CN108855095A - Methane reforming multicore shell hollow type catalyst nickel-nisiloy hydrochlorate-SiO2Preparation method - Google Patents
Methane reforming multicore shell hollow type catalyst nickel-nisiloy hydrochlorate-SiO2Preparation method Download PDFInfo
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- CN108855095A CN108855095A CN201810127056.1A CN201810127056A CN108855095A CN 108855095 A CN108855095 A CN 108855095A CN 201810127056 A CN201810127056 A CN 201810127056A CN 108855095 A CN108855095 A CN 108855095A
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- Prior art keywords
- nickel
- sio
- nisiloy
- nisiloy hydrochlorate
- hydrochlorate
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002407 reforming Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 85
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 75
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 75
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 75
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 75
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Substances [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 17
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 60
- 235000019441 ethanol Nutrition 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- 239000000908 ammonium hydroxide Substances 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 239000002563 ionic surfactant Substances 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 238000004781 supercooling Methods 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- ZDWSNKPLZUXBPE-UHFFFAOYSA-N 3,5-ditert-butylphenol Chemical group CC(C)(C)C1=CC(O)=CC(C(C)(C)C)=C1 ZDWSNKPLZUXBPE-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 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 2
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 2
- PXFAWKNRNHXITF-KVVVOXFISA-N nickel;(z)-octadec-9-enoic acid Chemical compound [Ni].CCCCCCCC\C=C/CCCCCCCC(O)=O PXFAWKNRNHXITF-KVVVOXFISA-N 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 17
- 239000006185 dispersion Substances 0.000 abstract description 12
- 238000009707 resistance sintering Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 37
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 description 18
- 238000001035 drying Methods 0.000 description 15
- 238000002156 mixing Methods 0.000 description 15
- 239000001569 carbon dioxide Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 230000003993 interaction Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000011068 loading method Methods 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- FMQXRRZIHURSLR-UHFFFAOYSA-N dioxido(oxo)silane;nickel(2+) Chemical compound [Ni+2].[O-][Si]([O-])=O FMQXRRZIHURSLR-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000003837 high-temperature calcination Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 238000006057 reforming reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052914 metal silicate Inorganic materials 0.000 description 2
- XIKYYQJBTPYKSG-UHFFFAOYSA-N nickel Chemical compound [Ni].[Ni] XIKYYQJBTPYKSG-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses methane reforming multicore shell hollow type catalyst nickel-nisiloy hydrochlorate-SiO2Preparation method, which is characterized in that this method includes following steps：（1）Nano SiO 2 particle is first made；（2）It takes nano SiO 2 particle of the partial size in 500nm~1 μm to be formulated as concentration 1g/L~10g/L, lye is added by pH and is adjusted to 8-13, the nickel presoma that concentration is 1g/L~10g/L is added, be 50 in temperatureoC~220oSynthesis nisiloy hydrochlorate hollow sphere is carried out under the conditions of C；（3）Nisiloy hydrochlorate hollow sphere is scattered in the mixed solution of surfactant and water, lye is added after stirring, pH is adjusted to 10-14,10mL ethyl orthosilicate is added in reacting under room temperature, nisiloy hydrochlorate-SiO is made2Nucleocapsid hollow sphere；（4）By nisiloy hydrochlorate-SiO2Nucleocapsid hollow sphere is 300 in temperatureoC~800oIt is restored under the hydrogen atmosphere of C, obtains nickel-nisiloy hydrochlorate-SiO of high degree of dispersion2Multicore shell hollow type catalyst.Catalyst prepared by the present invention has the advantages that highly resistance sintering, anti-carbon, high-temperature stability and high-specific surface area.
Description
Technical field
The present invention relates to methane reforming multicore shell hollow type catalyst nickel-nisiloy hydrochlorate-SiO2Preparation method, belonging to
Learn production technical field.
Background technique
Nickel-base catalyst is studied extensively both at home and abroad because its cheap price and high Reforming catalyst are active, when its application
In CH4When dry reforming is reacted, nickel-base catalyst carbon deposition phenomenon is than more serious, mainly since the sintering of nickel metal promotes carbon distribution pair
The generation of reaction.Especially work as CH4Dry reforming reaction temperature is lower than 600oWhen C, carbon deposition phenomenon is even more serious.This invention person was once
Catalyst with core-casing structure is developed, metal sintering can be effectively prevented.But the generally existing specific surface area of these core-shell structures
The low problem low with mass-transfer efficiency.
Metal silicate has many advantages, such as high-temperature stability and high-specific surface area, is widely used as because its is cheap
Catalyst.But these metal silicates are only used as the presoma of catalyst, after high temperature reduction, metal metasilicate at present
The advantages of salt decomposes completely, loses its high-specific surface area.
I.e.：A kind of methane reforming multicore shell hollow type catalyst is needed now, in CH4Dry reforming reaction temperature is 600oC item
Under part, still there is high anti-carbon, high-specific surface area and anti-sintering property.
Summary of the invention
The technical problem to be solved in the present invention is to provide methane reforming multicore shell hollow type catalyst nickel-nisiloy hydrochlorates-
SiO2Preparation method, in CH4Dry reforming reaction temperature is 600oUnder the conditions of C, still there is highly resistance sintering, anti-carbon, high-temperature stable
Property and high-specific surface area, with overcome the deficiencies in the prior art.
The technical scheme is that：Methane reforming multicore shell hollow type catalyst nickel-nisiloy hydrochlorate-SiO2Preparation side
Method, this method include following steps：（1）Ethyl alcohol, water and silicon source are 0oC~70oIt is mixed evenly under conditions of C, then plus
Enter lye and adjusts pH to 10, stirring, centrifuge separation, washing, final dry obtained nano SiO 2 particle；（2）Take partial size
Nano SiO 2 particle in 500nm~1 μm is formulated as concentration 1g/L~10g/L, and lye is added by pH and is adjusted to 8-13, adds
Enter the nickel presoma that concentration is 1g/L~10g/L, is 50 in temperatureoC~220oSynthesized under the conditions of C, finally through supercooling,
Obtained nisiloy hydrochlorate hollow sphere is washed in centrifuge separation；（3）Nisiloy hydrochlorate hollow sphere is scattered in the mixing of surfactant and water
In solution, lye is added after stirring, pH is adjusted to 10-14,10mL ethyl orthosilicate is added in reacting under room temperature, finally from
Heart separation, washing, dry obtained nisiloy hydrochlorate-SiO2Nucleocapsid hollow sphere；（4）By nisiloy hydrochlorate-SiO2Nucleocapsid hollow sphere is in temperature
It is 300oC~800oIt is restored under the hydrogen atmosphere of C, obtains nickel-nisiloy hydrochlorate-SiO of high degree of dispersion2The catalysis of multicore shell hollow type
Agent.
Above-mentioned step（1）In, the silicon source is one of ethyl orthosilicate, sodium silicate water glass, methyl orthosilicate
Or several combination.
Above-mentioned step（2）In, the nickel presoma is nickel nitrate, nickel acetate, nickel acetylacetonate, nickel oxalate, oleic acid nickel
One or more of combination.
Above-mentioned step（1）,（2）,（3）In, alkaline solution is one or more of sodium hydroxide, urea, ammonium hydroxide
Combination.
Above-mentioned step（1）,（2）,（3）In, washing cleaning solvent used is water, in ethyl alcohol, methanol, acetone, hexamethylene
One or more of combinations.
It is above-mentioned in step（3）In, the surfactant is nonionic surface active agent or ionic surfactant
Agent, wherein nonionic surface active agent is C14H22O(C2H4O)n, n=10~15, C15H24O(C2H4O)n, in n=5~10 one
Kind is several；Ionic surfactant is alkyl quaternaries surfactant CnTAB, one of n=10~15 or several
Kind.
Abovementioned steps（4）In, nickel-nisiloy hydrochlorate-silica core-shell hollow type specific surface area of catalyst is in 300m2•g-1
~600m2•g-1, silica shell thickness is in 30nm~80nm.
The prior art compares, methane reforming multicore shell hollow type catalyst nickel-nisiloy hydrochlorate-SiO of the present invention2Preparation side
Method, this method include following steps：（1）Ethyl alcohol, water and silicon source are 0oC~70oIt is mixed evenly under conditions of C, then plus
Enter lye and adjusts pH to 10, stirring, centrifuge separation, washing, final dry obtained nano SiO 2 particle；（2）Take partial size
Nano SiO 2 particle in 500nm~1 μm is formulated as concentration 1g/L~10g/L, and lye is added by pH and is adjusted to 8-13, adds
Enter the nickel presoma that concentration is 1g/L~10g/L, is 50 in temperatureoC~220oSynthesized under the conditions of C, finally through supercooling,
Obtained nisiloy hydrochlorate hollow sphere is washed in centrifuge separation；（3）Nisiloy hydrochlorate hollow sphere is scattered in the mixing of surfactant and water
In solution, lye is added after stirring, pH is adjusted to 10-14,10mL ethyl orthosilicate is added in reacting under room temperature, finally from
Heart separation, washing, dry obtained nisiloy hydrochlorate-SiO2Nucleocapsid hollow sphere；（4）By nisiloy hydrochlorate-SiO2Nucleocapsid hollow sphere is in temperature
It is 300oC~800oIt is restored under the hydrogen atmosphere of C, obtains nickel-nisiloy hydrochlorate-SiO of high degree of dispersion2The catalysis of multicore shell hollow type
Agent.Nickel made from such method-nisiloy hydrochlorate-SiO2With high degree of dispersion（Partial size is in 2nm~7nm）, high anti-carbon performance
（Carbon deposition quantity<11%）, especially in CH4Dry reforming reaction temperature is 600oUnder the conditions of C, anti-carbon performance still with higher, with
It is existing 700oThe catalyst of C or more just anti-carbon performance with higher compares, with the obvious advantage, applicability is wider；Meanwhile having
There is high-specific surface area（300m2·g-1~600m2·g-1）, the interaction of strong metal carrier（Reduction temperature is 655oC or more）, tool
There is high mass-transfer efficiency.Nano nickel particles are dispersed in nisiloy hydrochlorate hollow sphere and SiO2In shell, the hollow knot of multicore shell is formed
Structure, partial size is in 500nm~1 μm, with existing CH4Dry reforming nickel-base catalyst compares, and synthetic method is rapid, and synthesis material is easy
, it can be realized high-volume and synthesize, and the specific surface area of catalyst synthesized is high, dispersion degree is high, and metal-support interaction is strong, passes
Matter is high-efficient, and anti-carbon performance is good.
Detailed description of the invention
Fig. 1 is nickel-nisiloy hydrochlorate-SiO2The hollow type preparation method schematic diagram of multicore shell.
Fig. 2 is the transmission electron microscope picture of nisiloy hydrochlorate hollow sphere.
Fig. 3 is nisiloy hydrochlorate hollow sphere high-resolution-ration transmission electric-lens figure.
Fig. 4 is nisiloy hydrochlorate-SiO2The transmission electron microscope picture of hud typed hollow sphere.
Fig. 5 is nisiloy hydrochlorate-SiO2The high-resolution-ration transmission electric-lens figure of hud typed hollow sphere.
Fig. 6 is nickel-nisiloy hydrochlorate-SiO2The transmission electron microscope picture of multicore shell hollow type catalyst.
Fig. 7 is nickel-nisiloy hydrochlorate-SiO2The high-resolution-ration transmission electric-lens figure of multicore shell hollow type catalyst.
Fig. 8 is nisiloy hydrochlorate hollow sphere-nisiloy hydrochlorate-SiO2The temperature programmed reduction figure of nucleocapsid hollow sphere.
Fig. 9 is nisiloy hydrochlorate hollow sphere-nisiloy hydrochlorate-SiO2Nucleocapsid hollow type catalyst CH4Dry reforming reactivity figure.
Figure 10 is nisiloy hydrochlorate hollow sphere-nisiloy hydrochlorate-SiO2Nucleocapsid hollow type catalyst CH4Heat after dry reforming reaction
Weight analysis figure.
Specific embodiment
Methane reforming multicore shell hollow type catalyst nickel-nisiloy hydrochlorate-SiO2Preparation method, ethyl alcohol, water and silicon source exist
0oC~70oIt is mixed evenly under conditions of C, adds lye and adjust pH to 10, stirring, centrifuge separation, washing are final dry
Dry obtained nano SiO 2 particle；Take nano SiO 2 particle of the partial size in 500nm~1 μm be formulated as concentration 1g/L~
10g/L is added lye for pH and is adjusted to 8-13, and the nickel presoma that concentration is 1g/L~10g/L is added, and is 50 in temperatureoC~
220oIt is synthesized under the conditions of C, nisiloy hydrochlorate hollow sphere finally is made through supercooling, centrifuge separation, washing；Nisiloy hydrochlorate is empty
Bulbus cordis is scattered in the mixed solution of surfactant and water, and lye is added after stirring, and pH is adjusted to 10-14,10mL is being added just
Silester is finally centrifugated, washs, dry obtained nisiloy hydrochlorate-SiO in reacting under room temperature2Nucleocapsid hollow sphere；It will
Nisiloy hydrochlorate-SiO2Nucleocapsid hollow sphere is 300 in temperatureoC~800oIt is restored under the hydrogen atmosphere of C, obtains the nickel-of high degree of dispersion
Nisiloy hydrochlorate-SiO2Multicore shell hollow type catalyst.
Embodiment 1：
（1）200mL ethyl alcohol, 100mL water and 40mL methyl orthosilicate are 0oIt is mixed evenly under C.Be added urea adjust pH to
10.After stirring 2h, separated with centrifuge.With first alcohol and water mixing, washing.The nano SiO 2 particle of 600nm is finally obtained,
150oC is dry for 24 hours.
（2）2g silica is taken, ammonium hydroxide is added in 0.3g nickel nitrate, adjusts pH to 8.Mixed solution is put into reaction under high pressure
In kettle, 50 degree are heated to, after reaction for 24 hours, is cooled to room temperature.Centrifuge separation, and with methanol, ethyl alcohol after water is washed with this, is put into
100 degree of drying boxes.Obtain nisiloy hydrochlorate hollow sphere（Such as Fig. 2, shown in 3）, specific area 250m2·g-1。
（3）Nisiloy hydrochlorate hollow sphere is scattered in ethyl alcohol（30mL）, water（10mL）, CnTAB(n=10)（30mg）Mixing
In solution.After stirring 30min, ammonium hydroxide is added（30mL）.PH is adjusted to 10, after stirring 30min, 10mL ethyl orthosilicate is added.
After reacting 48h at room temperature, centrifuge separation, and washed 3 times with the mixed solution of first alcohol and water.It is put into drying box 100oC
Drying is for 24 hours.Obtain nisiloy hydrochlorate-SiO2Nucleocapsid hollow sphere, SiO2Shell thickness is 40nm, specific surface area 400m2·g-1（Such as
Fig. 4, shown in 5）.
（4）By nisiloy hydrochlorate-SiO2Nucleocapsid hollow sphere is put into Muffle furnace in 700 degree of calcining 4h.Pure hydrogen is then passed to,
In 700 degree of reduction 0.5h.Finally obtain nickel-nisiloy hydrochlorate-SiO2Multicore shell hollow ball catalyst（Such as Fig. 6, shown in 7）.By scheming
6, although 7 can be seen that by high-temperature calcination and reduction, acicular nickel silicate phase is still had.It can be seen that being closed with this
The catalyst obtained at method, there is no decompose completely for nisiloy hydrochlorate.The partial size of the nickel of high degree of dispersion is about 5nm.In addition, with
Nisiloy hydrochlorate hollow ball catalyst compares, nisiloy hydrochlorate-SiO2Nucleocapsid hollow ball catalyst has higher reduction temperature, table
The bright nucleocapsid catalyst has higher strong metal-support interaction（As shown in Figure 8）.
(5) under normal pressure, by CH4、CO2With He with 1:1:1 mode（Air speed 36Lg-1cat·h-1）, each lead into
Nickel-nisiloy hydrochlorate hollow sphere and nickel-nisiloy hydrochlorate-SiO2The catalyst fixed bed reactor of multicore shell hollow type（600oC）, reaction
50h.For nickel-nisiloy hydrochlorate hollow ball catalyst, although initial conversion is slightly higher, because of its higher nickel loading.But
The conversion ratio of methane and carbon dioxide declines 36% and 31% respectively.In comparison, for nickel-nisiloy hydrochlorate-SiO2Nucleocapsid is empty
The conversion ratio of bulbus cordis catalyst, methane and carbon dioxide declines 23% and 20% respectively（Fig. 9）.TG-DT A spectrum can be seen that
Nickel-nisiloy hydrochlorate-SiO2Multicore shell hollow ball catalyst nickel-nisiloy hydrochlorate-SiO2Nucleocapsid hollow ball catalyst weightlessness is only nickel-
The 1/7 of nisiloy phosphate catalyst shows that the former has high carbon accumulation resisting ability（Figure 10）.
Embodiment 2：
（1）200mL ethyl alcohol, 100mL water and 40mL methyl orthosilicate are 35oIt is mixed evenly under C.Be added urea adjust pH to
10.After stirring 2h, separated with centrifuge.With first alcohol and water mixing, washing.The nano SiO 2 particle of 600nm is finally obtained,
150oC is dry for 24 hours.
（2）2g silica is taken, ammonium hydroxide is added in 0.3g nickel nitrate, adjusts pH to 11.Mixed solution is put into reaction under high pressure
In kettle, 50 degree are heated to, after reaction for 24 hours, is cooled to room temperature.Centrifuge separation, and with methanol, ethyl alcohol after water is washed with this, is put into
100 degree of drying boxes.Obtain nisiloy hydrochlorate hollow sphere（Such as Fig. 2, shown in 3）, specific area 250m2·g-1。
（3）Nisiloy hydrochlorate hollow sphere is scattered in ethyl alcohol（30mL）, water（10mL）, CnTAB(n=10)（30mg）Mixing
In solution.After stirring 30min, ammonium hydroxide is added（30mL）.PH is adjusted to 12, after stirring 30min, 10mL ethyl orthosilicate is added.
After reacting 48h at room temperature, centrifuge separation, and washed 3 times with the mixed solution of first alcohol and water.It is put into drying box 100oC
Drying is for 24 hours.Obtain nisiloy hydrochlorate-SiO2Nucleocapsid hollow sphere, SiO2Shell thickness is 40nm, specific surface area 400m2·g-1（Such as
Fig. 4, shown in 5）.
（4）By nisiloy hydrochlorate-SiO2Nucleocapsid hollow sphere is put into Muffle furnace in 700 degree of calcining 4h.Pure hydrogen is then passed to,
In 700 degree of reduction 0.5h.Finally obtain nickel-nisiloy hydrochlorate-SiO2Multicore shell hollow ball catalyst（Such as Fig. 6, shown in 7）.By scheming
6, although 7 can be seen that by high-temperature calcination and reduction, acicular nickel silicate phase is still had.It can be seen that being closed with this
The catalyst obtained at method, there is no decompose completely for nisiloy hydrochlorate.The partial size of the nickel of high degree of dispersion is about 5nm.In addition, with
Nisiloy hydrochlorate hollow ball catalyst compares, nisiloy hydrochlorate-SiO2Nucleocapsid hollow ball catalyst has higher reduction temperature, table
The bright nucleocapsid catalyst has higher strong metal-support interaction（As shown in Figure 8）.
(5) under normal pressure, by CH4、CO2With He with 1:1:1 mode（Air speed 36Lg-1cat·h-1）, each lead into
Nickel-nisiloy hydrochlorate hollow sphere and nickel-nisiloy hydrochlorate-SiO2Multicore shell hollow ball catalyst fixed bed reactors（600oC）, reaction
50h.For nickel-nisiloy hydrochlorate hollow ball catalyst, although initial conversion is slightly higher, because of its higher nickel loading.But
The conversion ratio of methane and carbon dioxide declines 36% and 31% respectively.In comparison, for nickel-nisiloy hydrochlorate-SiO2Nucleocapsid is empty
The conversion ratio of bulbus cordis catalyst, methane and carbon dioxide declines 19% and 22% respectively.TG-DT A spectrum can be seen that nickel-nisiloy
Hydrochlorate-SiO2Multicore shell hollow ball catalyst weightlessness is nickel-nisiloy phosphate catalyst 1/8, shows that the former has high anti-product
Carbon ability.
Embodiment 3：
（1）200mL ethyl alcohol, 100mL water and 40mL methyl orthosilicate are 70oIt is mixed evenly under C.Be added urea adjust pH to
10.After stirring 2h, separated with centrifuge.With first alcohol and water mixing, washing.The nano SiO 2 particle of 600nm is finally obtained,
150oC is dry for 24 hours.
（2）2g silica is taken, ammonium hydroxide is added in 0.3g nickel nitrate, adjusts pH to 13.Mixed solution is put into reaction under high pressure
In kettle, 50 degree are heated to, after reaction for 24 hours, is cooled to room temperature.Centrifuge separation, and with methanol, ethyl alcohol after water is washed with this, is put into
100 degree of drying boxes.Obtain nisiloy hydrochlorate hollow sphere（Such as Fig. 2, shown in 3）, specific area 250m2·g-1。
（3）Nisiloy hydrochlorate hollow sphere is scattered in ethyl alcohol（30mL）, water（10mL）, CnTAB(n=10)（30mg）Mixing
In solution.After stirring 30min, ammonium hydroxide is added（30mL）.PH is adjusted to 14, after stirring 30min, 10mL ethyl orthosilicate is added.
After reacting 48h at room temperature, centrifuge separation, and washed 3 times with the mixed solution of first alcohol and water.It is put into drying box 100oC
Drying is for 24 hours.Obtain nisiloy hydrochlorate-SiO2Nucleocapsid hollow sphere, SiO2Shell thickness is 40nm, specific surface area 400m2·g-1（Such as
Fig. 4, shown in 5）.
（4）By nisiloy hydrochlorate-SiO2Nucleocapsid hollow sphere is put into Muffle furnace in 700 degree of calcining 4h.Pure hydrogen is then passed to,
In 700 degree of reduction 0.5h.Finally obtain nickel-nisiloy hydrochlorate-SiO2Multicore shell hollow ball catalyst（Such as Fig. 6, shown in 7）.By scheming
6, although 7 can be seen that by high-temperature calcination and reduction, acicular nickel silicate phase is still had.It can be seen that being closed with this
The catalyst obtained at method, there is no decompose completely for nisiloy hydrochlorate.The partial size of the nickel of high degree of dispersion is about 5nm.In addition, with
Nisiloy hydrochlorate hollow ball catalyst compares, nisiloy hydrochlorate-SiO2Nucleocapsid hollow ball catalyst has higher reduction temperature, table
The bright nucleocapsid catalyst has higher strong metal-support interaction（As shown in Figure 8）.
(5) under normal pressure, by CH4、CO2With He with 1:1:1 mode（Air speed 36Lg-1cat·h-1）, each lead into
Nickel-nisiloy hydrochlorate hollow sphere and nickel-nisiloy hydrochlorate-SiO2Multicore shell hollow ball catalyst fixed bed reactors（600oC）, reaction
50h.For nickel-nisiloy hydrochlorate hollow ball catalyst, although initial conversion is slightly higher, because of its higher nickel loading.But
The conversion ratio of methane and carbon dioxide declines 36% and 31% respectively.In comparison, for nickel-nisiloy hydrochlorate-SiO2Nucleocapsid is empty
The conversion ratio of bulbus cordis catalyst, methane and carbon dioxide declines 30% and 29% respectively.TG-DT A spectrum can be seen that nickel-nisiloy
Hydrochlorate-SiO2Multicore shell hollow ball catalyst weightlessness is nickel-nisiloy phosphate catalyst 90%, shows that the former has high anti-product
Carbon ability.
Embodiment 4：
（1）200mL ethyl alcohol, 100mL water and 40mL methyl orthosilicate are mixed evenly at room temperature.Be added urea adjust pH to
10.After stirring 2h, separated with centrifuge.With first alcohol and water mixing, washing.The nano SiO 2 particle of 600nm is finally obtained,
150oC is dry for 24 hours.
（2）2g silica is taken, ammonium hydroxide is added in 0.3g nickel nitrate, adjusts pH to 12.Mixed solution is put into reaction under high pressure
In kettle, 120 degree are heated to, after reaction for 24 hours, is cooled to room temperature.Centrifuge separation, and with methanol, ethyl alcohol after water is washed with this, is put
Enter 100 degree of drying boxes.Obtain nisiloy hydrochlorate hollow sphere（Such as Fig. 2, shown in 3）, specific area 250m2·g-1。
（3）Nisiloy hydrochlorate hollow sphere is scattered in ethyl alcohol（30mL）, water（10mL）, CnTAB(n=10)（30mg）Mixing
In solution.After stirring 30min, ammonium hydroxide is added（30mL）.After stirring 30min, 10mL ethyl orthosilicate is added.It reacts at room temperature
After 48h, centrifuge separation, and washed 3 times with the mixed solution of first alcohol and water.It is put into drying box 100oC is dry for 24 hours.It obtains
Nisiloy hydrochlorate-SiO2Nucleocapsid hollow sphere, SiO2Shell thickness is 40nm, specific surface area 400m2·g-1（Such as Fig. 4, shown in 5）.
（4）By nisiloy hydrochlorate-SiO2Nucleocapsid hollow sphere is put into Muffle furnace in 700 degree of calcining 4h.Pure hydrogen is then passed to,
In 700 degree of reduction 0.5h.Finally obtain nickel-nisiloy hydrochlorate-SiO2Multicore shell hollow ball catalyst（Such as Fig. 6, shown in 7）.By scheming
6, although 7 can be seen that by high-temperature calcination and reduction, acicular nickel silicate phase is still had.It can be seen that being closed with this
The catalyst obtained at method, there is no decompose completely for nisiloy hydrochlorate.The partial size of the nickel of high degree of dispersion is about 5nm.In addition, with
Nisiloy hydrochlorate hollow ball catalyst compares, nisiloy hydrochlorate-SiO2Nucleocapsid hollow ball catalyst has higher reduction temperature, table
The bright nucleocapsid catalyst has higher strong metal-support interaction（As shown in Figure 8）.
(5) under normal pressure, by CH4、CO2With He with 1:1:1 mode（Air speed 36Lg-1cat·h-1）, each lead into
Nickel-nisiloy hydrochlorate hollow sphere and nickel-nisiloy hydrochlorate-SiO2Multicore shell hollow ball catalyst fixed bed reactors（600oC）, reaction
50h.For nickel-nisiloy hydrochlorate hollow ball catalyst, although initial conversion is slightly higher, because of its higher nickel loading.But
The conversion ratio of methane and carbon dioxide declines 36% and 31% respectively.In comparison, for nickel-nisiloy hydrochlorate-SiO2Nucleocapsid is empty
The conversion ratio of bulbus cordis catalyst, methane and carbon dioxide declines 23% and 20% respectively（Fig. 9）.TG-DT A spectrum can be seen that
Nickel-nisiloy hydrochlorate-SiO2Multicore shell hollow ball catalyst weightlessness is only nickel-nisiloy phosphate catalyst 1/7, shows that the former has
High carbon accumulation resisting ability（Figure 10）.
Embodiment 5：
（1）200mL ethyl alcohol, 100mL water and 10mL sodium metasilicate are 0oIt is mixed evenly under C.Ammonium hydroxide is added and adjusts pH to 10.It stirs
After mixing 2h, separated with centrifuge.With second alcohol and water mixing, washing.The nano SiO 2 particle for finally obtaining 200nm, 150
Degree is dry for 24 hours.
（2）2g silica is taken, sodium hydroxide is added in 0.3g nickel acetate, adjusts pH to 12.Mixed solution is put into high pressure
In reaction kettle, 120 degree are heated to, after reaction for 24 hours, is cooled to room temperature.Centrifuge separation, and with methanol, ethyl alcohol, water is washed with this
Afterwards, 100 are preventedoC drying box.Obtain nisiloy hydrochlorate hollow sphere.Specific area is 230m2·g-1。
（3）Nisiloy hydrochlorate hollow sphere is scattered in ethyl alcohol（30mL）, water（10mL）, CnTAB(n=10)（30mg）Mixing
In solution.After stirring 30min, ammonium hydroxide is added（30mL）.After stirring 30min, 30mL ethyl orthosilicate is added.It reacts at room temperature
After 80h, centrifuge separation, and washed 3 times with the mixed solution of first alcohol and water.It is put into drying box 100oC is dry for 24 hours.It obtains
Nisiloy hydrochlorate-SiO2Nucleocapsid hollow sphere, SiO2Shell thickness is 80nm, specific surface area 600m2·g-1。
（4）By nisiloy hydrochlorate-SiO2Nucleocapsid hollow sphere is put into Muffle furnace in 700 degree of calcining 4h.5% hydrogen is then passed to,
In 700 degree of reduction 0.5h.Finally obtain nickel-nisiloy hydrochlorate-SiO2Multicore shell hollow ball catalyst.Although by high-temperature calcination with
And reduction, acicular nickel silicate phase still have.It can be seen that the catalyst obtained with this synthetic method, nisiloy hydrochlorate is not
There is complete decomposition.The partial size of the nickel of high degree of dispersion is about 6nm.In addition, compared with nisiloy hydrochlorate hollow ball catalyst, nisiloy
Hydrochlorate-SiO2Nucleocapsid hollow ball catalyst has higher reduction temperature, shows that the nucleocapsid catalyst is carried with higher metal
Body strong interaction.
(5) under normal pressure, by CH4、CO2With He with 1:1:1 mode（Air speed 36Lg-1cat·h-1）, each lead into
Nickel-nisiloy hydrochlorate hollow sphere and nickel-nisiloy hydrochlorate-SiO2Multicore shell hollow ball catalyst fixed bed reactors（600oC）, reaction
50h.For nickel-nisiloy hydrochlorate hollow ball catalyst, although initial conversion is slightly higher, because of its higher nickel loading.But
The conversion ratio of methane and carbon dioxide declines 36% and 31% respectively.In comparison, for nickel-nisiloy hydrochlorate-SiO2Multicore shell
The conversion ratio of hollow ball catalyst, methane and carbon dioxide declines 19% and 22% respectively.TG-DT A spectrum can be seen that nickel-nickel
Silicate-SiO2Nucleocapsid hollow ball catalyst weightlessness is nickel-nisiloy phosphate catalyst 1/8, shows that the former has high anti-product
Carbon ability.
Embodiment 6：
（1）200mL ethyl alcohol, 100mL water and 10mL sodium metasilicate are mixed evenly at room temperature.Ammonium hydroxide is added and adjusts pH to 10.
After stirring 12h, separated with centrifuge.With second alcohol and water mixing, washing.The nano SiO 2 particle for finally obtaining 1 μm, 150
Degree is dry for 24 hours.
（2）2g silica is taken, urea is added in 0.3g nickel acetylacetonate, adjusts pH to 12.Mixed solution is put into high pressure
In reaction kettle, 120 degree are heated to, after reaction for 24 hours, is cooled to room temperature.Centrifuge separation, and with methanol, ethyl alcohol, water is washed with this
Afterwards, 100 degree of drying boxes are put into.Obtain nisiloy hydrochlorate hollow sphere.Specific area is 328m2·g-1, nickel loading 35wt%.
（3）Nisiloy hydrochlorate hollow sphere is scattered in ethyl alcohol（30mL）, water（10mL）, CnTAB(n=10)（30mg）Mixing
In solution.After stirring 30min, ammonium hydroxide is added（30mL）.After stirring 30min, 1mL ethyl orthosilicate is added.It reacts at room temperature
After 1h, centrifuge separation, and washed 3 times with the mixed solution of first alcohol and water.It is put into drying box 100oC is dry for 24 hours.Obtain nickel
Silicate-SiO2Nucleocapsid hollow sphere, SiO2Shell thickness is 20nm, specific surface area 300m2·g-1。
（4）By nisiloy hydrochlorate-SiO2Nucleocapsid hollow sphere is put into Muffle furnace in 700 degree of calcining 4h.Then pass to 15% hydrogen
Gas, in 700 degree of reduction 0.5h.Finally obtain nickel-nisiloy hydrochlorate-SiO2Multicore shell hollow ball catalyst.Although being forged by high temperature
It burns and reduction, acicular nickel silicate phase still has.It can be seen that the catalyst obtained with this synthetic method, nisiloy hydrochlorate
There is no decompose completely.The partial size of the nickel of high degree of dispersion is about 7nm.In addition, compared with nisiloy hydrochlorate hollow ball catalyst,
Nisiloy hydrochlorate-SiO2Nucleocapsid hollow ball catalyst has higher reduction temperature, shows that the nucleocapsid catalyst has higher gold
Belong to carrier strong interaction.
(5) under normal pressure, by CH4、CO2With He with 1:1:1 mode（Air speed 36Lg-1cat·h-1）, each lead into
Nickel-nisiloy hydrochlorate hollow sphere and nickel-nisiloy hydrochlorate-SiO2Multicore shell hollow ball catalyst fixed bed reactors（600oC）, reaction
50h.For nickel-nisiloy hydrochlorate hollow ball catalyst, although initial conversion is slightly higher, because of its higher nickel loading.But
The conversion ratio of methane and carbon dioxide declines 36% and 31% respectively.In comparison, for nickel-nisiloy hydrochlorate-SiO2Multicore shell
The conversion ratio of hollow ball catalyst, methane and carbon dioxide declines 30% and 29% respectively.TG-DT A spectrum can be seen that nickel-nickel
Silicate-SiO2Nucleocapsid hollow ball catalyst weightlessness is nickel-nisiloy phosphate catalyst 90%, shows that the former has high anti-product
Carbon ability.
Claims (7)
1. methane reforming multicore shell hollow type catalyst nickel-nisiloy hydrochlorate-SiO2Preparation method, which is characterized in that this method packet
Include following steps：
（1）Ethyl alcohol, water and silicon source are 0oC~70oIt is mixed evenly under conditions of C, adds lye and adjust pH to 10, stir,
Centrifuge separation, washing, final dry obtained nano SiO 2 particle；
（2）It takes nano SiO 2 particle of the partial size in 500nm~1 μm to be formulated as concentration 1g/L~10g/L, lye is added by pH
It is adjusted to 8-13, the nickel presoma that concentration is 1g/L~10g/L is added, is 50 in temperatureoC~220oIt is synthesized under the conditions of C,
Nisiloy hydrochlorate hollow sphere finally is made through supercooling, centrifuge separation, washing；
（3）Nisiloy hydrochlorate hollow sphere is scattered in the mixed solution of surfactant and water, lye is added after stirring, by pH tune
To 10-14,10mL ethyl orthosilicate is added in reacting under room temperature, is finally centrifugated, washs, dry obtained nisiloy acid
Salt-SiO2Nucleocapsid hollow sphere；
（4）By nisiloy hydrochlorate-SiO2Nucleocapsid hollow sphere is 300 in temperatureoC~800oIt is restored under the hydrogen atmosphere of C, obtains height
The nickel of dispersion-nisiloy hydrochlorate-SiO2Multicore shell hollow type catalyst.
2. methane reforming multicore shell hollow type catalyst nickel-nisiloy hydrochlorate-SiO according to claim 12Preparation method,
It is characterized in that：Step（1）In, the silicon source is one of ethyl orthosilicate, sodium silicate water glass, methyl orthosilicate or several
The combination of kind.
3. methane reforming multicore shell hollow type catalyst nickel-nisiloy hydrochlorate-SiO according to claim 12Preparation method,
It is characterized in that：Step（2）In, the nickel presoma is nickel nitrate, in nickel acetate, nickel acetylacetonate, nickel oxalate, oleic acid nickel
One or more of combinations.
4. methane reforming multicore shell hollow type catalyst nickel-nisiloy hydrochlorate-SiO according to claim 12Preparation method,
It is characterized in that：The step（1）,（2）,（3）In, lye is the group of one or more of sodium hydroxide, urea, ammonium hydroxide
It closes.
5. methane reforming multicore shell hollow type catalyst nickel-nisiloy hydrochlorate-SiO according to claim 12Preparation method,
It is characterized in that：The step（1）,（2）,（3）In, washing cleaning solvent used is water, in ethyl alcohol, methanol, acetone, hexamethylene
One or more of combinations.
6. methane reforming multicore shell hollow type catalyst nickel-nisiloy hydrochlorate-SiO according to claim 12Preparation method,
It is characterized in that：In step（3）In, the surfactant be nonionic surface active agent or ionic surfactant,
Wherein nonionic surface active agent is C14H22O(C2H4O)n, n=10~15, C15H24O(C2H4O)n, one of n=5~10 or
It is several；Ionic surfactant is alkyl quaternaries surfactant CnTAB, one or more of n=10~15.
7. methane reforming multicore shell hollow type catalyst nickel-nisiloy hydrochlorate-SiO according to claim 12Preparation method,
It is characterized in that：Step（4）In, nickel-nisiloy hydrochlorate-silica core-shell hollow type specific surface area of catalyst is in 300m2•g-1~
600m2•g-1, silica shell thickness is in 30nm~80nm.
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