CN106238103A - Nitrile-group modification SiO2nano tube supported cobalt-based nanocatalyst and preparation method thereof - Google Patents
Nitrile-group modification SiO2nano tube supported cobalt-based nanocatalyst and preparation method thereof Download PDFInfo
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- 238000012986 modification Methods 0.000 title claims abstract description 61
- 230000004048 modification Effects 0.000 title claims abstract description 61
- 125000002560 nitrile group Chemical group 0.000 title claims abstract description 59
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 50
- 239000010941 cobalt Substances 0.000 title claims abstract description 50
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 25
- 239000002071 nanotube Substances 0.000 claims abstract description 110
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 76
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 76
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 76
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 76
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 76
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000011148 porous material Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 15
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000007598 dipping method Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000003426 co-catalyst Substances 0.000 claims description 18
- 229960004756 ethanol Drugs 0.000 claims description 16
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 238000002474 experimental method Methods 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000003863 metallic catalyst Substances 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000008187 granular material Substances 0.000 abstract description 9
- 238000004458 analytical method Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- BKXAWQXZFFNQHY-UHFFFAOYSA-N C(C)O.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] Chemical compound C(C)O.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] BKXAWQXZFFNQHY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
- B01J31/0248—Nitriles
-
- B01J35/30—
-
- B01J35/40—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
Abstract
The invention discloses a kind of nitrile-group modification SiO2Nano tube supported cobalt-based nanocatalyst and preparation method thereof, uses nitrile-group modification SiO2Nanotube, as carrier, prepares the nanocatalyst of Supported Co granule, nitrile-group modification SiO by alcohol dipping method2Nanotube, using cetyl trimethylammonium bromide as template, prepares SiO by sol-gal process2Nanotube, then reacts with azodiisobutyronitrile and obtains；SiO2The external diameter of nanotube is 200～300nm, a length of 900～1200nm, and thickness of pipe wall is 50～100nm；Mesoporous pore size is 3.2～8.6nm, and carrier specific surface area is 600～1100m2/ g, pore volume is 0.5～1.1cm3/ g, the mass loading amount of cobalt metal is 8～16.5%.The nanocatalyst that the present invention prepares has that good mechanical property, Stability Analysis of Structures, specific surface area be big, nano cobalt granule is uniformly dispersed, and the preferable advantage of stability, its size uniformity is controlled, and preparation method step is simple, it is simple to operation, it is adaptable to large batch of production.
Description
Technical field
The present invention relates to catalyst synthesis and technical field of nano material, particularly to a kind of nitrile-group modification SiO2Nanotube
Supported Co base nano-catalyst and preparation method thereof.
Background technology
Cobalt-base catalyst can carry out Fischer-Tropsch synthesis under relatively low reaction temperature, and the reactivity of Yin Qigao is higher
The selectivity of straight chain heavy hydrocarbon, low water gas shift reaction and receive much concern, the research for cobalt-base catalyst mainly collects
In at the aspect such as structure of carrier, the auxiliary agent of interpolation and catalyst.Owing to cobalt is higher relative to ferrum price, and cobalt resource is the most very
Limited, so improving the activity of catalyst and life-span while reducing the consumption of cobalt and to improve the selectivity of product be current
The emphasis of researcher research and focus.
In prior art, the catalytic performance of cobalt-base catalyst improves generally by the mode of porous material loading, many
Porous materials is frequently with mesoporous silicon oxide, mesoporous aluminium sesquioxide, mesoporous TiO 2, porous molecular screen, lamella porous graphite
The inorganic material such as alkene are as carrier, owing to, in the case of dispersion is identical, above-mentioned inorganic porous material is as carrier, and it compares table
Area, the character such as aperture and duct limits the ultimate load of cobalt；If the load capacity of cobalt is excessive simultaneously, then it is easy to assemble
Agglomerating, can reduce catalyst activity on the contrary, therefore, research good mechanical property, Stability Analysis of Structures, carrier material that specific surface area is big are
Problem demanding prompt solution.
Furthermore, in the loaded catalyst not obtained the method for vehicle treated, nano cobalt granule dispersion is uneven, stable
Property is poor.Thus, carrier surface is carried out different organic group modification and can improve the load dispersibility of catalyst carrier,
Catalyst granules can be anchored on carrier the profit of stability and the metallic cobalt being favorably improved catalyst by organic group simultaneously
By rate.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of research good mechanical property, Stability Analysis of Structures, specific surface area be big, cobalt
Granule finely dispersed nitrile-group modification SiO2Nano tube supported cobalt-based nanocatalyst.
Accordingly, another technical problem that the invention solves the problems that be to provide a kind of research good mechanical property, Stability Analysis of Structures,
Specific surface area is big, cobalt granule finely dispersed nitrile-group modification SiO2The preparation method of nano tube supported cobalt-based nanocatalyst.
In order to solve above-mentioned technical problem, the technical scheme is that
The invention provides a kind of nitrile-group modification SiO2Nano tube supported cobalt-based nanocatalyst, carrier is SiO2Nanotube,
The metallic catalyst of load is Co catalysts, SiO2Nanotube is using cetyl trimethylammonium bromide as template, by molten
Sol-gel prepares SiO2Nanotube, then reacts with azodiisobutyronitrile and obtains；With metallic cobalt component as core, nitrile-group modification
SiO2Nanotube is shell；SiO2The external diameter of nanotube is 200～400nm, a length of 10～22nm, and thickness of pipe wall is 50～100nm；
Being rich in mesoporous on the tube wall of nanotube, its aperture is 3.2～25nm, and carrier specific surface area is 600～1000m2/ g, pore volume is
1.2～1.8cm3/ g, the mass loading amount of cobalt metal is 8～16.5%.
As further technical scheme, Co catalysts is supported on nitrile-group modification SiO2In the pipe of nanotube.
As further technical scheme, Co catalysts loads to nitrile-group modification SiO by volume impregnation method2Nanotube
On.
The invention provides a kind of nitrile-group modification SiO2The preparation method of nano tube supported cobalt-based nanocatalyst, including:
a)SiO2The preparation of nanotube, b) load of Co catalysts；
The load of Co catalysts includes:
1) by appropriate Co (NO3)2·6H2O is dissolved in the dehydrated alcohol obtained by water saturation experiment, obtains cobalt nitrate
Ethanol solution；
2) by baked nitrile-group modification SiO2Nano-tube support impregnated in ethanol solution, after dipping, then changes to itrile group
Property SiO2Deionized water is added on the surface of nanotube；
3), after the catalyst sample evacuation on a rotary evaporator that will obtain, at room temperature place aging 24h, then exist
320 DEG C of dry 12h in Muffle furnace；
4) by dried catalyst sample at tube furnace N2In atmosphere, 620 DEG C of roasting 5h, obtain catalyst prod.
As further technical scheme, the step 2 of the load of Co catalysts) in, the pickup of ethanol solution is SiO2
The 2/3 of nanotube pore volume.
As further technical scheme, the step 2 of the load of Co catalysts) in, the amount of the deionized water of addition is
SiO2The 1/2 of nanotube pore volume.
As further technical scheme, SiO2The preparation of nanotube includes:
1) preparation of template, joins the sodium chloride solution that mass concentration is 3% by cetyl trimethylammonium bromide
In, stir 5～8h under 25～30 DEG C of water bath condition, be added dropwise to the ammonia that a certain amount of mass concentration is 25%；
2) preparation of nanotube, continues limit stirring and adds tetraethyl orthosilicate, continuously stirred 5～8h, after being placed in room temperature standing,
By solution through filtration, washing, 80 DEG C of dry 5h of vacuum.
3) by dried sample at tube furnace N2800 DEG C of roasting 5h in atmosphere, prepare SiO2Nanotube.
As further technical scheme, SiO2The step 2 of the preparation of nanotube) in, the feed postition of tetraethyl orthosilicate
For being quickly added dropwise over.
As further technical scheme, SiO2The step 2 of the preparation of nanotube) in, room temperature time of repose be 10～
15h, slurry and ethanol wash 2 times respectively.
As further technical scheme, SiO2The surface nitrile-group modification of nanotube processes and includes:
1) in dehydrated alcohol, SiO is added2Nanotube, azodiisobutyronitrile, seal after being stirred well to be completely dispersed, put
React while stirring in the water bath with thermostatic control of 60 DEG C；
2), after reaction 6h, room temperature places cooling, and vacuum filters, and then washs respectively 2 times with dehydrated alcohol, oxolane,
80 DEG C of dry 5h of vacuum；
3) by dried sample at tube furnace N2800 DEG C of roasting 5h in atmosphere, prepare nitrile-group modification SiO2Nanotube.
The present invention uses nitrile-group modification SiO2Nanotube, as carrier, prepares receiving of Supported Co granule by alcohol dipping method
Rice catalyst, prepared nanocatalyst has big excellent of good mechanical property, Stability Analysis of Structures, specific surface area load capacity big, cobalt
Point, its size uniformity is controlled, and preparation method step is simple, it is simple to operation, it is adaptable to large batch of production；Nitrile-group modification SiO2Receive
Mitron, using cetyl trimethylammonium bromide as template, prepares SiO by sol-gal process2Nanotube, then with azo
Bis-isobutyronitrile reaction obtains；With metallic cobalt component as core, nitrile-group modification SiO2Nanotube is shell；SiO2The external diameter of nanotube is 200
～300nm, a length of 900～1200nm, thickness of pipe wall is 50～100nm；Being rich in mesoporous on the tube wall of nanotube, its aperture is
3.2～8.6nm, carrier specific surface area is 600～1100m2/ g, pore volume is 0.5～1.1cm3/ g, the mass loading of cobalt metal
Amount is 8～16.5%.
To SiO2The surface of nano-tube support processes nitrile-group modification, nano cobalt granule dispersion in the loaded catalyst obtained
Uniformly, stability is preferable；Improve cobalt granule at SiO2The load dispersibility of nanotube and steadiness, improve nano-catalytic
The stability of agent and the utilization rate of metallic cobalt.
Detailed description of the invention
Below the detailed description of the invention of the present invention is described further.At this it should be noted that implement for these
The explanation of mode is adapted to assist in and understands the present invention, but is not intended that limitation of the invention.Additionally, invention described below
Just can be mutually combined as long as technical characteristic involved in each embodiment does not constitutes conflict each other.
Embodiment 1
SiO2The preparation of nanotube
Weigh 2.50g cetyl trimethylammonium bromide and join in the sodium chloride solution that 100ml mass concentration is 2%,
Stir 5h under 25 DEG C of water bath condition, be added dropwise to the ammonia that mass concentration is 25% of 6ml；Continue limit stirring and add the positive silicon of 2.5ml
Acetoacetic ester, continuously stirred 5h, after being placed in room temperature standing 10h, washs 2 times, 80 DEG C of vacuum by solution through filtration, water and ethanol respectively
It is dried 5h；By dried sample at tube furnace N2800 DEG C of roasting 5h in atmosphere, prepare SiO2Nanotube 1.
SiO prepared by the present embodiment2Nanotube 1, its external diameter is 230～300nm, a length of 960～1200nm, thickness of pipe wall
It is about 100nm；Being rich in mesoporous on the tube wall of nanotube, its aperture is 6.2～8.6nm, and carrier specific surface area is about 600m2/ g,
Pore volume is about 0.5cm3/g。
SiO2The surface nitrile-group modification of nanotube processes
The SiO that will prepare2Nanotube 1 and 6.0g azodiisobutyronitrile joins in 100ml dehydrated alcohol, seals fully
Stir to after being completely dispersed, be placed in the water bath with thermostatic control of 60 DEG C and react while stirring；After reaction 6h, room temperature places cooling, vacuum
Filter, then wash respectively 2 times with dehydrated alcohol, oxolane, 80 DEG C of dry 5h of vacuum；By dried sample at tube furnace
N2800 DEG C of roasting 5h in atmosphere, prepare nitrile-group modification SiO2Nanotube 1.
The load of Co catalysts
Weigh 5.0gCo (NO3)2·6H2O is dissolved in the 50ml dehydrated alcohol obtained by water saturation experiment, obtains nitric acid
The ethanol solution of cobalt；Take appropriate baked nitrile-group modification SiO2Nanotube 1 carrier impregnation is in this ethanol solution, and pickup is
SiO2The 2/3 of nanotube 1 pore volume.After dipping, then to nitrile-group modification SiO2Deionized water is added on the surface of nanotube 1, addition
The amount of deionized water is SiO2The 1/2 of nanotube pore volume；After the catalyst sample evacuation on a rotary evaporator that will obtain,
At room temperature place aging 24h, then 320 DEG C of dry 12h in Muffle furnace；By dried catalyst sample at tube furnace N2
620 DEG C of roasting 5h in atmosphere, obtain catalyst prod 1.
The nitrile-group modification SiO that the present embodiment obtains2Nano tube supported cobalt-based nanocatalyst product 1, the matter of its cobalt metal
Amount load capacity is about 8%.
Embodiment 2
SiO2The preparation of nanotube
Use the SiO of embodiment 1 preparation2Nanotube 1.
SiO2The surface nitrile-group modification of nanotube processes
Use the nitrile-group modification SiO of embodiment 1 preparation2Nanotube 1.
The load of Co catalysts
Weigh 10.0gCo (NO3)2·6H2O is dissolved in the 50ml dehydrated alcohol obtained by water saturation experiment, obtains nitric acid
The ethanol solution of cobalt；Take appropriate baked nitrile-group modification SiO2Nanotube 1 carrier impregnation is in this ethanol solution, and pickup is
SiO2The 2/3 of nanotube 1 pore volume.After dipping, then to nitrile-group modification SiO2Deionized water is added on the surface of nanotube 1, addition
The amount of deionized water is SiO2The 1/2 of nanotube pore volume；After the catalyst sample evacuation on a rotary evaporator that will obtain,
At room temperature place aging 24h, then 320 DEG C of dry 12h in Muffle furnace；By dried catalyst sample at tube furnace N2
620 DEG C of roasting 5h in atmosphere, obtain catalyst prod 2.
The nitrile-group modification SiO that the present embodiment obtains2Nano tube supported cobalt-based nanocatalyst product 2, the matter of its cobalt metal
Amount load capacity is about 10.5%.
Embodiment 3
SiO2The preparation of nanotube
Weigh 3.50g cetyl trimethylammonium bromide and join in the sodium chloride solution that 100ml mass concentration is 2%,
Stir 8h under 30 DEG C of water bath condition, be added dropwise to the ammonia that mass concentration is 25% of 6ml；Continue limit stirring and add the positive silicon of 3.0ml
Acetoacetic ester, continuously stirred 8h, after being placed in room temperature standing 10h, washs 2 times, 80 DEG C of vacuum by solution through filtration, water and ethanol respectively
It is dried 6h；By dried sample at tube furnace N2800 DEG C of roasting 5h in atmosphere, prepare SiO2Nanotube 2.
SiO prepared by the present embodiment2Nanotube 2, its external diameter is 200～260nm, a length of 900～1100nm, thickness of pipe wall
For 50nm；Being rich in mesoporous on the tube wall of nanotube, its aperture is 3.2～6.5nm, and carrier specific surface area is 1100m2/ g, pore volume
Amass as 1.1cm3/g。
SiO2The surface nitrile-group modification of nanotube processes
The SiO that will prepare2Nanotube 2 and 10g azodiisobutyronitrile joins in 100ml dehydrated alcohol, seals fully
Stir to after being completely dispersed, be placed in the water bath with thermostatic control of 60 DEG C and react while stirring；After reaction 6h, room temperature places cooling, vacuum
Filter, then wash respectively 2 times with dehydrated alcohol, oxolane, 80 DEG C of dry 5h of vacuum；By dried sample at tube furnace
N2800 DEG C of roasting 5h in atmosphere, prepare nitrile-group modification SiO2Nanotube 2.
The load of Co catalysts
Weigh 5.0gCo (NO3)2·6H2O is dissolved in the 50ml dehydrated alcohol obtained by water saturation experiment, obtains nitric acid
The ethanol solution of cobalt；Take appropriate baked nitrile-group modification SiO2Nanotube 2 carrier impregnation is in this ethanol solution, and pickup is
SiO2The 2/3 of nanotube pore volume.After dipping, then to nitrile-group modification SiO2Deionized water is added on the surface of nanotube 2, addition
The amount of deionized water is SiO2The 1/2 of nanotube pore volume；After the catalyst sample evacuation on a rotary evaporator that will obtain,
At room temperature place aging 24h, then 320 DEG C of dry 12h in Muffle furnace；By dried catalyst sample at tube furnace N2
620 DEG C of roasting 5h in atmosphere, obtain catalyst prod 3.
The nitrile-group modification SiO that the present embodiment obtains2Nano tube supported cobalt-based nanocatalyst product 3, the matter of its cobalt metal
Amount load capacity is about 15%.
Embodiment 4
SiO2The preparation of nanotube
Use the SiO of embodiment 3 preparation2Nanotube 2.
SiO2The surface nitrile-group modification of nanotube processes
Use the nitrile-group modification SiO of embodiment 3 preparation2Nanotube 2.
The load of Co catalysts
Weigh 10.0gCo (NO3)2·6H2O is dissolved in the 50ml dehydrated alcohol obtained by water saturation experiment, obtains nitric acid
The ethanol solution of cobalt；Take appropriate baked nitrile-group modification SiO2Nanotube 2 carrier impregnation is in this ethanol solution, and pickup is
SiO2The 2/3 of nanotube 2 pore volume.After dipping, then to nitrile-group modification SiO2Deionized water is added on the surface of nanotube 2, addition
The amount of deionized water is SiO2The 1/2 of nanotube pore volume；After the catalyst sample evacuation on a rotary evaporator that will obtain,
At room temperature place aging 24h, then 320 DEG C of dry 12h in Muffle furnace；By dried catalyst sample at tube furnace N2
620 DEG C of roasting 5h in atmosphere, obtain catalyst prod 4.
The nitrile-group modification SiO that the present embodiment obtains2Nano tube supported cobalt-based nanocatalyst product 4, the matter of its cobalt metal
Amount load capacity is about 16.5%.
Above embodiments of the present invention are explained in detail, but the invention is not restricted to described embodiment.Right
For those skilled in the art, in the case of without departing from the principle of the invention and spirit, these embodiments are carried out many
Kind changes, revises, replaces and modification, still falls within protection scope of the present invention.
Claims (10)
1. a nitrile-group modification SiO2Nano tube supported cobalt-based nanocatalyst, it is characterised in that carrier is nitrile-group modification SiO2Receive
Mitron, the metallic catalyst of load is Co catalysts, described SiO2Nanotube is using cetyl trimethylammonium bromide as template
Agent, prepares SiO by sol-gal process2Nanotube, then reacts with azodiisobutyronitrile and obtains；With metallic cobalt component as core,
Described nitrile-group modification SiO2Nanotube is shell；Described SiO2The external diameter of nanotube is 200～400nm, a length of 10～22nm, pipe
Wall thickness is 50～100nm；Being rich in mesoporous on the tube wall of nanotube, its aperture is 3.2～25nm, carrier specific surface area be 600～
1000m2/ g, pore volume is 0.5～1.1cm3/ g, the mass loading amount of cobalt metal is 8～16.5%.
Nitrile-group modification SiO the most according to claim 12Nano tube supported cobalt-based nanocatalyst, it is characterised in that described
Co catalysts is supported on described nitrile-group modification SiO2In the pipe of nanotube.
Nitrile-group modification SiO the most according to claim 22Nano tube supported cobalt-based nanocatalyst, it is characterised in that described
Co catalysts loads to described nitrile-group modification SiO by volume impregnation method2On nanotube.
4. the nitrile-group modification SiO that a kind is prepared as described in claims 1 to 32The method of nano tube supported cobalt-based nanocatalyst,
It is characterized in that, including:
a)SiO2The preparation of nanotube；
b)SiO2The surface nitrile-group modification of nanotube processes
C) load of Co catalysts；
The load of described Co catalysts includes:
1) by appropriate Co (NO3)2·6H2O is dissolved in the dehydrated alcohol obtained by water saturation experiment, obtains the second of cobalt nitrate
Alcoholic solution；
2) by baked nitrile-group modification SiO2Nano-tube support impregnated in described ethanol solution, after dipping, then to nitrile-group modification
SiO2Deionized water is added on the surface of nanotube；
3), after the catalyst sample evacuation on a rotary evaporator that will obtain, aging 24h is at room temperature placed, then in Muffle
320 DEG C of dry 12h in stove；
4) by dried catalyst sample at tube furnace N2In atmosphere, 620 DEG C of roasting 5h, obtain catalyst prod.
Nitrile-group modification SiO the most according to claim 42The preparation method of nano tube supported cobalt-based nanocatalyst, its feature
It is, the step 2 of the load of described Co catalysts) in, the pickup of described ethanol solution is SiO2The 2/ of nanotube pore volume
3。
Nitrile-group modification SiO the most according to claim 42The preparation method of nano tube supported cobalt-based nanocatalyst, its feature
It is, the step 2 of the load of described Co catalysts) in, the amount of the deionized water of addition is SiO2The 1/2 of nanotube pore volume.
Nitrile-group modification SiO the most according to claim 42The preparation method of nano tube supported cobalt-based nanocatalyst, its feature
It is, described SiO2The preparation of nanotube includes:
1) preparation of template, joins in the sodium chloride solution that mass concentration is 3% by cetyl trimethylammonium bromide, and 25
～under 30 DEG C of water bath condition, stir 5～8h, it is added dropwise to the ammonia that a certain amount of mass concentration is 25%；
2) preparation of nanotube, continues limit stirring and adds tetraethyl orthosilicate, continuously stirred 5～8h, after being placed in room temperature standing, by molten
Liquid is through filtration, washing, 80 DEG C of dry 5h of vacuum.
Nitrile-group modification SiO the most according to claim 72The preparation method of nano tube supported cobalt-based nanocatalyst, its feature
It is, described SiO2The step 2 of the preparation of nanotube) in, the feed postition of tetraethyl orthosilicate is for be quickly added dropwise over.
Nitrile-group modification SiO the most according to claim 72The preparation method of nano tube supported cobalt-based nanocatalyst, its feature
It is, described SiO2The step 2 of the preparation of nanotube) in, room temperature time of repose is 10～15h, and slurry and ethanol are respectively
Wash 2 times.
Nitrile-group modification SiO the most according to claim 42The preparation method of nano tube supported cobalt-based nanocatalyst, it is special
Levy and be, described SiO2The surface nitrile-group modification of nanotube processes and includes:
1) in dehydrated alcohol, SiO is added2Nanotube, azodiisobutyronitrile, seal after being stirred well to be completely dispersed, be placed in 60
DEG C water bath with thermostatic control in react while stirring；
2), after reaction 6h, room temperature places cooling, and vacuum filters, and then washs 2 times respectively with dehydrated alcohol, oxolane, vacuum
80 DEG C of dry 5h；
3) by dried sample at tube furnace N2800 DEG C of roasting 5h in atmosphere, prepare nitrile-group modification SiO2Nanotube.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002080885A1 (en) * | 2001-04-03 | 2002-10-17 | University Of Florida | Detoxification and decontamination using nanotechnology therapy |
| CN101856626A (en) * | 2010-05-07 | 2010-10-13 | 上海电力学院 | Preparation method of catalyst of carbon multi-wall nano tube loaded metal platinum nano particle with surface nitrile-group modification |
| WO2015080452A1 (en) * | 2013-11-28 | 2015-06-04 | 한국화학연구원 | Method for storing activated fischer-tropsch synthesis catalyst |
-
2016
- 2016-07-29 CN CN201610609330.XA patent/CN106238103A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002080885A1 (en) * | 2001-04-03 | 2002-10-17 | University Of Florida | Detoxification and decontamination using nanotechnology therapy |
| CN101856626A (en) * | 2010-05-07 | 2010-10-13 | 上海电力学院 | Preparation method of catalyst of carbon multi-wall nano tube loaded metal platinum nano particle with surface nitrile-group modification |
| WO2015080452A1 (en) * | 2013-11-28 | 2015-06-04 | 한국화학연구원 | Method for storing activated fischer-tropsch synthesis catalyst |
Non-Patent Citations (3)
| Title |
|---|
| 唐火强: ""硅纳米管负载钴基、钌基催化剂的费-托合成催化性能研究"", 《中国优秀硕士学位论文全文数据库（工程科技I辑）》 * |
| 翟秀静 等: "《还原与沉淀》", 31 July 2008, 冶金工业出版社 * |
| 靳蓓 等: ""二氧化硅纳米管的制备及表征"", 《化工新型材料》 * |
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