CN108636412A - Methane and carbon dioxide reforms the preparation method of multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate - Google Patents
Methane and carbon dioxide reforms the preparation method of multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate Download PDFInfo
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- CN108636412A CN108636412A CN201810126787.4A CN201810126787A CN108636412A CN 108636412 A CN108636412 A CN 108636412A CN 201810126787 A CN201810126787 A CN 201810126787A CN 108636412 A CN108636412 A CN 108636412A
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- Prior art keywords
- nickel
- type catalyst
- nisiloy hydrochlorate
- hollow type
- nisiloy
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 25
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000019441 ethanol Nutrition 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 238000004781 supercooling Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 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 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 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
- 229940078494 nickel acetate Drugs 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
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 239000003921 oil Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- 238000011068 loading method Methods 0.000 abstract description 6
- 238000009707 resistance sintering Methods 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000000377 silicon dioxide Substances 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000010189 synthetic method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 238000003837 high-temperature calcination Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 4
- 235000019795 sodium metasilicate Nutrition 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 229910052914 metal silicate Inorganic materials 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 238000006057 reforming reaction Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FXSGDOZPBLGOIN-UHFFFAOYSA-N trihydroxy(methoxy)silane Chemical class CO[Si](O)(O)O FXSGDOZPBLGOIN-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- XIKYYQJBTPYKSG-UHFFFAOYSA-N nickel Chemical compound [Ni].[Ni] XIKYYQJBTPYKSG-UHFFFAOYSA-N 0.000 description 1
- PXFAWKNRNHXITF-KVVVOXFISA-N nickel;(z)-octadec-9-enoic acid Chemical compound [Ni].CCCCCCCC\C=C/CCCCCCCC(O)=O PXFAWKNRNHXITF-KVVVOXFISA-N 0.000 description 1
- 238000001228 spectrum Methods 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
-
- B01J35/393—
-
- B01J35/51—
-
- B01J35/615—
-
- 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 present invention discloses the preparation method that methane and carbon dioxide reforms multinuclear shell hollow type catalyst nickel nisiloy hydrochlorate, and the method comprising the steps of：（1）0oC~70oUnder the conditions of C, ethyl alcohol, water, silicon source are mixed evenly, adjust pH7~10, after reacting 8~13h, is centrifuged, washing, finally 50oC~400oC is dried, nano SiO 2 particle of the obtained grain size in 100nm~1 μm；（2）Nano SiO 2 particle is added in aqueous solution makes its a concentration of 1g/L~10g/L, and lye is added, pH is adjusted to 8~13, the nickel presoma of a concentration of 1g/L~10g/L is added, and is 50 in temperatureoC~220oAfter carrying out 5~72h of reaction under the conditions of C, nisiloy hydrochlorate hollow ball is made by handling；（3）By nisiloy hydrochlorate hollow ball temperature be 300oC~800oIt under the conditions of C, is passed through hydrogen and is restored, multinuclear shell hollow type catalyst nickel nisiloy hydrochlorate is made.Multinuclear shell hollow type catalyst nickel nisiloy hydrochlorate prepared by the present invention has higher nickel loading, while having highly resistance sintering, anti-carbon performance.
Description
Technical field
The present invention relates to the preparation method that methane and carbon dioxide reforms multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate,
Belong to chemical production technical field.
Background technology
Nickel-base catalyst is studied extensively both at home and abroad because of its cheap and high Reforming catalyst activity.When it is applied to CH4With
CO2When reforming reaction, nickel-base catalyst carbon deposition phenomenon is than more serious, mainly since the sintering of nickel metal can promote carbon distribution secondary anti-
The generation answered, especially when the load capacity of nickel is relatively high, sintering phenomenon becomes apparent from, and carbon distribution is more serious.This invention person once opened
Sent out catalyst with core-casing structure, can inhibitory activity metal sintering, however, their low problems of generally existing mass-transfer efficiency.
Meanwhile metal silicate has many advantages, such as high-temperature stability and high-specific surface area because its is cheap, it is extensive
As catalyst.But these metal silicates are only used as the presoma of catalyst at present, these metal silicate presomas
After high temperature reduction, the advantages of decomposing completely, lose its high-specific surface area.In addition, the load capacity of these catalyst is less than
20wt%。
I.e.：A kind of CH is needed now4And CO2Catalyst has highly resistance sintering and anti-carbon performance under higher load amount.
Invention content
The technical problem to be solved in the present invention is to provide methane and carbon dioxides to reform multinuclear shell hollow type catalyst nickel-nickel
The preparation method of silicate, makes CH4And CO2Reforming catalyst has highly resistance sintering and anti-carbon performance under higher load amount,
It can be with overcome the deficiencies in the prior art.
The technical scheme is that：Methane and carbon dioxide reforms multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate
Preparation method, this method include following steps：（1）0oC~70oUnder conditions of C, ethyl alcohol, water and silicon source are mixed and stirred
It mixes uniformly, it is 7~10 to add lye and adjust pH, after reacting 8~13h, is detached with centrifuge, washing, finally 50oC~
400oC is dried, and nano SiO 2 particle is made；（2）Nano SiO 2 particle is added in aqueous solution makes its a concentration of 1g/
L~10g/L is added lye, pH is adjusted to 8~13, the nickel presoma of a concentration of 1g/L~10g/L is added, is in temperature
50oC~220oAfter carrying out 5~72h of reaction under the conditions of C, it is empty that nisiloy hydrochlorate is made through supercooling, centrifugation, washing, after dry
Bulbus cordis；（3）By nisiloy hydrochlorate hollow ball reduction temperature be 300oC~800oIt under conditions of C, is passed through hydrogen and is restored, be made
Multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate.
Above-mentioned step（1）In, the silicon source is one kind in 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 steps（1）、（2）In, lye is the combination of one or more of sodium hydroxide, urea, ammonium hydroxide.
Above-mentioned is rapid（1）、（2）In, it is one kind in water, ethyl alcohol, methanol, acetone, hexamethylene to wash cleaning solvent used
Or several combination.
Aforementioned step（3）In, the specific surface area of prepared nickel-nisiloy hydrochlorate is in 200m2·g-1~400m2·g-1,
Load capacity is in 30wt%~40wt%, and the grain size of nickel is in 2nm~10nm.
The prior art compares, and methane and carbon dioxide of the present invention reforms multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate
Preparation method, including following steps：（1）0oC~70oUnder conditions of C, ethyl alcohol, water and silicon source are mixed equal
Even, it is 7~10 to add lye and adjust pH, after reacting 8~13h, with centrifuge separation, is washed, finally 50oC~400oC is dry
It is dry, nano SiO 2 particle is made；（2）Nano SiO 2 particle is added in aqueous solution makes its a concentration of 1g/L~10g/
L is added lye, pH is adjusted to 8~13, the nickel presoma of a concentration of 1g/L~10g/L is added, and is 50 in temperatureoC~220oC
Under the conditions of carry out 5~72h of reaction after, through supercooling, centrifugation, washing, nisiloy hydrochlorate hollow ball is made after dry；（3）It will
Nisiloy hydrochlorate hollow ball is 300 in reduction temperatureoC~800oIt under conditions of C, is passed through hydrogen and is restored, it is hollow that multinuclear shell is made
Type catalyst nickel-nisiloy hydrochlorate.By test of many times, multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate has made from this method
There are following characteristics：700oUnder C reaction temperatures, there is higher anti-carbon performance, carbon deposition quantity<5%；Load capacity be up to 30wt%~
40wt%, catalyst of the more conventional load capacity less than 20wt% obviously have advantage；High degree of dispersion（Grain size is in 2nm~10nm）、
High-specific surface area（200m2·g-1~400m2·g-1）, there is high mass-transfer efficiency.It is empty that nano nickel particles are dispersed in nisiloy hydrochlorate
In bulbus cordis, nucleocapsid hollow-core construction is formed, grain size is in 500nm~1 μm.With existing CH4And CO2Dry reforming nickel-base catalyst phase
Compare, the application synthetic method is rapid, and synthesis material is easy to get, and can realize that high-volume synthesizes, the specific surface area of catalyst of synthesis
Height, load capacity is high, and dispersion degree is high, and mass-transfer efficiency is high, and anti-carbon performance is good.
Description of the drawings
Fig. 1 is the preparation method schematic diagram of multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate.
Fig. 2 is the transmission electron microscope picture of nisiloy hydrochlorate hollow ball.
Fig. 3 is nisiloy hydrochlorate hollow ball high-resolution-ration transmission electric-lens figure.
Fig. 4 is the transmission electron microscope picture of multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate.
Fig. 5 is the high-resolution-ration transmission electric-lens figure of multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate.
Fig. 6 is the X-ray diffractogram of nisiloy hydrochlorate hollow ball and multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate.
Fig. 7 is multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate CH4And CO2Reforming reaction activity figure.
Fig. 8 is multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate CH4And CO2Thermogravimetric, heating differential analysis figure after reforming reaction.
Specific implementation mode
Methane and carbon dioxide reforms the preparation method of multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate, and this method includes
Following steps：（1）0oC~70oUnder conditions of C, ethyl alcohol, water and silicon source are mixed evenly, add lye tune
It is 7~10 to save pH, after reacting 8~13h, with centrifuge separation, is washed, finally 50oC~400oC is dried, and grain size is made and exists
The nano SiO 2 particle of 100nm~1 μm；（2）Nano SiO 2 particle is added in aqueous solution makes its a concentration of 1g/L
~10g/L is added lye, pH is adjusted to 8~13, the nickel presoma of a concentration of 1g/L~10g/L is added, and is 50 in temperatureoC
~220oAfter carrying out 5~72h of reaction under the conditions of C, it is hollow that nisiloy hydrochlorate is made through supercooling, centrifugation, washing, after dry
Ball；（3）By nisiloy hydrochlorate hollow ball reduction temperature be 300oC~800oIt under conditions of C, is passed through hydrogen and is restored, be made more
Nucleocapsid hollow type catalyst nickel-nisiloy hydrochlorate.
Embodiment 1
（1）200mL ethyl alcohol, 100mL water and 40mL methyl orthosilicates are 0oBe mixed evenly under C, be added urea adjust pH to
10.After stirring 2h, first detached with centrifuge, again with methanol and water mixing, washing.Finally obtain the silica nanometer of 600nm
Grain, 150oC is dried for 24 hours.
（2）Take grain size in the 2g silica of 500nm, ammonium hydroxide is added in 0.3g nickel nitrates, adjusts pH to 8.By mixed solution
It is put into autoclave, is heated to 50oC is cooled to room temperature after reaction for 24 hours.It centrifuges, methanol, ethyl alcohol, washing is used in combination
After washing, 100 degree of drying boxes are placed.Obtain nisiloy hydrochlorate hollow ball（Such as Fig. 2, shown in 3,6）.Specific area is 250m2·g-1, nickel is negative
Carrying capacity is 30wt%.
（3）Nisiloy hydrochlorate hollow ball is put into Muffle furnace 300oC calcines 4h, pure hydrogen is then passed to, 300oC is also
Former 0.5h finally obtains multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate（Such as Fig. 4, shown in 5,6）.It can be seen by Fig. 4,5,6
Go out, although by high-temperature calcination and reduction, acicular nickel silicate phase still has.It can be seen that being obtained with this synthetic method
Catalyst, nisiloy hydrochlorate there is no completely decompose, the grain size of the nickel of high degree of dispersion is about 5nm.Under normal pressure, by CH4、CO2
With He with 1:1:1 mode（Air speed 36Lg-1cat·h-1）, it is passed through multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate and fixes
Bed reactor（700oC）, after reacting 70h, the conversion ratio of methane and carbon dioxide is kept stable at 77.5% and 86.6%（Fig. 7）.
TG-DT A spectrum can be seen that weightlessness is less than 5%, show that catalyst has high carbon accumulation resisting ability（Fig. 8）.
Embodiment 2
（1）200mL ethyl alcohol, 100mL water and 10mL sodium metasilicate are mixed evenly at room temperature, add ammonium hydroxide adjust pH to
10.It after stirring 2h, is first detached with centrifuge, then with second alcohol and water mixing, washing.Finally obtain the silica nanometer of 200nm
Grain is dried for 24 hours at 150 degree.
（2）Take grain size in the silica of 750nm, ammonium hydroxide is added in 0.3g nickel acetates, adjusts pH to 12.By mixed solution
It is put into autoclave, is heated to 120 degree, after reaction for 24 hours, is cooled to room temperature.Centrifuge, be used in combination methanol, ethyl alcohol, water with
After this washing, 100 are placedoC drying boxes.Obtain nisiloy hydrochlorate hollow ball, specific area 230m2·g-1, nickel loading is
40wt%。
（3）Nisiloy hydrochlorate hollow ball is put into Muffle furnace 550oC calcines 4h, pure hydrogen is then passed to, 550oC is also
Former 0.5h finally obtains multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate.Although acicular by high-temperature calcination and reduction
Nickel silicate phase still has.It can be seen that the catalyst obtained with this synthetic method, nisiloy hydrochlorate is high there is no decomposition completely
The grain size for spending the nickel of dispersion is about 7nm.
Embodiment 3
（1）200mL ethyl alcohol, 100mL water and 10mL sodium metasilicate are 70oIt is mixed evenly under C, ammonium hydroxide is added and adjusts pH to 10.
It after stirring 12h, is first detached with centrifuge, then with second alcohol and water mixing, washing.1 μm of nano SiO 2 particle is finally obtained,
It is dried for 24 hours at 150 degree.
（2）It is 1 μm of 2g silica to take grain size, and sodium hydroxide is added in 0.3g nickel acetylacetonates, adjusts pH to 13.It will
Mixed solution is put into autoclave, is heated to 220oC is cooled to room temperature after reaction for 24 hours, centrifuges, methanol is used in combination,
Ethyl alcohol after water is washed with this, is put into 100 degree of drying boxes, after drying, obtains nisiloy hydrochlorate hollow ball, specific area is
328m2·g-1, nickel loading 35wt%.
（3）Nisiloy hydrochlorate hollow ball is put into Muffle furnace 800oC calcines 4h, 5% hydrogen is then passed to, 800oUnder C
0.5h is restored, multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate is finally obtained.Although needle-shaped by high-temperature calcination and reduction
Nickel silicate phase still have.It can be seen that the catalyst obtained with this synthetic method, there is no decompose completely for nisiloy hydrochlorate.
The grain size of the nickel of high degree of dispersion is about 6nm.
Embodiment 4
（1）200mL ethyl alcohol, 100mL water and 40mL methyl orthosilicates are mixed evenly at room temperature, be added urea adjust pH to
10.After stirring 2h, first detached with centrifuge, again with methanol and water mixing, washing.Finally obtain the silica nanometer of 600nm
Grain, 150oC is dried for 24 hours.
（2）It takes 2g silica, 0.3g nickel nitrates that ammonium hydroxide is added, 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.It centrifuges, methanol, ethyl alcohol is used in combination after water is washed with this, to put
Enter 100 degree of drying boxes.Obtain nisiloy hydrochlorate hollow ball（Such as Fig. 2, shown in 3,6）.Specific area is 250m2·g-1, nickel loading is
30wt%。
（3）Nisiloy hydrochlorate hollow ball is put into Muffle furnace the calcining 4h at 700 degree.Pure hydrogen is then passed to, also at 700 degree
Former 0.5h.Finally obtain multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate（Such as Fig. 4, shown in 5,6）.It can be seen by Fig. 4,5,6
Go out, although by high-temperature calcination and reduction, acicular nickel silicate phase still has.It can be seen that being obtained with this synthetic method
Catalyst, nisiloy hydrochlorate there is no completely decompose, the grain size of the nickel of high degree of dispersion is about 5nm.Under normal pressure, by CH4、CO2
With He with 1:1:1 mode（Air speed 36Lg-1cat·h-1）, it is passed through multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate and fixes
Bed reactor（700oC）, react 70h.The conversion ratio of methane and carbon dioxide is kept stable at 77.5% and 86.6%（Fig. 7）.Heat
Method of double differences heat analysis can be seen that weightlessness is less than 5%, show that catalyst has high carbon accumulation resisting ability（Fig. 8）.
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
It after mixing 2h, is first detached with centrifuge, then with second alcohol and water mixing, washing.The nano SiO 2 particle for finally obtaining 200nm,
150 degree of dryings are for 24 hours.
（2）It takes 2g silica, 0.3g nickel acetates that ammonium hydroxide is added, 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.It centrifuges, methanol, ethyl alcohol is used in combination after water is washed with this, to put
Enter 100oC drying boxes.Obtain nisiloy hydrochlorate hollow ball, specific area 230m2·g-1, nickel loading 40wt%.
（3）Nisiloy hydrochlorate hollow ball is put into Muffle furnace the calcining 4h at 700 degree, then passes to pure hydrogen, also at 700 degree
Former 0.5h finally obtains multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate.Although acicular by high-temperature calcination and reduction
Nickel silicate phase still has.It can be seen that the catalyst obtained with this synthetic method, nisiloy hydrochlorate is high there is no decomposition completely
The grain size for spending the nickel of dispersion is about 7nm.
Embodiment 6
（1）200mL ethyl alcohol, 100mL water and 10mL sodium metasilicate are mixed evenly at room temperature, and ammonium hydroxide is added and adjusts pH to 10,
It after stirring 12h, is first detached with centrifuge, then with second alcohol and water mixing, washing.1 μm of nano SiO 2 particle is finally obtained,
It is dried for 24 hours at 150 degree.
（2）It takes 2g silica, 0.3g nickel acetylacetonates that sodium hydroxide is added, adjusts pH to 12.Mixed solution is put into
In autoclave, 120 degree are heated to, after reaction for 24 hours, is cooled to room temperature.It centrifuges, methanol, ethyl alcohol, water is used in combination to be washed with this
After washing, it is put into 100 degree of drying boxes.Obtain nisiloy hydrochlorate hollow ball.Specific area is 328m2·g-1, nickel loading 35wt%.
（3）Nisiloy hydrochlorate hollow ball is put into Muffle furnace the calcining 4h at 700 degree.5% hydrogen is then passed to, also at 700 degree
Former 0.5h finally obtains multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate.Although acicular by high-temperature calcination and reduction
Nickel silicate phase still has, it can be seen that the catalyst obtained with this synthetic method, there is no decompose completely for nisiloy hydrochlorate.It is high
The grain size for spending the nickel of dispersion is about 6nm.
Claims (7)
1. methane and carbon dioxide reforms the preparation method of multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate, which is characterized in that should
Method includes following steps：
（1）0oC~70oUnder conditions of C, ethyl alcohol, water and silicon source are mixed evenly, add lye adjust pH be 7~
10, after reacting 8~13h, with centrifuge separation, wash, finally 50oC~400oC is dried, and nano SiO 2 particle is made；
（2）Nano SiO 2 particle is added in aqueous solution makes its a concentration of 1g/L~10g/L, and lye is added, pH is adjusted
To 8~13, the nickel presoma of a concentration of 1g/L~10g/L is added, is 50 in temperatureoC~220oCarried out under the conditions of C reaction 5~
After 72h, through supercooling, centrifugation, washing, nisiloy hydrochlorate hollow ball is made after dry；
（3）By nisiloy hydrochlorate hollow ball reduction temperature be 300oC~800oIt under conditions of C, is passed through hydrogen and is restored, be made
Multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate.
2. methane and carbon dioxide according to claim 1 reforms the system of multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate
Preparation Method, it is characterised in that：Step（1）In, the silicon source is in ethyl orthosilicate, sodium silicate water glass, methyl orthosilicate
One or more of combinations.
3. methane and carbon dioxide according to claim 1 reforms the system of multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate
Preparation Method, it is characterised in that：The step（1）In, nano SiO 2 particle grain size obtained is 100nm~1 μm.
4. methane and carbon dioxide according to claim 1 reforms the system of multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate
Preparation Method, it is characterised in that：Step（2）In, the nickel presoma is nickel nitrate, nickel acetate, nickel acetylacetonate, nickel oxalate, oil
The combination of one or more of sour nickel.
5. methane and carbon dioxide according to claim 1 reforms the system of multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate
Preparation Method, it is characterised in that：The step（1）、（2）In, lye is one or more of sodium hydroxide, urea, ammonium hydroxide
Combination.
6. methane and carbon dioxide according to claim 1 reforms the system of multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate
Preparation Method, it is characterised in that：The step（1）、（2）In, it is water, ethyl alcohol, methanol, acetone, hexamethylene to wash cleaning solvent used
The combination of one or more of alkane.
7. methane and carbon dioxide according to claim 1 reforms the system of multinuclear shell hollow type catalyst nickel-nisiloy hydrochlorate
Preparation Method, it is characterised in that：Step（3）In, the specific surface area of prepared nickel-nisiloy hydrochlorate is in 200m2·g-1~400m2·
g-1, load capacity is in 30wt%~40wt%, and the grain size of nickel is in 2nm~10nm.
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