liquor of 2.5ml and the mixed solution of 12.5mL deionized water, Zhi Houhuan is added
It is slow that 10mL TEOS is added, isopropanol demulsification is added after hydrolyzing 30h, and be centrifuged.It is finally that obtained sample is dry at 70 DEG C
Then 12h is calcined at 700 DEG C with the rate of 5 DEG C/min in air atmosphere, obtain bimetal nano capsule catalyst
6。
By calcined 6 tabletting of catalyst, sieving, the catalyst of 40~60 mesh of 0.1g is taken, after mixing with quartz sand
It is packed into reaction tube, then leads to nitrogen and hydrogen mixture at 650 DEG C and restores 1h, be passed through methane and carbon dioxide and N later2Gas into
Row catalytic reforming reaction, CH4:CO2:N2=1.3:1:4, the total air speed of gas are 48Lg-1·h-1, reaction temperature is 750 DEG C, is used
Gas-chromatography analyzes its product.Within the reaction time of 200h, the conversion ratio of methane and carbon dioxide is stablized 77%
With 85%.
Embodiment 7: the mono- 4- nonylplenyl ether of 20g polyethylene glycol and 10g polyoxyethylene (10) cetyl ether are weighed in taper
Bottle is added hexamethylene to 100mL, heats and stir at 50 DEG C.When the change clarification to be seen to solution, it is added 5mL 2mol/L's
Nickel chloride and copper chloride mixed solution (Ni:Cu molar ratio is 1:1), 7mL hydrazine hydrate is added to after mixing in stirring.Then aging
After for 24 hours, increases revolving speed and the concentrated ammonia liquor of 3ml and the mixed solution of 12mL deionized water is added, be slowly added to 7.5mL later
Isopropanol demulsification is added after hydrolyzing 40h, and is centrifuged by TEOS.Finally by obtained sample, drying for 24 hours, then exists at 50 DEG C
It is calcined at 750 DEG C under air atmosphere with the rate of 2 DEG C/min, obtains bimetal nano capsule catalyst 7.
By calcined 7 tabletting of catalyst, sieving, the catalyst of 20~40 mesh of 0.1g is taken, after mixing with quartz sand
It is packed into reaction tube, then leads to nitrogen and hydrogen mixture at 700 DEG C and restores 1h, be passed through methane and carbon dioxide and N later2Gas into
Row catalytic reforming reaction, CH4:CO2:N2=1.2:1:2, the total air speed of gas are 18Lg-1·h-1, reaction temperature is 750 DEG C, is used
Gas-chromatography analyzes its product.Within the reaction time of 200h, the conversion ratio of methane and carbon dioxide is stablized 78%
With 86%.
The structural property parameter of catalyst in each embodiment of table 1
Claims (7)
1. a kind of Ni bimetallic Nano capsule catalyst, which is characterized in that be made of capsule shell and metal inner core；Described
Capsule shell is silica, and the metal inner core is bimetallic ambrose alloy or nickel cobalt particle；In the Nano capsule catalyst
Ambrose alloy or nickel cobalt total content in 10~20wt%, ambrose alloy or nickel cobalt bimetal granule partial size in 1~4nm, capsule cavity (6.5~
7.5) nm × (15~60) nm, 5.5 ± 3nm of capsule shell thickness；The Nano capsule catalyst has twin-stage cellular structure,
In, from the duct that penetrates of shell, the hole of 12~15nm derives from capsule hollow body lumen in the hole of 3~4nm.
2. the preparation method of Nano capsule catalyst as described in claim 1, which comprises the steps of:
(1) 10~50g surfactant is weighed in container, and hexamethylene is added to 100mL, heats and stirs at 40~60 DEG C
It mixes；
(2) the Ni-Co mixed salt solution or Ni-Cu mixed salt solution, Ni-Co or Ni- of 5~10mL, 1.5~2.0mol/L is added
The molar ratio of Cu is 4~1:1, and 2~8mL hydrazine hydrate is added to after mixing in stirring；
(3) it after aging 0.5~for 24 hours, increases speed of agitator and the concentrated ammonia liquor of 15mL and the mixed solution of deionized water simultaneously is added, later
It is slowly added to 7.5~15mL TEOS；
(4) acetone demulsification is added after hydrolyzing 1~48h, and is centrifuged；
(5) by the sample of upper step dry 12 at 50~120 DEG C~for 24 hours, then in air atmosphere with the speed of 1~5 DEG C/min
Rate is calcined at 500~800 DEG C.
3. the preparation method of Nano capsule catalyst as claimed in claim 2, which is characterized in that surface described in step (1) is living
Property agent be one or both of polyoxyethylene (10) cetyl ether, the mono- 4- nonylplenyl ether of polyethylene glycol.
4. the preparation method of Nano capsule catalyst as claimed in claim 2, which is characterized in that Ni-Co described in step (2)
Mixed salt solution be the mixed solution of nickel nitrate and cobalt nitrate, the mixed solution of nickel chloride and cobalt chloride or nickel acetylacetonate and
The mixed solution of acetylacetone cobalt；The Ni-Cu mixed salt solution be the mixed solution of nickel nitrate and copper nitrate, nickel chloride and
The mixed solution or nickel acetylacetonate of copper chloride and the mixed solution of acetylacetone copper.
5. the preparation method of Nano capsule catalyst as claimed in claim 2, which is characterized in that in step (3) in mixed solution
The amount of concentrated ammonia liquor is 1~3mL.
6. application of the Nano capsule catalyst as described in claim 1 in biogas reforming reaction.
7. application as claimed in claim 6, the biogas mole group become CH4:CO2:N2=1.1~1.4:1:1~5.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113023788A (en) * | 2019-12-25 | 2021-06-25 | 洛阳尖端技术研究院 | Nickel-cobalt hollow composite particle, preparation method and application thereof |
| CN114733524A (en) * | 2022-03-07 | 2022-07-12 | 东南大学 | Methane dry reforming catalyst using waste allochroic silica gel and preparation method thereof |
| CN115888725A (en) * | 2022-09-20 | 2023-04-04 | 山西大学 | C 2 Catalyst for conversion reaction of alkane and carbon dioxide to synthesis gas and preparation |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0741107A2 (en) * | 1995-05-03 | 1996-11-06 | Foundation for Research and Technology Hellas, (Institute of Chemical Engineering and High Temperature Chemical Processes) | Catalysts for the partial oxidation of light hydrocarbons to synthesis gas |
| CN101352687A (en) * | 2008-08-29 | 2009-01-28 | 同济大学 | Catalyst for carbon dioxide dry-reforming of methane, and preparation method and use thereof |
| CN103007945A (en) * | 2012-12-24 | 2013-04-03 | 南京大学 | Supported copper-nickel alloy nanoparticle catalyst and preparation method of catalyst and application in methane and carbon dioxide reforming synthesis gas |
| CN105771995A (en) * | 2016-03-31 | 2016-07-20 | 山西大学 | Encapsulating nanometer material and preparation method thereof |
| CN106268822A (en) * | 2015-05-13 | 2017-01-04 | 新加坡国立大学 | M-SiO2 catalyst, its preparation method and the application in methane carbon dioxide reformation thereof |
-
2018
- 2018-07-03 CN CN201810712246.XA patent/CN108940287B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0741107A2 (en) * | 1995-05-03 | 1996-11-06 | Foundation for Research and Technology Hellas, (Institute of Chemical Engineering and High Temperature Chemical Processes) | Catalysts for the partial oxidation of light hydrocarbons to synthesis gas |
| CN101352687A (en) * | 2008-08-29 | 2009-01-28 | 同济大学 | Catalyst for carbon dioxide dry-reforming of methane, and preparation method and use thereof |
| CN103007945A (en) * | 2012-12-24 | 2013-04-03 | 南京大学 | Supported copper-nickel alloy nanoparticle catalyst and preparation method of catalyst and application in methane and carbon dioxide reforming synthesis gas |
| CN106268822A (en) * | 2015-05-13 | 2017-01-04 | 新加坡国立大学 | M-SiO2 catalyst, its preparation method and the application in methane carbon dioxide reformation thereof |
| CN105771995A (en) * | 2016-03-31 | 2016-07-20 | 山西大学 | Encapsulating nanometer material and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| FAGEN WANG ET AL.: ""CO2 reforming with methane over small-sized Ni@SiO2 catalysts with unique features of sintering-free and low carbon"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| FAGEN WANG ET AL.: ""Syngas production from CO2 reforming with methane over core-shell Ni@SiO2 catalysts"", 《JOURNAL OF CO2 UTILIZATION》 * |
| XINGYUAN GAO ET AL.: ""Highly reactive Ni-Co/SiO2 bimetallic catalyst via complexation witholeylamine/oleic acid organic pair for dry reforming of methane"", 《CATALYSIS TODAY》 * |
| 吴韬: ""铜镍合金纳米催化剂在甲烷二氧化碳重整方面的应用"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113023788A (en) * | 2019-12-25 | 2021-06-25 | 洛阳尖端技术研究院 | Nickel-cobalt hollow composite particle, preparation method and application thereof |
| CN113023788B (en) * | 2019-12-25 | 2023-06-30 | 洛阳尖端技术研究院 | Nickel-cobalt hollow composite particle, preparation method and application thereof |
| CN114733524A (en) * | 2022-03-07 | 2022-07-12 | 东南大学 | Methane dry reforming catalyst using waste allochroic silica gel and preparation method thereof |
| CN114733524B (en) * | 2022-03-07 | 2024-03-12 | 东南大学 | Methane dry reforming catalyst utilizing waste allochroic silica gel and preparation method thereof |
| CN115888725A (en) * | 2022-09-20 | 2023-04-04 | 山西大学 | C 2 Catalyst for conversion reaction of alkane and carbon dioxide to synthesis gas and preparation |
| CN115888725B (en) * | 2022-09-20 | 2024-04-16 | 山西大学 | C (C)2+Catalyst for conversion reaction of alkane and carbon dioxide to synthesis gas and preparation thereof |
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