CN106000443A - Method for preparing efficient and stable methane dry-reforming catalyst by means of one-step synthesis - Google Patents
Method for preparing efficient and stable methane dry-reforming catalyst by means of one-step synthesis Download PDFInfo
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- CN106000443A CN106000443A CN201610347143.9A CN201610347143A CN106000443A CN 106000443 A CN106000443 A CN 106000443A CN 201610347143 A CN201610347143 A CN 201610347143A CN 106000443 A CN106000443 A CN 106000443A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 238000002407 reforming Methods 0.000 title claims abstract description 37
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000010453 quartz Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 14
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 11
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- 230000009467 reduction Effects 0.000 claims description 4
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- 238000005245 sintering Methods 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 239000002923 metal particle Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 238000011068 loading method Methods 0.000 abstract 1
- 239000002210 silicon-based material Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 33
- 238000006555 catalytic reaction Methods 0.000 description 16
- 235000012239 silicon dioxide Nutrition 0.000 description 16
- 238000012360 testing method Methods 0.000 description 14
- 239000012467 final product Substances 0.000 description 13
- 238000010998 test method Methods 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000008187 granular material Substances 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000013589 supplement 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
- B01J29/0356—Iron group metals or copper
-
- B01J35/60—
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
Abstract
The invention discloses a method for preparing an efficient and stable methane dry-reforming catalyst by means of one-step synthesis. The methane dry-reforming catalyst takes a high thermal stability silicon-based material having an ordered mesoporous channel as a carrier, thus being capable of enabling active nickel species to be effectively confined within the mesoporous channel. The methane dry-reforming catalyst is obtained by directly mixing metal precursor salt and a solvent by means of one-step synthesis, filtering, washing, drying, then carrying out high-temperature calcination and reducing, and the active species of the obtained catalyst are highly and stably dispersed. The catalyst is uniform in distribution of the active species, and active metal particles have small sizes so as to be well confined within the mesoporous carrier. Furthermore, the methane dry-reforming catalyst is simple in preparation method, easy to obtain and lower in active component loading capacity, and has very high metal-carrier interaction. Therefore, the methane dry-reforming catalyst has very high sintering resistance and carbon deposition resistance, thus showing excellent catalytic activity and stability. The method is simple in preparation technology and low in preparation cost, and the catalyst prepared by the method has potential application prospect.
Description
Technical field
The invention belongs to reforming catalyst preparation technology and environmental protection technical field, relate to a kind of one-step synthesis the most steady
The preparation method of fixed methane dry reforming catalyst.
Background technology
World energy sources is mainly built upon coal, the basis of oil and natural gas these three inflammable minerals resource at present
On.Through the development of decades, petrochemical industry has been developed as the mainstay industry of modern civilization society.But due to
The long-term exploitation of petroleum resources and a large amount of consumption, reserves are the deficientest, and the time limit being available for exploitation the most drastically reduces.Natural gas provides
Source not only rich reserves and be that a kind of clean energy resource is just favored by people.There is deep change in world energy sources structure
Changing, natural gas will become the main fossil energy of 21 century.Gas chemical industry will become the important supplement of petrochemical industry.Due to first
Alkane is as the main component in natural gas, and therefore effectively utilizing of methane is the most important research direction.Methane is converted into conjunction
Becoming gas is the effective way being further converted into a series of important chemical products, is currently also the most industrialized technology.
Methane synthesis gas has three approach at present: i.e. steam reforming, methane portion oxidation is reformed and carbon dioxide weight
Whole.Methane carbon dioxide reformation (dry reforming) producing synthesis gas is not only effectively utilized CH4And CO2Two kinds of greenhouse gases, and should
The synthesis gas H that process produces2/ CO ratio about 1, can be directly as oxo process and the raw material of F-T synthesis.Methane dry reforming is urged
Agent mainly includes noble metal catalyst (Pt, Rh, Pd, Ir, Ru etc.) and non-precious metal catalyst (Ni, Co, Fe, Cu etc.).Though
So noble metal catalyst has higher catalysis activity and stability and preferable anti-carbon performance, but due to expensive limit
Make its commercial Application.In non-precious metal catalyst, most research work is concentrated mainly on Ni base catalyst, this be by
Best in Ni base catalyst activity and suitable with noble metal catalyst activity, low price.But Ni base catalyst is easy to produce
Raw carbon distribution, thus cause the inactivation of catalyst.
Ni base catalyst not only active center dispersion prepared by tradition infusion process is uneven, easily causes the stifled of mesopore orbit
Plug, and the interaction of Metal-Support is more weak, and anti-carbon anti-sintering property is poor.Theoretical research proves, nickel is smaller in size than one
Determine degree, there is stronger anti-carbon performance；Ni base catalyst has the phase interaction of good confinement effect and strong metal-carrier
With can effectively suppress metal sintering largely, and then strengthen to anti-carbon performance.Therefore, exploitation efficient stable
And the catalyst with high anti-carbon performance is very important.In recent years, order mesoporous silica-base material is studied widely.
Because these materials have specific surface area height, greatly, the advantages such as heat stability height is adjustable with aperture, it is used as catalyst carrier to pore volume
Be conducive to the fine dispersion of active metal component, there is stronger Metal-Support and interact, thus improve catalyst activity and
Anti-carbon and anti-sintering property.One-step synthesis prepares the methane dry reforming catalyst of efficient stable, it is possible to promote nickel precursor salt
Uniform dispersion, compares the preparation method of tradition catalyst for reforming, and preparation technology is simple, saves the energy, has Modulatory character.
Summary of the invention
It is an object of the invention to provide the preparation method of the methane dry reforming catalyst of a kind of one-step synthesis efficient stable,
Obtain the methane dry reforming catalyst of a kind of efficient stable.
The technical scheme realizing the object of the invention sequentially includes the following steps:
A. the preparation of catalyst: weigh neutral amine and be dissolved in ethanol and solution that deionized water volume ratio is 1:1, be stirred vigorously
After being completely dissolved, being added dropwise over tetraethyl orthosilicate, neutral amine and tetraethyl orthosilicate mol ratio are 1:0.27, continue stirring
Uniform mixed solution；Weighing nickel precursor salt, be dissolved in above-mentioned mixed solution, Ni/Si mol ratio is 0.025～0.15,
Under room temperature continue stirring 20～24h, it is thus achieved that aaerosol solution be filtered, washed and dried after, forge for 500～700 DEG C under air atmosphere
Burning 4～6h, heating rate is 1 DEG C/min；
B. the reduction of catalyst: the catalyst that step A prepares is placed in miniature fixed-bed quartz reactor at 500～700 DEG C
Pure H2Reduction 1h, H under conditions of atmosphere2Flow velocity is 15～30mL/min, obtains the methane dry reforming catalyst of efficient stable.
Described neutral amine is the one in dodecyl amine, tetradecylamine, cetylamine, octadecylamine.
Described nickel precursor salt is the one in nickel nitrate, nickel acetate, Nickel dichloride., nickel acetylacetonate.Of the present invention
Preparation method, can preferably make nickel granule be embedded on mesoporous supports.
Described Ni/Si mol ratio is 0.025～0.15, by the mol ratio of modulation Ni/Si, obtains different degree of scatter
Catalyst.Ni/Si mol ratio is less than 0.025, and nickel active component is very little, it is impossible to be effectively improved catalysis activity；Ni/Si mol ratio
More than 0.15, nickel active component is too many, is easily caused gathering of nickel granule.
Described prepared catalyst nickel metal particle size is 2～5nm.
The present invention compared with prior art has the advantage that
(1) mesopore silicon oxide HMS is a kind of hexagonal mesoporous silica with vermiform duct, and its specific surface area is big, and hole wall is thick,
Hole link is preferable, is good catalyst carrier.It is essential that HMS is in neutral conditions, by the positive silicic acid of predecessor four
The self assembly under the effect of H key of ethyl ester and template neutral amine completes, and this just provides possibility for being introduced directly into of Ni.With
Unlike the mesoporous materials such as MCM-41 and TUD-1, the self assembling process of HMS is the most at room temperature carried out, without hydrothermal crystallizing,
Synthesis condition gentleness is easily controlled, and synthesis cycle is shorter.So far, also not about HMS base catalyst at anti-carbon or
Report in terms of anti-sintering.Compared with the Ni/HMS using infusion process to prepare, the Ni-HMS of one-step synthesis is used to show excellence
Catalysis active and anti-sintering anti-carbon performance；
(2) present invention uses one-step synthesis to prepare the methane dry reforming catalyst of efficient stable, compares tradition catalyst for reforming
Preparation method, preparation technology is simple, saves the energy, has Modulatory character；
(3) present invention is by utilizing different neutral amines, uses one-step synthesis, not only obtains the nickel species of high degree of dispersion, and
And substantially reduce the size of nickel granule, and the good confinement of nickel metal is in the duct of mesoporous supports；
(4) the methane dry reforming catalyst that the inventive method obtains has stronger Metal-Support and interacts, the most anti-long-pending
Carbon and anti-sintering property, therefore activity and stability are more preferable.
Accompanying drawing explanation
Fig. 1 is the methane dry reforming catalyst H of embodiment 2 preparation2After reduction transmission electron microscope (TEM) image；
Fig. 2 is methane dry reforming catalyst 100h reacted transmission electron microscope (TEM) image of embodiment 2 preparation.
Specific embodiment
Below in conjunction with specific embodiments and the drawings, the present invention will be further described, and the present invention is not limited by following embodiment
System, can determine specific embodiment according to technical scheme and practical situation.
Embodiment 1
Weigh in the solution that 1.2g dodecyl amine is dissolved in 14mL ethanol and 14mL deionized water, be stirred vigorously to after being completely dissolved,
It is added dropwise over 5g tetraethyl orthosilicate, continues the mixed solution that stirs to obtain, weigh 0.17g nickel nitrate, be dissolved in above-mentioned mixing molten
In liquid, Ni/Si mol ratio is 0.025, at room temperature continue stirring 20h, it is thus achieved that aaerosol solution be filtered, washed and dried
After, the lower 500 DEG C of calcining 4h of air atmosphere, heating rate is 1 DEG C/min；It is subsequently placed in miniature fixed-bed quartz reactor,
700 DEG C of pure H2Reduction 1h, H under ambient conditions2Flow velocity is 15mL/min, to obtain final product.
Catalysis active testing: weigh catalyst prepared for 50mg and put in fixed bed miniature quartz reactor, by CH4And CO2
Reaction gas (V (CH4):V(CO2)=1:1) it is passed through in reactor, the results are shown in Table 1.
Methane dry reforming catalyst activity test (700～800 DEG C) that table 1 embodiment 1 prepares
。
Embodiment 2
Weigh in the solution that 1.2g dodecyl amine is dissolved in 14mL ethanol and 14mL deionized water, be stirred vigorously to after being completely dissolved,
It is added dropwise over 5g tetraethyl orthosilicate, continues the mixed solution that stirs to obtain, weigh 0.52g nickel nitrate, be dissolved in above-mentioned mixing molten
In liquid, Ni/Si mol ratio is 0.074, at room temperature continue stirring 20h, it is thus achieved that aaerosol solution be filtered, washed and dried
After, the lower 550 DEG C of calcining 5h of air atmosphere, heating rate is 1 DEG C/min；It is subsequently placed in miniature fixed-bed quartz reactor,
700 DEG C of pure H2Reduction 1h, H under ambient conditions2Flow velocity is 15mL/min, to obtain final product.It will be seen from figure 1 that nickel in the catalyst prepared
Even particulate dispersion and well confinement are in mesopore orbit.
Catalysis activity test method, with embodiment 1, the results are shown in Table 2.
Stability test: through the reaction of 100h, CH at 700 DEG C4And CO2Conversion ratio be still kept at 75% He
82%, nickel granule is almost without growing up and gathering (see figure 2).
Methane dry reforming catalyst activity test (700～800 DEG C) that table 2 embodiment 2 prepares
。
Embodiment 3
Weigh in the solution that 1.2g tetradecylamine is dissolved in 14mL ethanol and 14mL deionized water, be stirred vigorously to after being completely dissolved,
It is added dropwise over 5g tetraethyl orthosilicate, continues the mixed solution that stirs to obtain, weigh 0.52g nickel nitrate, be dissolved in above-mentioned mixing molten
In liquid, Ni/Si mol ratio is 0.074, at room temperature continue stirring 20h, it is thus achieved that aaerosol solution be filtered, washed and dried
After, the lower 550 DEG C of calcining 4h of air atmosphere, heating rate is 1 DEG C/min；It is subsequently placed in miniature fixed-bed quartz reactor,
700 DEG C of pure H2Reduction 1h, H under ambient conditions2Flow velocity is 15mL/min, to obtain final product.
Catalysis activity test method, with embodiment 1, the results are shown in Table 3.
Methane dry reforming catalyst activity test (700～800 DEG C) that table 3 embodiment 3 prepares
。
Embodiment 4
Weigh in the solution that 1.2g cetylamine is dissolved in 14mL ethanol and 14mL deionized water, be stirred vigorously to after being completely dissolved,
It is added dropwise over 5g tetraethyl orthosilicate, continues the mixed solution that stirs to obtain, weigh 0.52g nickel nitrate, be dissolved in above-mentioned mixing molten
In liquid, Ni/Si mol ratio is 0.074, at room temperature continue stirring 20h, it is thus achieved that aaerosol solution be filtered, washed and dried
After, the lower 550 DEG C of calcining 4h of air atmosphere, heating rate is 1 DEG C/min；It is subsequently placed in miniature fixed-bed quartz reactor,
700 DEG C of pure H2Reduction 1h, H under ambient conditions2Flow velocity is 15mL/min, to obtain final product.
Catalysis activity test method, with embodiment 1, the results are shown in Table 4.
Methane dry reforming catalyst activity test (700～800 DEG C) that table 4 embodiment 4 prepares
。
Embodiment 5
Weigh in the solution that 1.2g octadecylamine is dissolved in 14mL ethanol and 14mL deionized water, be stirred vigorously to after being completely dissolved,
It is added dropwise over 5g tetraethyl orthosilicate, continues the mixed solution that stirs to obtain, weigh 0.52g nickel nitrate, be dissolved in above-mentioned mixing molten
In liquid, Ni/Si mol ratio is 0.074, at room temperature continue stirring 20h, it is thus achieved that aaerosol solution be filtered, washed and dried
After, the lower 550 DEG C of calcining 4h of air atmosphere, heating rate is 1 DEG C/min；It is subsequently placed in miniature fixed-bed quartz reactor,
700 DEG C of pure H2Reduction 1h, H under ambient conditions2Flow velocity is 15mL/min, to obtain final product.
Catalysis activity test method, with embodiment 1, the results are shown in Table 5.
Methane dry reforming catalyst activity test (700～800 DEG C) that table 5 embodiment 5 prepares
。
Embodiment 6
Weigh in the solution that 1.2g dodecyl amine is dissolved in 14mL ethanol and 14mL deionized water, be stirred vigorously to after being completely dissolved,
It is added dropwise over 5g tetraethyl orthosilicate, continues the mixed solution that stirs to obtain, weigh 1.0468g nickel nitrate, be dissolved in above-mentioned mixing
In solution, Ni/Si mol ratio is 0.15, at room temperature continue stirring 22h, it is thus achieved that aaerosol solution through filtration, wash and do
After dry, the lower 600 DEG C of calcining 4h of air atmosphere, heating rate is 1 DEG C/min；It is subsequently placed in miniature fixed-bed quartz reactor,
At 700 DEG C of pure H2Reduction 1h, H under ambient conditions2Flow velocity is 15mL/min, to obtain final product.
Catalysis activity test method, with embodiment 1, the results are shown in Table 6.
Methane dry reforming catalyst activity test (700～800 DEG C) that table 6 embodiment 6 prepares
。
Embodiment 7
Weigh in the solution that 1.2g dodecyl amine is dissolved in 14mL ethanol and 14mL deionized water, be stirred vigorously to after being completely dissolved,
It is added dropwise over 5g tetraethyl orthosilicate, continues the mixed solution that stirs to obtain, weigh 0.6978g nickel acetate, be dissolved in above-mentioned mixing
In solution, Ni/Si mol ratio is 0.1, at room temperature continue stirring 21h, it is thus achieved that aaerosol solution be filtered, washed and dried
After, the lower 550 DEG C of calcining 4h of air atmosphere, heating rate is 1 DEG C/min；It is subsequently placed in miniature fixed-bed quartz reactor,
700 DEG C of pure H2Reduction 1h, H under ambient conditions2Flow velocity is 15mL/min, to obtain final product.
Catalysis activity test method, with embodiment 1, the results are shown in Table 7.
Methane dry reforming catalyst activity test (700～800 DEG C) that table 7 embodiment 7 prepares
。
Embodiment 8
Weigh in the solution that 1.2g dodecyl amine is dissolved in 14mL ethanol and 14mL deionized water, be stirred vigorously to after being completely dissolved,
It is added dropwise over 5g tetraethyl orthosilicate, continues the mixed solution that stirs to obtain, weigh 0.52g Nickel dichloride., be dissolved in above-mentioned mixing molten
In liquid, Ni/Si mol ratio is 0.074, at room temperature continue stirring 21h, it is thus achieved that aaerosol solution be filtered, washed and dried
After, the lower 600 DEG C of calcining 4h of air atmosphere, heating rate is 1 DEG C/min；It is subsequently placed in miniature fixed-bed quartz reactor,
700 DEG C of pure H2Reduction 1h, H under ambient conditions2Flow velocity is 15mL/min, to obtain final product.
Catalysis activity test method, with embodiment 1, the results are shown in Table 8.
Methane dry reforming catalyst activity test (700～800 DEG C) that table 8 embodiment 8 prepares
。
Embodiment 9
Weigh in the solution that 1.2g octadecylamine is dissolved in 14mL ethanol and 14mL deionized water, be stirred vigorously to after being completely dissolved,
It is added dropwise over 5g tetraethyl orthosilicate, continues the mixed solution that stirs to obtain, weigh the nickel acetylacetonate of 0.52g, be dissolved in above-mentioned
In mixed solution, Ni/Si mol ratio is 0.074, at room temperature continue stirring 21h, it is thus achieved that aaerosol solution through filtration, washing
After drying, the lower 500 DEG C of calcining 4h of air atmosphere, heating rate is 1 DEG C/min；It is subsequently placed in miniature fixed-bed quartz reactor
In, at 700 DEG C of pure H2Reduction 1h, H under ambient conditions2Flow velocity is 30mL/min, to obtain final product.
Catalysis activity test method, with embodiment 1, the results are shown in Table 9.
Methane dry reforming catalyst activity test (700～800 DEG C) that table 9 embodiment 9 prepares
。
Embodiment 10
Weigh in the solution that 1.2g octadecylamine is dissolved in 14mL ethanol and 14mL deionized water, be stirred vigorously to after being completely dissolved,
It is added dropwise over 5g tetraethyl orthosilicate, continues the mixed solution that stirs to obtain, weigh 0.52g nickel acetylacetonate, be dissolved in above-mentioned mixed
Closing in solution, Ni/Si mol ratio is 0.074, at room temperature continues stirring 22h, it is thus achieved that aaerosol solution through filtering, washing and
After drying, the lower 500 DEG C of calcining 4h of air atmosphere, heating rate is 1 DEG C/min；It is subsequently placed in miniature fixed-bed quartz reactor
In, at 700 DEG C of pure H2Reduction 1h, H under ambient conditions2Flow velocity is 15mL/min, to obtain final product.
Catalysis activity test method, with embodiment 1, the results are shown in Table 10.
Methane dry reforming catalyst activity test (700～800 DEG C) that table 10 embodiment 10 prepares
。
Embodiment 11
Weigh in the solution that 1.2g dodecyl amine is dissolved in 14mL ethanol and 14mL deionized water, be stirred vigorously to after being completely dissolved,
It is added dropwise over 5g tetraethyl orthosilicate, continues the mixed solution that stirs to obtain, weigh 0.6978g nickel nitrate, be dissolved in above-mentioned mixing
In solution, Ni/Si mol ratio is 0.1, at room temperature continue stirring 22h, it is thus achieved that aaerosol solution be filtered, washed and dried
After, the lower 700 DEG C of calcining 4h of air atmosphere, heating rate is 1 DEG C/min；It is subsequently placed in miniature fixed-bed quartz reactor,
500 DEG C of pure H2Reduction 1h, H under ambient conditions2Flow velocity is 20mL/min, to obtain final product.
Catalysis activity test method, with embodiment 1, the results are shown in Table 11.
Methane dry reforming catalyst activity test (700～800 DEG C) that table 11 embodiment 11 prepares
。
Embodiment 12
Weigh in the solution that 1.2g dodecyl amine is dissolved in 14mL ethanol and 14mL deionized water, be stirred vigorously to after being completely dissolved,
It is added dropwise over 5g tetraethyl orthosilicate, continues the mixed solution that stirs to obtain, weigh 0.6978g nickel nitrate, be dissolved in above-mentioned mixing
In solution, Ni/Si mol ratio is 0.1, at room temperature continue stirring 22h, it is thus achieved that aaerosol solution be filtered, washed and dried
After, the lower 700 DEG C of calcining 4h of air atmosphere, heating rate is 1 DEG C/min；It is subsequently placed in miniature fixed-bed quartz reactor,
600 DEG C of pure H2Reduction 1h, H under ambient conditions2Flow velocity is 25mL/min, to obtain final product.
Catalysis activity test method, with embodiment 1, the results are shown in Table 12.
Methane dry reforming catalyst activity test (700～800 DEG C) that table 12 embodiment 12 prepares
。
Embodiment 13
Weigh in the solution that 1.2g dodecyl amine is dissolved in 14mL ethanol and 14mL deionized water, be stirred vigorously to after being completely dissolved,
It is added dropwise over 5g tetraethyl orthosilicate, continues the mixed solution that stirs to obtain, weigh 0.3489g nickel nitrate, be dissolved in above-mentioned mixing
In solution, Ni/Si mol ratio is 0.05, at room temperature continue stirring 24h, it is thus achieved that aaerosol solution through filtration, wash and do
After dry, the lower 700 DEG C of calcining 6h of air atmosphere, heating rate is 1 DEG C/min；It is subsequently placed in miniature fixed-bed quartz reactor,
At 600 DEG C of pure H2Reduction 1h, H under ambient conditions2Flow velocity is 25mL/min, to obtain final product.
Catalysis activity test method, with embodiment 1, the results are shown in Table 13.
Methane dry reforming catalyst activity test (700～800 DEG C) that table 13 embodiment 13 prepares
。
Claims (5)
1. the preparation method of the methane dry reforming catalyst of an one-step synthesis efficient stable, it is characterised in that the method is by following
Step is carried out:
A. the preparation of catalyst: weigh in the solution that neutral amine is dissolved in ethanol and deionized water, is stirred vigorously to after being completely dissolved,
Being added dropwise over tetraethyl orthosilicate, neutral amine and tetraethyl orthosilicate mol ratio are 1:0.27, continue to stir mixing is molten
Liquid；Weighing nickel precursor salt, be dissolved in above-mentioned mixed solution, Ni/Si mol ratio is 0.025～0.15, at room temperature continues to stir
Mix 20～24h, it is thus achieved that aaerosol solution after being filtered, washed and dried, under air atmosphere 500～700 DEG C calcining 4～6h,
Heating rate is 1 DEG C/min；
B. the reduction of catalyst: by step A prepare catalyst be placed in miniature fixed-bed quartz reactor, with flow velocity be 15～
The pure H of 30mL/min2, under the conditions of 500～700 DEG C, reduction 1h, obtains the methane dry reforming catalyst of efficient stable.
Preparation method the most according to claim 1, it is characterised in that in the solution of described ethanol and deionized water ethanol and
The volume ratio of deionized water is 1:1.
Preparation method the most according to claim 1, it is characterised in that described neutral amine be dodecyl amine, tetradecylamine, ten
One in six alkanamines, octadecylamine.
Preparation method the most according to claim 1, it is characterised in that described nickel precursor salt is nickel nitrate, nickel acetate, chlorine
Change the one in nickel, nickel acetylacetonate.
5. the methane dry reforming catalyst of the efficient stable that the preparation method described in claims 1 to 3 any one prepares, it is special
Levy and be that nickel particle size is 2～5nm.
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