CN102078818A - Catalyst using SBA-16 molecular sieve as carrier, and preparation method and application thereof - Google Patents
Catalyst using SBA-16 molecular sieve as carrier, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a catalyst using an SBA-16 molecular sieve as a carrier, and a preparation method and application thereof. The catalyst is prepared by using a mesoporous SBA-16 molecular sieve with cage structures as the carrier, and is a cobalt-based catalyst for Fischer-Tropsch synthesis. The catalyst contains 10-45 wt% of element cobalt and 0-20.5 wt% of assistant metallic element. The catalyst disclosed by the invention has a three-dimensional porous channel system, has the advantages of high specific area, high cobalt loading capacity, high reaction activity, high hydrothermal stability, high selectivity for heavy hydrocarbons, and the like, and is hopeful to be used for Fischer-Tropsch synthesis reaction.
Description
Technical field
The present invention relates to the technical field of organic catalyst preparation, being specifically related to a kind of is catalyst and the method for making and the application of carrier with the SBA-16 molecular sieve, and this catalyst is applicable to the catalysis Fischer-Tropsch synthesis.
Background technology
Fischer-Tropsch is synthetic to be the reaction that the gaseous mixture (being commonly referred to synthesis gas) of carbon monoxide and hydrogen is converted into hydrocarbon compound under the effect of catalyst, and Fischer-Tropsch synthesis selects for use the metal of VIII family as catalyst usually, and removing Fe can be directly with oxide Fe
3O
4Form catalysis Fischer-Tropsch synthetic outside, other metal all loads to the form of oxide as Co, Ru, Pt etc. and forms catalyst on the inert carrier, when this class catalyst is applied to Fischer-Tropsch synthesis, can significantly improve the selectivity of the conversion ratio and the heavy hydrocarbon of carbon monoxide.
Being suitable for the material of making catalyst carrier has multiple, all there is a general character in these materials, promptly have loose microcellular structure and very high specific area, can adsorb metal salt solution, again by after drying, the roasting, make metal or its oxide species be attached to the surfaces externally and internally of carrier, greatly degree has increased the decentralization of reactive metal component, thereby improves its catalytic activity.
Bessel etc. impregnated in cobalt nitrate on the zeolite molecular sieve zsm-5 carrier with cage structure, prepare the catalyst that contains Co 9wt%, at 240 ℃, 2.0MPa, H
2/ CO volume ratio=2 and GHSV=1000h
-1Reaction condition under, find that this catalyst has higher Fischer-Tropsch synthesis catalytic activity and gasoline selective.(ZSM-5as?a?support?for?cobalt?Fischer-Tropsch?catalysts，in?Studies?in?Surface?Science?and?Catalysis，H.E.Curry-Hyde?and?R.R.Howe，Editors.1994，Elsevier.P461-466.)
Shanxi coal chemical research institute of Chinese Academy of Sciences employing supercritical drying is prepared the SiO with high-ratio surface and the distribution of middle hole characteristic
2, ZrO
2The aeroge superfine powder is made the cobalt-base catalyst carrier, (P=2.0MPa, T=220 ℃, H under near the commerical test condition
2/ CO volume ratio=2, GHSV=500h
-1) operation, find that Co that the aeroge oxide of mesopore supports is catalyst based and have an active and heavy hydrocarbon selectivity of product of very high Fischer-Tropsch synthesis catalytic, show that mesoporous support helps the generation of heavy hydrocarbon product.
Studies show that more than activity and the selectivity of product of catalyst in Fischer-Tropsch synthesis has inseparable relation with the carrier material and the pore structure thereof of catalyst.In addition, the high capacity amount of metal also has crucial effects to activity of such catalysts and catalytic stability and life-span, and the catalyst of high pore volume, high capacity amount shows high activity and high stability, also has the selectivity of higher C5+.(Xiong，H.，Y.Zhang，K.Liew，and?J.Li，Ruthenium?promotion?of?Co/SBA-15?catalysts?with?high?cobalt?loading?for?Fischer-Tropsch?synthesis.Fuel?Processing?Technology，2009.90(2)：P237-246.)。
Therefore, adopt to have central hole structure, the material of large pore volume will help to improve activity of such catalysts and heavy hydrocarbon selectivity as the carrier of fischer-tropsch synthetic catalyst.
The hole that the synthetic conventional oxide carrier that often adopts of Fischer-Tropsch has accumulation property in the prior art, pore-size distribution is wide, is difficult to optionally synthesize the product of a certain cut section.In recent years, caused people's extensive interest with molecular sieve such as HMS, MCM-41, SBA-15 etc. as catalyst carrier.The outstanding feature of this class carrier is to have regular pore structure, and specific area is bigger, the pore-size distribution homogeneous, and the aperture is adjustable, thermally-stabilised and good hydrothermal stability.The regular pore structure of mesoporous molecular sieve can deviate to provide good transmission channel for reactant spreads near catalyst active center and product, the hole shape of mesoporous molecular sieve is selected also to provide a comparatively desirable approach for controlling synthetic secondary response of Fischer-Tropsch and product selectivity effectively, particularly select molecular screen material ZSM-5 with cage structure, SBA-16 etc. not only can provide excellent mass transfer channel for reactant and product, can also form hole confinement stabilization to the active metal particles in the catalyst, prevent the reunion and the sintering of active nano metallic particles, improve the service life of catalyst.
Therefore, adopt to have regular mesopore cage structure, the molecular screen material of large pore volume will help to improve the performance of catalyst as the carrier of fischer-tropsch synthetic catalyst.
Summary of the invention
At the deficiencies in the prior art, the object of the present invention is to provide a kind of is catalyst and the method for making and the application of carrier with the SBA-16 molecular sieve.Catalyst carrier provided by the present invention is a kind of silica-based mesoporous molecular sieve material SBA-16 with cage structure, it has regular pore structure, by changing kind and consumption and the synthesis condition such as the crystallization temperature of template agent, aperture and specific area are all adjustable, and heat endurance and hydrothermal stability are all better.
The synthetic method of the carrier S BA-16 molecular sieve that catalyst of the present invention is used is with reference to existing document (Dongyuan Zhao, Qisheng Huo, Jianglin Feng, Bradley F.Chmelka, and Galen D.Stucky, Nonionic Triblock and Star Diblock Copolymer and Oligomeric Surfactant Syntheses of Highly Ordered, Hydrothermally Stable, Mesoporous Silica Structures, J.Am.Chem.Soc.1998,120:6024-6036), the synthetic operation process is: under normal temperature or low-grade fever condition, with triblock polymer surfactant P-123 (Aldrich, EO
20PO
70EO
20, M
A=5800) and polymeric surfactant F-127 (C
3H
6OC
2H
4O)
XBe dissolved in a certain amount of 2mol/L hydrochloric acid, be stirred to dissolving fully, under 35 ℃, add ethyl orthosilicate (TEOS) again, stir 24h, transfer to again in the polytetrafluoroethylene (PTFE) retort, in 70～140 ℃ of crystallization 24h, filter, wash the back in 120 ℃ of dry 5h, at last at 550 ℃ of following roasting 5h, obtaining the aperture is 6～20nm, has the white powder SBA-16 molecular sieve of cage type microstructure.
And then be that the SBA-16 molecular sieve of 6～20nm is a carrier with above aperture, adopt the method for dipping that cobalt salt solution once or is at twice immersed carrier, perhaps with cobalt salt be selected from Mg, Ca, Sr, Ru, Zr, Ti, Re, La, Pt, the solution of one or more promoter metal salt mixed configuration among Rh and the Ce once or at twice immerses carrier, with metallic element weight to total catalyst weight as benchmark, the content of cobalt metal element is 10～45wt% in the gained catalyst, assistant metal element content is 0～20.5wt%, the content that the two preferable range is respectively cobalt metal element is 20-35wt%, assistant metal element content is 0.5-15wt%, the content that optimum content is respectively cobalt metal element is 30wt%, and assistant metal element content is 1.5wt%.
Of the present invention a kind of be that the concrete preparation method of the catalyst of carrier is with the SBA-16 molecular sieve: synthetic good SBA-16 carrier is placed on dry 5h in 150 ℃ the baking oven, mixture with cobalt salt or cobalt salt and promoter metal salt is dissolved in the proper amount of deionized water again, once or at twice be impregnated on the carrier S BA-16, dipping catalyst precursor well is in drying, place baking oven in 120 ℃ of dry 12h then, place Muffle furnace at 300-500 ℃ of following roasting 5h, promptly at last.
The catalyst of preparation in the invention is reduced and Fischer-Tropsch synthesis on fixed bed Fischer-Tropsch synthesis device.The reducing condition of selecting is: 0.1MPa pressure, 5NL/hg air speed, 350～450 ℃, 10～20h.Be chosen in 2.0MPa, 210 ℃, CO/H
2Carry out Fischer-Tropsch synthesis under volume ratio=1: 2,6SL/gh air speed (promptly per hour the gas flow by every gram catalyst the is 6 liters) condition, the CO conversion ratio is all more than 40% under this reaction condition, and the C5+ selectivity is all more than 82%.When the cobalt load capacity surpassed 25wt%, the conversion ratio of CO reached more than 45% under the same terms, and the C5+ selectivity is more than 85%.
Catalyst of the present invention is than the catalyst of the same active component of silica supports load of routine, and catalytic activity is doubled, and methane selectively has reduced half, and performance has tangible lifting.
Compared with prior art, advantage of the present invention and beneficial effect are as follows:
Catalyst provided by the invention has the 3 D pore canal system, has optionally characteristics of high-specific surface area, high cobalt load capacity, high reaction activity, high hydrothermal stability and high heavy hydrocarbon.Because of the cage structure of its controlled size and a large amount of little connecting pipes (as shown in Figure 1), help the dispersion of active component, help the control of active metal particles size, help to improve activity of such catalysts; It has the 3 D pore canal of connection, compared to other one-dimensional channels System Catalyst, can significantly reduce the product plug-hole phenomenon in the course of reaction, more helps the diffusion of material transmission and reaction molecular; The SBA-16 molecular sieve carrier that employing has cage structure can also effectively be limited in the sintering and the reunion of cobalt metal in the course of reaction, thereby has effectively improved the stability of catalyst; In addition, adopt cage structure carrier can also utilize the shape of carrier hole to be elected to be with the selectivity of product that improves catalyst with pore structure homogeneous.
Description of drawings
Fig. 1 is the pore structure schematic diagram of SBA-16 molecular sieve.
Specific implementation method
Below in conjunction with specific embodiment the present invention is done further and to elaborate.
Embodiment 1
Under 35 ℃ of conditions, with 12g triblock polymer surfactant P123 (Aldrich, EO
20PO
70EO
20, M
A=5800) and 61g polymeric surfactant F-127 (C
3H
6OC
2H
4O)
XBe dissolved in the 2mol/L hydrochloric acid of 3400ml, be stirred to dissolving fully, add 283ml ethyl orthosilicate (TEOS) again, stir 24h, transfer to again in the polytetrafluoroethylene (PTFE) retort, in 70 ℃ of crystallization 24h, filter, wash, in 120 ℃ of dry 5h, at last at 550 ℃ of following roasting 5h, obtaining the aperture is the cage structure molecular sieve SBA-16 (1) of 6nm.
Take by weighing 150 ℃ of dried SBA-16 (1) molecular sieve 10.0g, take by weighing 13.6g Co (NO again
3)
26H
2O adds water and is configured to 6ml solution, and solution impregnation is arrived on the SBA-16 (1), after drying, place 120 ℃ of following dry 12h of baking oven, place Muffle furnace promptly to get 20%Co/SBA-16 (1) catalyst at 400 ℃ of following roasting 5h at last, be labeled as Cat.1, cobalt element content is 20wt% in this catalyst.
Embodiment 2
Under 35 ℃ of conditions, with 12g triblock polymer surfactant P123 (Aldrich, EO
20PO
70EO
20, M
A=5800) and 61g polymeric surfactant F-127 (C
3H
6OC
2H
4O)
XBe dissolved in the 2mol/L hydrochloric acid of 3400ml, be stirred to dissolving fully, add 283ml ethyl orthosilicate (TEOS) again, stir 24h, transfer to again in the polytetrafluoroethylene (PTFE) retort, in 90 ℃ of crystallization 24h, filter, wash, in 120 ℃ of dry 5h, at last at 550 ℃ of following roasting 5h, obtaining the aperture is the cage structure molecular sieve SBA-16 (2) of 10nm.
Take by weighing 150 ℃ of dried SBA-16 (2) molecular sieve 10.0g, take by weighing 18.8g Co (NO again
3)
26H
2O adds water and is configured to 8ml solution, and solution impregnation is arrived on the SBA-16 (2), after drying, place 120 ℃ of following dry 12h of baking oven, place Muffle furnace promptly to get 25%Co/SBA-16 (2) catalyst at 400 ℃ of following roasting 5h at last, be labeled as Cat.2, cobalt element content is 25wt% in this catalyst.
Embodiment 3
Under 35 ℃ of conditions, with 12g triblock polymer surfactant P123 (Aldrich, EO
20PO
70EO
20, M
A=5800) and 61g polymeric surfactant F-127 (C
3H
6OC
2H
4O)
XBe dissolved in the 2mol/L hydrochloric acid of 3400ml, be stirred to dissolving fully, add 283ml ethyl orthosilicate (TEOS) again, stir 24h, transfer to again in the polytetrafluoroethylene (PTFE) retort, in 120 ℃ of crystallization 24h, filter, wash, in 120 ℃ of dry 5h, at last at 550 ℃ of following roasting 5h, obtaining the aperture is the cage structure molecular sieve SBA-16 (3) of 12nm.
Take by weighing 150 ℃ of dried SBA-16 (3) molecular sieve 10.0g, take by weighing 16.5g Co (NO again
3)
26H
2O adds water and is configured to 9ml solution, and to SBA-16 (3), after drying, dry 12h makes intermediate under 120 ℃ in baking oven, takes by weighing 16.5g Co (NO for the second time again with solution impregnation
3)
26H
2O adds water and is configured to 9ml solution, with solution impregnation to intermediate, after drying, dry 12h under 120 ℃ in baking oven, place Muffle furnace promptly to get 35%Co/SBA-16 (3) catalyst at 400 ℃ of following roasting 5h at last, be labeled as Cat.3, cobalt element content is 35wt% in this catalyst.
Embodiment 4
Under 35 ℃ of conditions, with 12g triblock polymer surfactant P123 (Aldrich, EO
20PO
70EO
20, M
A=5800) and 61g polymeric surfactant F-127 (C
3H
6OC
2H
4O)
XBe dissolved in the 2mol/L hydrochloric acid of 3400ml, be stirred to dissolving fully, add 283ml ethyl orthosilicate (TEOS) again, stir 24h, transfer to again in the polytetrafluoroethylene (PTFE) retort, in 140 ℃ of crystallization 24h, filter, wash, in 120 ℃ of dry 5h, at last at 550 ℃ of following roasting 5h, obtaining the aperture is the cage structure molecular sieve SBA-16 (4) of 18nm.
Take by weighing 150 ℃ of dried SBA-16 (4) molecular sieve 10.0g, take by weighing 21.75g Co (NO again
3)
26H
2O adds water and is configured to 10ml solution, and to SBA-16 (4), after drying, dry 12h makes intermediate under 120 ℃ in baking oven, takes by weighing 21.75g Co (NO for the second time again with solution impregnation
3)
26H
2O adds water and is configured to 10ml solution, with solution impregnation to intermediate, after drying, dry 12h under 120 ℃, place Muffle furnace promptly to get 40%Co/SBA-16 (4) catalyst at 400 ℃ of following roasting 5h at last, be labeled as Cat.4, cobalt element content is 40wt% in this catalyst.
Embodiment 5
Get molecular sieve carrier SBA-16 (2) 10g synthetic among the embodiment 2, with 21.75g Co (NO
3)
26H
2O is dissolved in water and is made into 8ml solution, and solution is dipped on SBA-16 (2) carrier, after drying, places 120 ℃ of following dry 12h of baking oven to make intermediate, takes by weighing 21.75g Co (NO for the second time again
3)
26H
2O adds water and is configured to 8ml solution, with solution impregnation to intermediate, after drying, dry 12h under 120 ℃, place Muffle furnace to make 40%Co/SBA-16 (2) catalyst at 400 ℃ of roasting 5h at last, be labeled as Cat.5, cobalt element content is 40wt% in this catalyst.
Embodiment 6
Get molecular sieve carrier SBA-16 (3) 10g synthetic among the embodiment 3, take by weighing 28.8g Co (NO again
3)
26H
2O adds water and is configured to 9ml solution, and to SBA-16 (3), after drying, dry 12h makes intermediate under 120 ℃ in baking oven, takes by weighing 28.8g Co (NO for the second time again with solution impregnation
3)
26H
2O adds water and is configured to 9ml solution, with solution impregnation to intermediate, after drying, dry 12h under 120 ℃ in baking oven, place Muffle furnace to make 45%Co/SBA-16 (3) catalyst at 400 ℃ of roasting 5h at last, be labeled as Cat.6, cobalt element content is 45wt% in this catalyst.
Embodiment 7
Get molecular sieve carrier SBA-16 (2) 10g synthetic among the embodiment 2, take by weighing 25.0g Co (NO
3)
26H
2O and 0.015g nitrosonitric acid ruthenium add deionized water and are made into 8ml solution, solution is dipped on SBA-16 (2) carrier, after drying, place 120 ℃ of following dry 12h of baking oven, place Muffle furnace at 400 ℃ of roasting 5h at last, make 25%Co, 0.05%Ru/SBA-16 (2) catalyst, be labeled as Cat.7, the content of cobalt element and ruthenium element is respectively 25wt%Co and 0.05wt% in this catalyst.
Embodiment 8
Get molecular sieve carrier SBA-16 (2) 9.7g synthetic among the embodiment 2, take by weighing 0.93g lanthanum nitrate hexahydrate [La (NO
3)
36H
2O] being dissolved in water is made into 8ml solution, and solution is immersed among the molecular sieve carrier SBA-16 (2), dries the back in 120 ℃ of dry 12h, again in 550 ℃ of roasting 5h, takes by weighing 13.6g Co (NO again
3)
26H
2O and 0.083g dinitroso diammonia platinum add deionized water and are made into the 8ml mixed solution, this mixed solution is dipped on above-mentioned SBA-16 (2) carrier that adds the lanthanum auxiliary agent, after drying, place 120 ℃ of following dry 12h of baking oven, place Muffle furnace to get 20%Co at last, 0.5%Pt/SBA-16 (2)-3La catalyst at 450 ℃ of following roasting 5h, be labeled as Cat.8, cobalt element content is 20wt% in this catalyst, and the platinum constituent content is 0.5wt%, and lanthanum element content is 3wt%.
Embodiment 9
Get molecular sieve carrier SBA-16 (3) 7.3g synthetic among the embodiment 3, take by weighing 9.4g five water zirconium nitrate [Zr (NO
3)
45H
2O] being dissolved in water is made into 9ml solution, and solution is immersed among the molecular sieve carrier SBA-16 (3), dries the back in 120 ℃ of dry 12h, again in 550 ℃ of roasting 5h, takes by weighing 9.3g Co (NO again
3)
26H
2O and 0.15g nitrosonitric acid ruthenium [Ru (NO) (NO
3)
3] add deionized water and be made into the 8ml mixed solution, this mixed solution is dipped on above-mentioned SBA-16 (3) carrier that adds the zirconium metal promoter, dry under the room temperature, 120 ℃ of following dry 12h in baking oven place Muffle furnace to get 15%Co at 450 ℃ of following roasting 5h, 0.5%Ru/SBA-16 (3)-20Zr catalyst at last again, be labeled as Cat.9, cobalt element content is 15wt% in this catalyst, and ruthenium element content is 0.5wt%, and zr element content is 20wt%.
Embodiment 10
Get molecular sieve carrier SBA-16 (3) 9.3g synthetic among the embodiment 3, take by weighing 2.95g four water-calcium nitrate [Ca (NO
3)
24H
2O] being dissolved in water is made into 9ml solution, and solution is immersed among the molecular sieve carrier SBA-16 (3), dries the back in 120 ℃ of dry 12h, in 550 ℃ of roasting 5h, takes by weighing 25.1gCo (NO more again
3)
26H
2O adds deionized water and is made into 9ml solution, this solution is dipped on above-mentioned SBA-16 (3) carrier that adds the calcium metal promoter, dry under the room temperature, 120 ℃ of following dry 12h in baking oven again, place Muffle furnace to get 30%Co/SBA-16 (3)-5Ca catalyst at last at 450 ℃ of following roasting 5h, be labeled as Cat.10, cobalt element content is 30wt% in this catalyst, and calcium element content is 5wt%.
Embodiment 11
Get molecular sieve carrier SBA-16 (4) 10.0g synthetic among the embodiment 4, take by weighing 0.30g six water cerous nitrate [Ce (NO
3)
36H
2O] and 25.1gCo (NO
3)
26H
2O is dissolved in water and is made into the 10ml mixed solution, this solution is dipped on SBA-16 (4) carrier, dry under the room temperature, 120 ℃ of following dry 12h in baking oven again, place Muffle furnace to get 30%Co at 450 ℃ of following roasting 5h at last, 1%Ce/SBA-16 (4) catalyst is labeled as Cat.11, cobalt element content is 30wt% in this catalyst, and Ce elements content is 1wt%.
Embodiment 12
Under 35 ℃, with 6g triblock polymer surfactant P123 (Aldrich, EO
20PO
70EO
20, M
A=5800) and 30g polymeric surfactant F-127 (C
3H
6OC
2H
4O)
XBe dissolved in the 2mol/L hydrochloric acid solution of 1700ml, be stirred to dissolving fully, add 127.1ml ethyl orthosilicate (TEOS) and 14.2ml tetrabutyl titanate (C again
16H
36O
4Ti), stir 24h, transfer to again in the polytetrafluoroethylene (PTFE) retort, in 120 ℃ of crystallization 24h, filter, wash, in 120 ℃ of dry 5h, at last at 550 ℃ of following roasting 5h, obtain the aperture and be the cage structure molecular sieve SBA-16 (5) that the titanium of 12nm is inlayed, wherein titanium elements content is 2wt%.
Take by weighing 150 ℃ of dry down SBA-16 (5) molecular sieve 10.0g that cross, take by weighing 13.6gCo (NO again
3)
26H
2O and 0.06g nitrosonitric acid ruthenium [Ru (NO) (NO
3)
3] add water and be configured to 9ml solution, solution impregnation is arrived on the SBA-16 (5), after drying, dry 12h under 120 ℃, place Muffle furnace promptly to get 20%Co at 400 ℃ of following roasting 5h at last, 0.2%Ru/Ti-SBA-16 (5) catalyst is labeled as Cat.12, cobalt content is 20wt% in this catalyst, and ruthenium content is 0.2wt%.
Titanium adds in the carrier building-up process in the present embodiment, is doped in the pore structure skeleton of carrier, is not simply to impregnated in the surface, and such purpose is that promoter metal is combined with carrier better, improves the catalytic effect that helps of auxiliary agent.
Embodiment 13
Get molecular sieve carrier SBA-16 (2) 10.0g synthetic among the embodiment 2, take by weighing 0.31g lanthanum nitrate hexahydrate [La (NO
3)
36H
2O] being dissolved in water is made into 8ml solution, and solution is immersed among the molecular sieve carrier SBA-16 (2), dries the back in 120 ℃ of dry 12h, again in 550 ℃ of roasting 5h, takes by weighing 6.8g Co (NO again
3)
26H
2O and 0.083g dinitroso diammonia platinum add deionized water and are made into the 8ml mixed solution, this mixed solution is dipped on above-mentioned SBA-16 (2) carrier that adds the lanthanum auxiliary agent, after drying, place 120 ℃ of following dry 12h of baking oven, place Muffle furnace to get 10%Co at last, 0.5%Pt/SBA-16 (2)-1La catalyst at 450 ℃ of following roasting 5h, be labeled as Cat.13, cobalt element content is 10wt% in this catalyst, and the platinum constituent content is 0.5wt%, and lanthanum element content is 1wt%.
Embodiment 14
Get molecular sieve carrier SBA-16 (3) 7.3g synthetic among the embodiment 3, take by weighing 7.1g five water zirconium nitrate [Zr (NO
3)
45H
2O] being dissolved in water is made into 9ml solution, and solution is immersed among the molecular sieve carrier SBA-16 (3), dries the back in 120 ℃ of dry 12h, again in 550 ℃ of roasting 5h, takes by weighing 12.4g Co (NO again
3)
26H
2O and 0.15g nitrosonitric acid ruthenium [Ru (NO) (NO
3)
3] add deionized water and be made into the 8ml mixed solution, this mixed solution is dipped on above-mentioned SBA-16 (3) carrier that adds the zirconium metal promoter, dry under the room temperature, 120 ℃ of following dry 12h in baking oven place Muffle furnace to get 20%Co at 450 ℃ of following roasting 5h, 0.5%Ru/SBA-16 (3)-15Zr catalyst at last again, be labeled as Cat.14, cobalt element content is 20wt% in this catalyst, and ruthenium element content is 0.5wt%, and zr element content is 15wt%.
Embodiment 15
Get molecular sieve carrier SBA-16 (4) 10.0g synthetic among the embodiment 4, take by weighing 0.45g six water cerous nitrate [Ce (NO
3)
36H
2O] being dissolved in water is made into 10ml solution, and solution is immersed among the molecular sieve carrier SBA-16 (3), dries the back in 120 ℃ of dry 12h, in 550 ℃ of roasting 5h, takes by weighing 25.1gCo (NO more again
3)
26H
2O and 0.083g dinitroso diammonia platinum add deionized water dissolving and are made into the 10ml mixed solution, this solution is dipped on above-mentioned SBA-16 (4) carrier that adds the ce metal auxiliary agent, dry under the room temperature, 120 ℃ of following dry 12h in baking oven place Muffle furnace to get 30%Co at 450 ℃ of following roasting 5h, 0.5%Pt/SBA-16 (4)-1.5Ce catalyst at last again, be labeled as Cat.15, cobalt element content is 30wt% in this catalyst, and the platinum constituent content is 0.5wt%, and Ce elements content is 1.5wt%.
The comparative example
A kind of SiO
2Load cobalt catalyst contains cobalt element 20wt% in this catalyst, platinum element 0.5wt%, lanthanum element 3wt%.Its preparation method is as follows:
Get commercially available spherical SiO
2Carrier 61.6g adopts the method dipping of full hole dipping to add 6.1gLa (NO
3)
36H
2The 45ml solution that O is made into leaves standstill behind the 2h in 120 ℃ of dry 4h, in 400 ℃ of roasting 4h, makes the SiO that contains La
2Carrier adds with 49.4gCo (NO again after the cooling
3)
26H
2O and 0.41gPt (NO
3)
4The 45ml mixed solution that is made into leaves standstill and dries the back at 140 ℃ of dry 4h, adds with 49.4gCo (NO after the taking-up once more
3)
26H
2O and 0.41gPt (NO
3)
4The 45ml mixed solution dipping that is made into dries, and at 120 ℃ of dry 4h, in 400 ℃ of roasting 4h, makes 20%Co again, 0.5%Pt, 3%La/SiO
2Catalyst is labeled as Cat.16.
Get above each catalyst of 3 grams and be respectively charged in the Φ 12mm fixed bed reactors, at 0.1MPa pressure, the 5NL/hg air speed, is used H by 450 ℃
2Reduction 10h.Be chosen in 2.0MPa pressure, 210 ℃ of temperature, gas volumes compare CO/H
2=1: 2, the condition of 6SL/gh air speed is carried out Fischer-Tropsch synthesis, records that the results are shown in Table 1.
Table 1
| Title | Catalyst is formed | The CO conversion ratio | ?CH 4Selectivity | The C5+ selectivity |
| Cat.1 | 20％Co/SBA-16(1) | 42.5％ | 8.1％ | 82.2％ |
| Cat.2 | 25％Co/SBA-16(2) | 47.0％ | 7.6％ | 85.0％ |
| Cat.3 | 35％Co/SBA-16(3) | 51.2％ | 6.7％ | 85.1％ |
| Cat.4 | 40％Co/SBA-16(4) | 55.4％ | 5.8％ | 85.9％ |
| Cat.5 | 40％Co/SBA-16(2) | 58.6％ | 6.1％ | 85.6％ |
| Cat.6 | 45％Co/SBA-16(3) | 62.5％ | 5.3％ | 86.2％ |
| Cat.7 | 25％Co，0.05％Ru/SBA-16(2) | 58.5％ | 4.9％ | 87.5％ |
| Cat.8 | 20％Co，0.5％Pt/SBA-16(2)-3La | 59.5％ | 4.8％ | 87.8％ |
| Cat.9 | 15％Co，0.5％Ru/SBA-16(3)-20Zr | 57.5％ | 5.3％ | 86.3％ |
| Cat.10 | 30％Co/SBA-16(3)-5Ca | 51.5％ | 6.5％ | 86.1％ |
| Cat.11 | 30％Co，1％Ce/SBA-16(4) | 49.3％ | 6.6％ | 85.1％ |
| Cat.12 | 20％Co，0.2％Ru/Ti-SBA-16(5) | 63.1％ | 4.7％ | 89.3％ |
| Cat.13 | 10％Co，0.5％Pt/SBA-16(2)-1La | 45.3％ | 6.9％ | 84.8％ |
| Cat.14 | 20％Co，0.5％Ru/SBA-16(3)-15Zr | 61.2％ | 4.6％ | 88.0％ |
| Cat.15 | 30％Co，0.5％Pt/SBA-16(4)-1.5Ce | 69.5％ | 3.9％ | 90.2％ |
| Cat.16 | 20％Co，0.5％Pt，3％La/SiO 2 | 28.5％ | 8.3％ | 81.3％ |
Claims (10)
1. one kind is the catalyst of carrier with the SBA-16 molecular sieve, it is characterized in that: contain cobalt element 10～45wt% in the described catalyst, contain assistant metal element 0～20.5wt%, described assistant metal element is selected from one or more among Mg, Ca, Sr, Ru, Zr, Ti, Re, La, Pt, Rh and the Ce.
2. catalyst as claimed in claim 1 is characterized in that: contain cobalt element 20-35wt% in the described catalyst, contain assistant metal element 1.0-15.5wt%.
3. catalyst as claimed in claim 1 or 2 is characterized in that: contain cobalt element 30wt% in the described catalyst, contain assistant metal element 1.5wt%.
4. catalyst as claimed in claim 1 is characterized in that: the aperture of described SBA-16 molecular sieve is 6 ~ 20nm.
5. as claim 1 or 4 described catalyst, it is characterized in that: the aperture of described SBA-16 molecular sieve is 10 ~ 18nm.
6. as claim 1,2 or 4 described catalyst, it is characterized in that: described assistant metal element is Pt.
7. as claim 1,2 or 4 described catalyst, it is characterized in that: described assistant metal element is Ti.
8. as claim 1,2 or 4 described catalyst, it is characterized in that: described assistant metal element is Zr.
9. as claim 1,2 or 4 described catalyst, it is characterized in that: described assistant metal element is Ce.
10. the application of the described catalyst of claim 1 in Fischer-Tropsch synthesis.
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