CN101288851A - SBA-15 loaded high dispersion nickel catalyst modified by hole wall carbon and its preparation method - Google Patents
SBA-15 loaded high dispersion nickel catalyst modified by hole wall carbon and its preparation method Download PDFInfo
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- CN101288851A CN101288851A CNA2007100216449A CN200710021644A CN101288851A CN 101288851 A CN101288851 A CN 101288851A CN A2007100216449 A CNA2007100216449 A CN A2007100216449A CN 200710021644 A CN200710021644 A CN 200710021644A CN 101288851 A CN101288851 A CN 101288851A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 134
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000006185 dispersion Substances 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 239000000969 carrier Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000007868 Raney catalyst Substances 0.000 claims description 19
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 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 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 6
- 239000003595 mist Substances 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 33
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 229910052759 nickel Inorganic materials 0.000 abstract description 13
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 10
- 239000011148 porous material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005034 decoration Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 27
- 230000009467 reduction Effects 0.000 description 15
- 239000012153 distilled water Substances 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 11
- 150000002739 metals Chemical class 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a high-dispersion nickel catalyst loaded by SBA-15 with pore wall decorated by carbon and a preparation method thereof. The SBA-15 which is provided with a pore wall that is decorated by carbon is synthesized by taking the P123 as a template and roasted by inert gases, so as to lead the gained SBA-15 to contain little carbon (accounting for about 3% of the mass percentage), thus having decoration effects on the surface of the gained SBA-15. Compared with normal SBA-15 carriers, the nickel catalyst prepared by taking the SBA-15 with the pore wall decorated by the carbon as the carrier has higher nickel surface and nickel dispersion. The catalyst of the invention is used for toluene hydrogenation and leads the reaction temperature to be reduced by 40-75 DEG C.
Description
One, technical field:
The present invention relates to a kind of high dispersing nickel catalyst and preparation method thereof of SBA-15 load of modified by hole wall carbon.
Two, background technology:
Industrial Raney nickel can be used for hydrogenation, reformation and hydrocarbon synthetic reaction (U.S. Pat 4,142,962).Typical hydrogenation reaction comprises (U.S. Pat 3,868,332) such as aromatic hydrogenation such as hydrogenation of olefins system saturated hydrocarbons, benzene and toluene.Traditional nickel catalyst carried oxide such as SiO that is to use high-ratio surface
2, Al
2O
3Deng what prepare for the carrier impregnation nickel salt.Studies show that the effective surface area of metallic nickel is directly related on nickel catalyst carried catalytic activity and the catalyst, the surface area of nickel is big more on the unit mass catalyst, and its catalytic activity is high more, catalyst life also long more (U.S. Pat 3,868,332).And the load capacity of nickel and the decentralization of nickel are directly proportional on the nickel surface area of unit mass catalyst and the catalyst.The decentralization of so-called metal is meant the real surface ratio long-pending and desirable, the metal surface area when individual layer disperses of the metal of unit mass.Therefore, explore high capacity amount and high-dispersion loading type metallic nickel Preparation of catalysts method, be the hot subject in Preparation of Catalyst field always.
It is the pure silicon mesopore material of representative with MCM-41 that people in 1992 have synthesized.Thereafter, mesopore materials such as HMS, SBA-15 and KIT-1 also grow up thereupon.These materials are compared with traditional amorphous silica, have specific area height, pore distribution concentration, the aperture is bigger and architectural feature such as adjustable, have a good application prospect as catalyst carrier.At present, methods such as directly synthetic, dipping and ion-exchange are arranged for the preparing carriers metallic catalyst with the mesopore material, but all there are some defectives in these methods.For example, the ion-exchange content of metal is low; The infusion process metallic easily stops up the duct; Direct He Cheng supported catalyst pore structure instability etc.Therefore, for utilizing the design feature of mesopore material better, be necessary the method by changing the metal load or on the basis that does not change carrier structure, carrier surface carried out modification, to obtain higher load amount and high-dispersion loading type metallic catalyst.
SBA-15 is a kind of catalyst carrier that has a good application prospect.But it is the pure silicon material, and mesomorphism is unfavorable for the dispersion of metal on its surface.Therefore, about how the metallic high degree of dispersion being had a large amount of research to the SBA-15 surface.For example, people such as Cho to SBA-15, are flooded nickel salt with ethylenediamine tetra-acetic acid (EDTA) grafting again, prepare nickel catalyst carried, when nickel content reaches 7.77%, do not detect the characteristic diffraction peak of NiO with X-ray diffraction (XRD) method, show that the decentralization of nickel on this catalyst is very high; And be the catalyst of the identical nickel content that obtains of carrier impregnation with common SBA-15, stronger NiO characteristic diffraction peak is arranged on XRD figure, show that the crystal grain of nickel on this catalyst is bigger, metal dispersity low (Catal.Lett., 2002,81:89).People such as G ó mez-reynoso are carrier with SBA-15, use deposition-deposition method (by the urea OH that hydrolysis produces in the 463K salpeter solution
-Nickel is slowly evenly separated out on the SBA-15 surface) obtain the Raney nickel of high dispersive, when nickel content was 10.3wt%, particle diameter was 2.54nm, and to the aromatic hydrocarbon hydrogenation have high reaction activity and high (Catal.Today, 2005,107-108:926).These methods are compared with common infusion process, improved the decentralization of metallic nickel on the SBA-15 surface, but the preparation method are more loaded down with trivial details, are unfavorable for the industrial implementation of catalyst and reduce production costs.
Three, summary of the invention
The present invention is by the research to SBA-15 mesopore material preparation method, use inert atmosphere roasting SBA-15 presoma when finding preparation, in the SBA-15 that obtains, can contain a spot of carbon, because decomposing, the template agent that these carbon use during by synthetic SBA-15 generates, these carbon are distributed on the hole wall of SBA-15, though they only account for about 3% of finished product SBA-15 quality, but can produce good modification to the SBA-15 surface, can strengthen the interaction between metal species and the carrier, help the dispersion of metal species on carrier.The SBA-15 that modifies through carbon with hole wall is carrier loaded nickel nitrate, again through high-temperature roasting and H
2Nickel decentralization height on the Raney nickel that makes of reduction, metallic nickel surface area are big, the catalyst activity height of unit mass.Can be used for hydrogenation, reforming reaction etc.
Technical scheme of the present invention is as follows:
A kind of high dispersion metal Raney nickel of SBA-15 load of modified by hole wall carbon is characterized by: contain mass percent among the employed SBA-15 and be 3% carbon, the quality percentage composition of metallic nickel is 5~20% in the catalyst.
The SBA-15 that described hole wall is modified through carbon prepares in order to the below method:
P123 is dissolved in H with the template agent
2Among the O, add 2mol/L HCl solution again, behind 35-38 ℃ of stirred in water bath 1h, add ethyl orthosilicate (hereinafter to be referred as TEOS), make that the ratio of each amount is in the system: TEOS: HCl: P123: H
2O=1: 6: 0.017: 166.Continuation is at 35-38 ℃ of stirred in water bath 24h, then in 80 ℃ of following ageing 24h.Filter, room temperature dry the back in slumpability gas at 500 ℃ of roasting 6h, obtain the SBA-15 (abbreviating SBA-15C as) that hole wall is modified through carbon.
Above-mentioned hole wall is in the preparation method of the SBA-15C that carbon is modified, and used inert gas is N
2, Ar, He a kind of or its mist wherein, flow velocity is 60ml/min.
A kind of SBA-15C that modifies through carbon with hole wall is the method for preparing carriers support type high dispersing nickel catalyst.It is that the SBA-15C that will measure joins in the nickel nitrate aqueous solution of metering, stirs 10min, and room temperature is placed 24h, and again at room temperature vacuum drying 24h, 400 ℃ of roasting 4h in the inert gas that flows obtain the nickel catalyst carried of Dark grey then.This Raney nickel contains nickel oxide, need use H before using
2Be reduced to metallic nickel.Reducing condition is: 400 ℃, and 4h, H
2Flow velocity 30ml/min.
The concentration of above-mentioned nickel nitrate aqueous solution is to contain Ni (NO in every 100ml water
3)
26H
2O 7.5~36.5g.
Among the preparation method of above-mentioned high dispersing nickel catalyst, inert gas is N
2, a kind of or its mist among Ar, the He.Flow velocity is 60ml/min.
A kind of SBA-15C that modifies through carbon with hole wall is the method for preparing carriers support type high dispersing nickel catalyst.It is that the SBA-15C that will measure joins in the nickel nitrate aqueous solution of metering, stirs 10min, and room temperature is placed 24h, again at room temperature vacuum drying 24h, then in the H that flows
2Be warming up to 400 ℃ in the atmosphere, roasting 4h, heating rate are 1 ℃/min, H
2Flow is 30ml/min, obtains the load type metal Raney nickel.
The concentration of above-mentioned nickel nitrate aqueous solution is to contain Ni (NO in every 100ml water
3)
26H
2O 7.5~36.5g.
Four, the specific embodiment
The invention will be further described with following embodiment and reference example:
Embodiment 1:
Take by weighing 12.0g P123 and put into beaker, add 90ml H
2O and 360ml 2mol/L HCl at 35-38 ℃ of stirred in water bath 1h, add the 25.5g ethyl orthosilicate, continue at 35-38 ℃ of stirred in water bath 24h, again in 80 ℃ of following ageing 24h; After drying under the filter cake room temperature that filters out, put into and be connected with high-purity N
2Tube furnace at 500 ℃ of following roasting 6h, heating rate is 1 ℃/min, N
2Flow is 60ml/min.Obtain the light grey powder of SBA-15C that hole wall is modified through carbon, surface area 719m
2/ g.
Reference example 1:
Take by weighing 12.0g P123 and put into beaker, add 90ml H
2O and 360ml 2mol/L HCl at 35-38 ℃ of stirred in water bath 1h, then, add the 25.5g ethyl orthosilicate, continue at 35-38 ℃ of stirred in water bath 24h, again in 80 ℃ of following ageing 24h; With the filter cake that filters out with distilled water washing 3 times, after at room temperature drying, put into be connected with air muffle furnace at 500 ℃ of following roasting 6h, heating rate is 1 ℃/min, air mass flow is 60ml/min.Make the SBA-15 powder of white, surface area 747m
2/ g.
X-ray diffraction (XRD), N
2Absorption and transmission electron microscope signs such as (TEM) show that the SBA-15C of the SBA-15 of above-mentioned reference example 1 preparation and embodiment 1 preparation all has the central hole structure of six side's homogeneous, and the aperture is 5.2nm.Thermogravimetric-differential thermal and results of elemental analyses show that the quality percentage composition of carbon is about 3% among the SBA-15C.
Embodiment 2:
Take by weighing 1.30g Ni (NO
3)
26H
2O puts into evaporating dish, adds the stirring of 17.0ml distilled water and makes its dissolving, takes by weighing 5.15g SBA-15C again and adds in the above-mentioned solution, stirs 10min, and room temperature is placed the dry 24h of 24h final vacuum, puts into then and is connected with high-purity N
2Tube furnace in, at 400 ℃ of following roasting 4h, heating rate is 2 ℃/min, N
2Flow is 60ml/min.Obtain the nickel catalyst carried of Dark grey.The quality percentage composition that records Ni in this catalyst is 5.2%.Use H
2The decentralization of determination of adsorption method metallic nickel is 26%, and reduction degree is 100% (Raney nickel H before measuring
2Reduction, reducing condition is 400 ℃, 4h, heating rate are 1 ℃/min, H
2Flow velocity is 30ml/min), H
2Adsorbance 120 μ mol/g-catalyst, active metals surface area 9.4m
2The Ni/g-catalyst.
Reference example 2:
Take by weighing 1.30g Ni (NO
3)
26H
2O puts into evaporating dish, adds the stirring of 17.5ml distilled water and makes its dissolving, takes by weighing 5.0g SBA-15 again and adds in the above-mentioned solution, stir 10min, room temperature is placed the dry 24h of 24h final vacuum, puts into the 400 ℃ of following roasting 4h of muffle furnace that are connected with air then, heating rate is 2 ℃/min, N
2Flow is 60ml/min.Obtain the nickel catalyst carried of Dark grey.The quality percentage composition that records the Ni of this catalyst is 5.1%.Use H
2The decentralization of determination of adsorption method metallic nickel is 12%, and reduction degree is 100% (Raney nickel H before measuring
2Reduction, reducing condition is 400 ℃, 4h, heating rate are 1 ℃/min, H
2Flow velocity is 30ml/min), H
2Adsorbance 55 μ mol/g-catalyst, active metals surface area 4.3m
2The Ni/g-catalyst.
Embodiment 3:
Take by weighing 2.45g Ni (NO
3)
26H
2O puts into evaporating dish, adds the stirring of 17.0ml distilled water and makes its dissolving, takes by weighing 5.15g SBA-15C again and adds in the above-mentioned solution, stirs 10min, and room temperature is placed the dry 24h of 24h final vacuum, puts into then and is connected with high-purity N
2Tube furnace in, at 400 ℃ of following roasting 4h, heating rate is 2 ℃/min, N
2Flow is 60ml/min, obtains the nickel catalyst carried of Dark grey.The Ni content that records this catalyst is 9.0%.Use H
2Determination of adsorption method metallic nickel decentralization is 32%, and reduction degree is 100% (Raney nickel H before measuring
2Reduction, reducing condition is 400 ℃, 4h, heating rate are 1 ℃/min, H
2Flow velocity is 30ml/min), H
2Adsorbance 239 μ mol/g-catalyst, active metals surface area 18.7m
2The Ni/g-catalyst.
Reference example 3:
Take by weighing 2.45g Ni (NO
3)
26H
2O puts into evaporating dish, adds the stirring of 17.5ml distilled water and makes its dissolving, takes by weighing 5.0g SBA-15 again and adds in the above-mentioned solution, stir 10min, room temperature is placed the dry 24h of 24h final vacuum, puts into the muffle furnace that is connected with air then, at 400 ℃ of following roasting 4h, heating rate is 2 ℃/min, N
2Flow is 60ml/min.Obtain the nickel catalyst carried of Dark grey.The quality percentage composition that records the Ni of this catalyst is 8.9%.Use H
2The decentralization of determination of adsorption method metallic nickel is 6%, and reduction degree is 100% (Raney nickel H before measuring
2Reduction, reducing condition is 400 ℃, 4h, heating rate are 1 ℃/min, H
2Flow velocity is 30ml/min), H
2Adsorbance 49 μ mol/g-catalyst, active metals surface area 3.8m
2The Ni/g-catalyst.
Embodiment 4:
Take by weighing 4.37g Ni (NO
3)
26H
2O puts into evaporating dish, adds the stirring of 17.0ml distilled water and makes its dissolving, takes by weighing 5.15g SBA-15C again and adds in the above-mentioned solution, stirs 10min, and room temperature is placed the dry 24h of 24h final vacuum, puts into then and is connected with high-purity N
2Tube furnace in, at 400 ℃ of following roasting 4h, heating rate is 2 ℃/min, N
2Flow is 60ml/min, obtains the nickel catalyst carried of Dark grey.The Ni content that records this catalyst is 15.2%.Use H
2Determination of adsorption method metallic nickel decentralization is 23%, and reduction degree is 100% (Raney nickel H before measuring
2Reduction, reducing condition is 400 ℃, 4h, heating rate are 1 ℃/min, H
2Flow velocity is 30ml/min), H
2Adsorbance 290 μ mol/g-catalyst, active metals surface area 22.7m
2The Ni/g-catalyst.
Reference example 4:
Take by weighing 4.37g Ni (NO
3)
26H
2O puts into evaporating dish, adds the stirring of 17.5ml distilled water and makes its dissolving, takes by weighing 5.0g SBA-15 again and adds in the above-mentioned solution, stir 10min, room temperature is placed the dry 24h of 24h final vacuum, puts into the muffle furnace that is connected with air then, at 400 ℃ of following roasting 4h, heating rate is 2 ℃/min, N
2Flow is 60ml/min.Obtain the nickel catalyst carried of Dark grey.The quality percentage composition that records the Ni of this catalyst is 15.1%.Use H
2The decentralization of determination of adsorption method metallic nickel is 12%, and reduction degree is 100% (Raney nickel H before measuring
2Reduction, reducing condition is 400 ℃, 4h, heating rate are 1 ℃/min, H
2Flow velocity is 30ml/min), H
2Adsorbance 144 μ mol/g-catalyst, active metals surface area 11.3m
2The Ni/g-catalyst.
Embodiment 5:
Take by weighing 6.19g Ni (NO
3)
26H
2O puts into evaporating dish, adds the stirring of 17.0ml distilled water and makes its dissolving, takes by weighing 5.15g SBA-15C again and adds in the above-mentioned solution, stirs 10min, and room temperature is placed the dry 24h of 24h final vacuum, puts into then and is connected with high-purity N
2Tube furnace at 400 ℃ of following roasting 4h, heating rate is 2 ℃/min, N
2Flow is 60ml/min.Obtain the nickel catalyst carried of Dark grey.The quality percentage composition that records the Ni of this catalyst is 20.0%.Use H
2The decentralization of determination of adsorption method metallic nickel is 22%, and reduction degree is 99% (Raney nickel H before measuring
2Reduction, reducing condition is 400 ℃, 4h, heating rate are 1 ℃/min, H
2Flow velocity is 30ml/min), H
2Adsorbance 356 μ mol/g-catalyst, active metals surface area 27.9m
2The Ni/g-catalyst.
Reference example 5:
Take by weighing 6.19g Ni (NO
3)
26H
2O puts into evaporating dish, adds the stirring of 17.5ml distilled water and makes its dissolving, takes by weighing 5.0g SBA-15 again and adds in the above-mentioned solution, stir 10min, room temperature is placed the dry 24h of 24h final vacuum, puts into the muffle furnace that is connected with air then, at 400 ℃ of following roasting 4h, heating rate is 2 ℃/min, N
2Flow is 60ml/min.Obtain the nickel catalyst carried of Dark grey.The quality percentage composition that records the Ni of this catalyst is 20.1%.Use H
2The decentralization of determination of adsorption method metallic nickel is 8%, and reduction degree is 98% (Raney nickel H before measuring
2Reduction, reducing condition is 400 ℃, 4h, heating rate are 1 ℃/min, H
2Flow velocity is 30ml/min), H
2Adsorbance 124 μ mol/g-catalyst, active metals surface area 9.7m
2The Ni/g-catalyst.
Embodiment 6:
Take by weighing 10.62g Ni (NO
3)
26H
2O puts into evaporating dish, adds the stirring of 17.0ml distilled water and makes its dissolving, takes by weighing 5.15g SBA-15C again and adds in the above-mentioned solution, stirs 10min, and room temperature is placed the dry 24h of 24h final vacuum, puts into then and is connected with high-purity N
2Tube furnace in, at 400 ℃ of following roasting 4h, heating rate is 2 ℃/min, N
2Flow is 60ml/min.Obtain the nickel catalyst carried of grey.The quality percentage composition that records the Ni of this catalyst is 29.9%.Use H
2The decentralization of determination of adsorption method metallic nickel is 7%, and reduction degree is 100% (Raney nickel H before measuring
2Reduction, reducing condition is 400 ℃, 4h, heating rate are 1 ℃/min, H
2Flow velocity is 30ml/min), H
2Adsorbance 163 μ mol/g-catalyst, active metals surface area 12.8m
2The Ni/g-catalyst.
Reference example 6:
Take by weighing 10.62g Ni (NO
3)
26H
2O puts into evaporating dish, adds the stirring of 17.5ml distilled water and makes its dissolving, takes by weighing 5.0g SBA-15 again and adds in the above-mentioned solution, stir 10min, room temperature is placed the dry 24h of 24h final vacuum, puts into the muffle furnace that is connected with air then, at 400 ℃ of following roasting 4h, heating rate is 2 ℃/min, N
2Flow is 601/min.Obtain the nickel catalyst carried of Dark grey.The quality percentage composition that records the Ni of this catalyst is 30.2%.Use H
2The decentralization of determination of adsorption method metallic nickel is 6%, and reduction degree is 100% (Raney nickel H before measuring
2Reduction, reducing condition is 400 ℃, 4h, heating rate are 1 ℃/min, H
2Flow velocity is 30ml/min), H
2Adsorbance 134 μ mol/g-catalyst, active metals surface area 10.5m
2The Ni/g-catalyst.
Embodiment 7:
Take by weighing the nickel catalyst carried sample 0.2g of embodiment 5 preparation, the internal diameter of packing into is in 8 millimeters the glass reaction tube, to use H
2(heating rate is 1 ℃/min to reduction 4h, H under 400 ℃
2Flow velocity is 30ml/min).Then with H
2Feed reaction tube with the mist of toluene, measure the reactivity worth of the toluene gas phase hydrogenation system hexahydrotoluene of catalyst, the reaction normal pressure carries out, and reaction temperature is 50-180 ℃, gas space velocity 3600h
-1, H in the reaction gas
2With the mol ratio of toluene be 20: 1.With the composition of gas-chromatography on-line analysis reactor feed gas and reaction end gas, calculate toluene conversion and selectivity.When reaction temperature was 120 ℃, toluene conversion reached more than 99.8%, and the selectivity of hexahydrotoluene is 100%.
Reference example 7:
Take by weighing the support type nickel oxide sample 0.2g of reference example 5 preparations, press the method for embodiment 6 and measure toluene hydrogenation performance.When reaction temperature was 160 ℃, toluene conversion reached more than 99.8%, and the selectivity of hexahydrotoluene is 100%.
Embodiment 8:
Take by weighing 6.19g Ni (NO
3)
26H
2O puts into evaporating dish, adds the stirring of 17.0ml distilled water and makes its dissolving, takes by weighing 5.15g SBA-15C again and adds in the above-mentioned solution, stirs 10min, and room temperature is placed the dry 24h of 24h final vacuum, obtains the nickel catalyst carried of Dark grey.Put into then and be connected with high-purity H
2Tube furnace in, at 400 ℃ of following reduction 4h, heating rate is 1 ℃/min, H
2Flow is 30ml/min.The quality percentage composition that records the Ni of this catalyst is 19.8%.Use H
2The decentralization of determination of adsorption method metallic nickel is 42%, and reduction degree is 95% (Raney nickel H before measuring
2Reduction, reducing condition is 400 ℃, 4h, heating rate are 1 ℃/min, H
2Flow velocity is 30ml/min), H
2Adsorbance 650 μ mol/g-catalyst, active metals surface area 50.9m
2The Ni/g-catalyst.
Embodiment 9:
Take by weighing the support type nickel oxide sample 0.35g of embodiment 8 preparations, press the method for embodiment 7 and measure toluene hydrogenation performance.When reaction temperature was 85 ℃, toluene conversion reached more than 99.8%, and the selectivity of hexahydrotoluene is 100%.
Table 1 has gathered the main character of the metallic nickel catalyst of embodiment and reference example.
The main character of the metallic nickel catalyst that table 1, SBA-15 and SBA-15C support
Example | Carrier | Ni content (%) | Decentralization (%) | Reduction degree (%) | Metallic area m 2The Ni/g-catalyst |
Embodiment 2 | SBA-15C | 5.2 | 26 | 100 | 9.4 |
Reference example 2 | SBA-15 | 5.1 | 12 | 100 | 4.3 |
Embodiment 3 | SBA-15C | 9.0 | 32 | 100 | 18.7 |
Reference example 3 | SBA-15 | 8.9 | 6 | 100 | 3.8 |
Embodiment 4 | SBA-15C | 15.2 | 23 | 100 | 22.7 |
Reference example 4 | SBA-15 | 15.1 | 12 | 100 | 11.3 |
Embodiment 5 | SBA-15C | 20.0 | 22 | 99 | 27.9 |
Reference example 5 | SBA-15 | 20.1 | 8 | 98 | 9.7 |
Embodiment 6 | SBA-15C | 29.9 | 7 | 100 | 12.8 |
Reference example 6 | SBA-15 | 30.2 | 6 | 100 | 10.5 |
Embodiment 8 | SBA-15C | 19.8 | 42 | 95 | 50.9 |
Claims (8)
1. the high dispersion metal Raney nickel of the hole wall SBA-15 load of modifying through carbon is characterized by: employed hole wall contains mass percent in the SBA-15 that carbon is modified be 3% carbon, and the quality percentage composition of metallic nickel is 5~20% in the catalyst.
2. the preparation method of the SBA-15 that modifies through carbon of the described hole wall of claim 1: P123 is dissolved in H
2Among the O, add 2mol/L HCl solution again, behind 35-38 ℃ of stirred in water bath 1h, add ethyl orthosilicate (hereinafter to be referred as TEOS), make that the ratio of each amount is in the system: TEOS: HCl: P123: H
2O=1: 6: 0.017: 166.Continuation is at 35-38 ℃ of stirred in water bath 24h, then in 80 ℃ of following ageing 24h.Filter, room temperature dry the back in slumpability gas at 500 ℃ of roasting 6h, obtain the SBA-15 (hereinafter representing) that hole wall is modified through carbon with SBA-15/C.
3. hole wall according to claim 2 is through the preparation method of the SBA-15 of carbon modification, and used inert gas is N
2, Ar, He a kind of or its mist wherein, flow velocity is 60ml/min.
One kind with hole wall through carbon modify SBA-15 be the method for preparing carriers support type high dispersing nickel catalyst, it is characterized in that: the hole wall of metering is added in the nickel nitrate aqueous solution of metering through the SBA-15 that carbon is modified, at room temperature place 24h after stirring 10min, vacuum drying 24h at room temperature again, then in the inert gas that flows at 400 ℃ of roasting 4h, obtain the nickel catalyst carried of Dark grey.This Raney nickel need be used H before using
2Reduction is reduced to metallic nickel with nickel oxide.Reducing condition is: 400 ℃, and 4h, H
2Flow velocity 30ml/min.
5. nickel nitrate aqueous solution concentration is to contain Ni (NO in every 100ml water among the high dispersing nickel catalyst preparation method according to claim 4
3)
26H
2O 7.5~36.5g.
6. among the high dispersing nickel catalyst preparation method according to claim 4, inert gas is N
2, Ar, He a kind of or its mist wherein, flow velocity is 60ml/min.
7. a SBA-15C who modifies through carbon with hole wall is the method for preparing carriers support type high dispersing nickel catalyst.It is that the SBA-15C that will measure joins in the nickel nitrate aqueous solution of metering, stirs 10min, and room temperature is placed 24h, again at room temperature vacuum drying 24h, then in the H that flows
2Be warming up to 400 ℃ in the atmosphere, roasting 4h, heating rate are 1 ℃/min, H
2Flow is 30ml/min, obtains the load type metal high dispersing nickel catalyst.
8. according to claim 7, nickel nitrate aqueous solution concentration is to contain Ni (NO in every 100ml water among the described high dispersing nickel catalyst preparation method
3)
26H
2O 7.5~36.5g.
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