CN101327441A - Cobalt-based catalyst for selectively synthesizing middle distillate from synthesis gas and production method and use - Google Patents
Cobalt-based catalyst for selectively synthesizing middle distillate from synthesis gas and production method and use Download PDFInfo
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Abstract
The present invention relates to a cobalt-based catalyst for selectively synthesizing medium fraction from synthesis gas. The cobalt-based catalyst is characterized in that the catalyst consists of 5wt percent to 45wt percent of Co, 20wt percent to 95wt percent of porous support, 0wt percent to 20wt percent of metal accessory ingredient and 0wt percent to 8wt percent on organic group in the weight percentage. The catalyst is prepared in a dipping method or a sol-gel method. The cobalt-based catalyst has the advantages of good stability and high selectivity.
Description
Technical field
The invention belongs to a kind of cobalt-base catalyst and preparation method and application, relate in particular to a kind of cobalt-base catalyst and method for making and application by the synthetic intermediate oil of synthesis gas selectivity.
Technical background
Under the promotion of modern revolution of science and technology, social economy's fast development also causes particularly a large amount of consumption of petroleum resources of fossil resource simultaneously.Except the important source material source as the modern chemistry product, oil products such as the gasoline that oil is produced by series of steps such as fractionation, hydrofinishings, diesel oil are the of paramount importance power resources of modern society.Along with consuming day by day of petroleum resources and increasing sharply of demand, seek that non-petroleum path is obtained power source and even chemicals becomes the strategy that receives much concern at present.Fischer-Tropsch synthesis is to utilize specific catalyst to realize CO hydrogenation (is raw material with the synthesis gas) production generate longer-chain hydrocarbons under middle pressure and moderate temperature, its raw material sources are extensive, comprise that coal, natural gas and living beings etc. contain carbon resource, so Fischer-Tropsch synthesis is the approach that an important non-petroleum path life/product obtains oil product and chemicals.
Fischer-Tropsch synthesis is quite complicated, and the product that relates to has more than hundreds of, about the arguement of reaction mechanism up to now all neither one make us well-content conclusion.However, the rigorous basic research of forefathers has still drawn some useful conclusions.Studies show that in the product of Fischer-Tropsch synthesis, straight-chain hydrocarbons is (from methane to C
100 +) be primary product (being meant mainly that herein the low temperature Fischer-Tropsch is synthetic), the logarithm value and the carbon number of hydrocarbon amount and carbon number ratio are linear under each given carbon number, straight slope is the so-called chain growth factor, this distribution is called ASF (Anderson-Schulz-Flory) distribution, and (Fischer-Tropsch is synthetic, Science Press, New York, 1984).According to this theory, on traditional catalyst, can not synthesize a kind of the have hydrocarbon of specific carbon number or the narrow cut of synthetic carbon number distribution of high selectivity by Fischer-Tropsch synthesis.In fact, Fischer-Tropsch synthesis process under many circumstances therewith rule be consistent.This is to being a production bad news beyond doubt of purpose so that the power support to be provided to transporting equipment.Common way is a preparation high activity fischer-tropsch synthetic catalyst at present, optimizes concrete reaction operating mode and type of reactor, improves chain growth factor-alpha value as far as possible, reduces gaseous light hydrocarbon yield; Repeated hydrogenation refining (cracking etc.) receive heavy hydrocarbon produce vapour, diesel oil distillate.The famous SMDS technology of Shell company is exactly this method that adopts.But obviously, the cost of technologys such as cracking will account for the vapour that the Fischer-Tropsch synthesis technology makes, the major part of diesel oil cost; In addition, if the major part oil product derives from the lifting that step such as cracking is unfavorable for oil quality (as octane number, cold resistance etc.).So the technology of centre carbon number fraction such as comparatively desirable non-petroleum path system vapour, diesel oil is that a step is synthetic, makes great efforts to make Fischer-Tropsch synthetic to be non-ASF and distribute.
In fact, had been found that the phenomenon that non-ASF distributes in the relevant process of Fischer-Tropsch study on the synthesis.(the Fischer-Tropsch synthesis product distributes and controls new method people such as Fujimoto, Kaoru.Fujimoto, Li Fan et al, the catalysis proposition, 1995,2 (1): 259-266) find: when introduce long-chain alpha-olefin in supercritical medium after, very large variation can take place in Fischer-Tropsch synthetic, product distributes and obviously departs from the ASF distribution, and the long chain hydrocarbon selectivity significantly increases.Iglesia (design of Co base fischer-tropsch synthetic catalyst, synthetic and application, Enrique.Iglesia, applied catalysis A: introduction, 1997,161 (1-2), 59-78) think that non-ASF distributes and derive from alpha-olefin as one of Fischer-Tropsch synthesis principal product and adsorb again and cause new chain propagation reaction that appropriate design catalyst granules (as the catalyst granules of preparation reactive metal non-uniform Distribution etc.) can obtain to be beneficial to the catalyst that long chain hydrocarbon generates.Studies show that further Fischer-Tropsch synthetic distributes and is subjected to multifactor impact, aperture, reactive metal state, carrier surface character etc. all can have influence on the amount of each carbon number hydrocarbon in the fischer-tropsch product.
Generally speaking, through constantly effort of researchers, on non-ASF distribution Fischer-Tropsch study on the synthesis, achieve initial success, the possibility that breaks through the synthetic mesophase cut oil of ASF distribution, high selectivity has, but still very wide according to the Fischer-Tropsch synthesis product carbon number distribution scope that existing method obtains, C
18 +Heavy hydrocarbon account for relatively large proportion (20-50wt%), really do not realize that the high selectivity of vapour, diesel oil distillate section is synthetic; Methane selectively is also generally higher.
Summary of the invention
The purpose of this invention is to provide a kind of Co based Fischer-Tropsch synthesis catalyst and preparation method and application of synthetic mesophase cut oil of high selectivity.
The intermediate oil here refers in particular to carbon number at C
5-C
18Between hydro carbons, through producing oil products such as gasoline, diesel oil, aviation kerosine after the deep processing.The present invention from the carrier duct, reactive metal (Co) presoma existence form, aspect such as organically-modified, approach such as the restriction of passing hole channel space structure, the cracking of highly acid carrier situ, catalyst parent/hydrophobicity and active matter microstate modulation reach the purpose of the synthetic intermediate oil of selectivity.Carry out Fischer-Tropsch synthesis according to method described in the invention and process conditions, the product that obtains distributes and has tangible non-ASF distribution characteristics, thereby the selectivity that realizes midbarrel carbon number section hydrocarbon is synthetic.
Catalyst weight percentage of the present invention consists of:
Co:5-45wt%, porous carrier: 20-95wt%, metal promoter: 0-20wt%, organic group: 0-8wt%.
Aforesaid metal promoter is one or more of IIA family or transition metal, and IIA family metal comprises Be, Mg or Ca, and transition metal is Cr, Mn, Fe, Ni, Cu, Zn, Ru, Rh, Pd, La, Ce or Th etc.
Aforesaid organic group is meant that the carrier organic precursor of introducing remains in the organic group in the matrix after roasting in sol-gel process synthetic catalyst process, also comprise catalyst through after the organic groups such as methyl, methylene, dimethyl, trimethyl, ethyl, acetenyl or phenyl introduced of grafting.
The Preparation of catalysts method that the present invention relates to is as follows:
(1) porous carrier load C o is catalyst based
(1) the solubility cobalt salt is a presoma preparation dipping solution, according to the mol ratio of complexing agent and Co at 0-10: 1 ratio adds complexing agent in dipping solution, with incipient impregnation normal direction porous carrier load C o, the gained sample descended dry 10-24 hour at 60-150 ℃, 300-800 ℃ following roasting 2-10 hour, unmodified catalyst;
(2) when the unmodified catalyst that makes with metal promoter modification procedure (1), with equi-volume impregnating, with soluble metal builder salts carried metal auxiliary agent on the unmodified catalyst of step (1), descended dry 10-24 hour at 60-150 ℃ again, 300-800 ℃ following roasting 2-10 hour, make the catalyst of metal promoter modification;
(3) when adding organic group modified catalyst, then adopt the back grafting to introduce the organic additive that contains organic group to the catalyst that step (1) or step (2) make: the catalyst that step (1) or step (2) are made is immersed in organic additive or its steam 2-10 hour, filter, after using organic solvent extracting 3-48 hour again, descended dry 8-48 hour at 40-150 ℃, it is catalyst based promptly to make organically-modified Co.
Aforesaid porous material is meant: have regular duct and the molecular sieve (the BJH pore size distribution has most probable value, and peak width is less than 100nm) of the pore-size distribution concentrated as MCM-41, MCM-48, SBA-15, HMS etc.; Or molecular sieve that the highly acid center has hydrocracking, an isomery isoreactivity is arranged as ZSM-5, ZSM-22, SAPO-11, SAPO-41, Y type or beta molecular sieve etc.; And make template with three block polyoxyethylene-type non-ionic surface active agents according to Chinese patent CN1631796, with diglycol etc. is the complexing stabilizing agent, make the mesoporous ZrO 2 of the slow hydrolysis in zirconium source, polycondensation preparation in suitable pH scope, concrete preparation method sees Chinese patent CN1631796; Chinese patent CN1686821 with the titanium source with after triethanolamine mixes, with water or low-carbon alcohols is solvent, regulates pH and makes mixture form homogeneous phase gel, after the sealing crystallization, with making mesoporous TiO 2 after alcoholic solution extraction or the roasting, concrete preparation method sees Chinese patent CN1686821; Chinese patent CN1594102 adopts sol-gel process earlier, the titanium alkoxide is hydrolyzed into the nano particle of Detitanium-ore-type under uniform temperature, specific pH value, be bridging agent then with the surfactant, the titanium dioxide nano-particle of Detitanium-ore-type is assembled, finalize the design through Overheating Treatment, become the titanium dioxide mesoporous material that hole wall is the anatase phase, concrete preparation method sees Chinese patent CN1594102.
The solubility cobalt salt comprises cobalt salts such as cobalt nitrate, cobalt acetate and carbonyl cobalt as mentioned above.
Complexing agent comprises ethylenediamine, EDTA, nitrilotriacetic acid etc. as mentioned above.
When carrier is introduced metal promoter, can adopt the stable soluble-salt of metal promoter, and tend to use the nitrate or the nitrite of respective metal as mentioned above.
The aforesaid organic additive that contains organic group is MTES, dimethyldiethoxysilane, ethyl triethoxysilane, VTES, phenyl triethoxysilane, trim,ethylchlorosilane, vinyl trichlorosilane or HMDS.
The solvent that is used for extracting as mentioned above is meant acetone, benzene, toluene, ethanol, n-hexane or cyclohexane etc.
(2) to prepare Co catalyst based for sol-gel process
Under 0-60 ℃ preparation condition, the mixture of soluble cobalt salt or soluble cobalt salt and soluble metal builder salts composition is dissolved in the ethanol, wherein the mol ratio of Co and ethanol is 1: 30-200, after waiting to dissolve, under stirring condition, add the porous carrier presoma, the mol ratio of Co and porous carrier presoma is 1: 0.5-30, the amount of pressing the mol ratio 1 of Co and base catalyst: 0.1-10 adds base catalyst, mol ratio by the water yield and porous carrier presoma is 1: the amount of 1-50 adds entry, stir after 10-48 hour, 25-80 ℃ aging 0-48 hour down, be 40-150 ℃ of oven dry down at baking temperature, 200-800 ℃ following roasting 2-10 hour.
The porous carrier presoma is organosilicon source, organic zirconium source, organic titanium source etc. as mentioned above; The organosilicon source comprises poly-methyl hydrogen-containing siloxane, ethyl orthosilicate and aminopropyl triethoxysilane etc.; The organic zirconium source comprises propyl alcohol zirconium, zirconium iso-propoxide etc.; The organic titanium source comprises butyl titanate etc.
Aforesaid base catalyst comprises organic base and inorganic base, recommends to use ethylenediamine or ammoniacal liquor herein.
The solubility cobalt salt comprises cobalt salts such as cobalt nitrate, cobalt acetate and carbonyl cobalt as mentioned above.
When carrier is introduced metal promoter, can adopt the stable soluble-salt of metal promoter, and tend to use the nitrate or the nitrite of respective metal as mentioned above.
Zhi Bei Co is catalyst based as mentioned above can be applicable in fixed bed or the paste state bed reactor preparation intermediate oil of high selectivity; Concrete application conditions is as follows: reaction temperature 170-350 ℃, and reaction pressure 0.5-8MPa, gas space velocity 500-5000h
-1, unstripped gas hydrogen-carbon ratio H
2/ CO=1.5-4.0.
The present invention compared with prior art has following characteristics:
(1) the present invention starts with from the structure-activity relationship of catalyst, and the gained Fischer-Tropsch synthetic distributes and is non-ASF distribution, has realized that really the selectivity of intermediate oil is synthetic.
(2) catalyst has good stable, and lighter hydrocarbons selectivity such as methane are low, utilizes the economy of process that further guarantee is provided for Fischer-Tropsch is synthetic.
(3) catalyst of the catalyst preparation process preparation of describing according to the present invention is not limited by type of reactor, applicable to polytype reactors such as fixed bed, slurry attitude beds, has saved in the actual application expenses such as process and equipment modification.
Concrete enforcement
Provide several illustrative rather than restrictive example below
Embodiment 1:
Press incipient impregnation normal direction porous material loading metal Co.Select for use commercially available SBA-15 as catalyst carrier.Account for the preparation cobalt nitrate solution of 35.0wt% by Co in the catalyst, the incipient impregnation carrier, the gained sample 120 ℃ down after dry 20 hours in 350 ℃ of following roastings 6 hours, promptly get last catalyst.Catalyst is formed: 35.0wt%Co/SBA-15.
The gained catalyst obtains 200-400 purpose catalyst granules after compressing tablet, screening.Adopting offline restore, catalyst to be reduced the back transfers in the reactor under indifferent gas (as Ar etc.) protection.Reducing condition: 450 ℃ of reduction temperatures, hydrogen gas space velocity are 1200h
-1, reduction pressure 0.6MPa.Reaction condition is as follows: 230 ℃ of reaction temperatures, reaction pressure 4.5MPa, gas space velocity 3000h
-1, unstripped gas hydrogen-carbon ratio H
2/ CO=2.0.Evaluating catalyst the results are shown in Table 1.
Embodiment 2:
Press incipient impregnation normal direction porous material loading metal Co.Select for use commercially available HMS molecular sieve as catalyst carrier.Account for the preparation cobalt nitrate solution of 35.0wt% by Co in the catalyst, in the mol ratio of ethylenediamine and Co is that 2: 1 ratio adds ethylenediamine to cobalt nitrate solution, and incipient impregnation carrier then, gained sample are at 60 ℃ down after dry 24 hours, in 300 ℃ of following roastings 6 hours, promptly get last catalyst.Catalyst is formed: 35.0wt%Co/HMS.
The gained catalyst obtains 60-80 purpose catalyst granules after compressing tablet, screening, get 2ml and be filled in the single tube reactor.Adopt pure hydrogen in-situ reducing, 400 ℃ of reduction temperatures, hydrogen gas space velocity is 1200h
-1, reduction pressure 0.3MPa.Reaction condition: 200 ℃ of reaction temperatures, reaction pressure 2.0MPa, gas space velocity 3000h
-1, unstripped gas hydrogen-carbon ratio H
2/ CO=2.0.Evaluating catalyst the results are shown in Table 1.
Embodiment 3:
Press incipient impregnation normal direction porous material loading metal Co.According to the Co load capacity of 25.0wt% preparation cobalt nitrate aqueous solution, be that 3: 1 ratio adds EDTA, the ZSM-5 that incipient impregnation is commercially available in cobalt nitrate solution in the mol ratio of EDTA and Co.The gained sample descended dry 16 hours at 100 ℃, in 750 ℃ of following roastings 3 hours, got not metal-modified catalyst.
Press the not metal-modified catalyst of amount preparation palladium nitrate solution dipping of 3.0wt%Pd.The gained sample 60 ℃ dry 24 hours down, 600 ℃ of following roastings 5 hours make last catalyst.Catalyst is formed: 25.0wt%Co/3.0wt%Pd/ZSM-5.
The gained catalyst obtains 200-400 purpose catalyst granules after compressing tablet, screening.Adopting offline restore, catalyst to be reduced the back transfers in the reactor under indifferent gas (as Ar etc.) protection.Reducing condition: 400 ℃ of reduction temperatures, hydrogen gas space velocity are 1000h
-1, reduction pressure 0.2MPa.Reaction condition is as follows: 210 ℃ of reaction temperatures, reaction pressure 3.0MPa, gas space velocity 3000h
-1, unstripped gas hydrogen-carbon ratio H
2/ CO=2.0.Evaluating catalyst the results are shown in Table 1.
Embodiment 4:
CN1136972 prepares mesoporous ZrO 2 according to Chinese patent.Under 30 ℃, 0.79gP123 is dissolved in 10.5ml ethanol-9.5ml deionized water, stirred 0.5 hour, get solution A; At room temperature, 3ml diglycol, 3.5ml propyl alcohol zirconium are added in the 20ml ethanol successively, stirred 0.5 hour, get solution B; Under 30 ℃, magnetic agitation, solution B is added in the solution A, drip nitric acid, regulate pH value 2.5, continue to stir 1 hour, change in the closed container, wore out 72 hours at 40 ℃.In 60 ℃ of following evaporating solvents, reflow treatment is 48 hours in the ammoniacal liquor of pH=8 in air for the gained gel, after filtration, washing, the drying, is placed in the Muffle furnace 650 ℃ of roastings 5 hours, promptly gets mesoporous ZrO 2.
Adopt equi-volume impregnating load C o, requiring the mass fraction of Co in final catalyst is 20.0wt%, preparation carbonyl cobalt solution, impregnated carrier.The gained sample descended dry 12 hours at 80 ℃, in 600 ℃ of following roastings 4 hours, got not metal-modified metallic catalyst.
Press the not metal-modified catalyst of amount preparation copper nitrate solution incipient impregnation of 15.0wt%Cu.The gained sample 80 ℃ dry 20 hours down, 500 ℃ of following roastings 5 hours make last catalyst.Catalyst is formed: the 20.0wt%Co/15.0wt%Cu/ mesoporous ZrO 2.
The gained catalyst obtains 60-80 purpose catalyst granules after compressing tablet, screening, get 2ml and be filled in the single tube reactor.Adopt pure hydrogen in-situ reducing, 400 ℃ of reduction temperatures, hydrogen gas space velocity is 1200h
-1, reduction pressure 0.8MPa.Reaction condition: 200 ℃ of reaction temperatures, reaction pressure 3.0MPa, gas space velocity 4000h
-1, unstripped gas hydrogen-carbon ratio H
2/ CO=2.8.Evaluating catalyst the results are shown in Table 1.
Embodiment 5:
The method of describing according to Chinese patent CN1686821 prepares mesoporous TiO 2.At room temperature mix 12ml butyl titanate and 4.7ml triethanolamine, back dropping 16ml water stirs, recording the pH value is 8, continue to stir and to obtain homogeneous mixture, 12 hours after coagulations of 100 ℃ of above-mentioned homogeneous mixtures of drying form a kind of homogeneous phase gel, then gel are moved in the reactor 150 ℃ of following crystallization 12 hours, obtain block gel, again above-mentioned product is warmed up to 600 ℃ with 1 ℃/min speed and calcined 10 hours down, grind and obtain white powder, be the mesoporous TiO 2 sample.
Adopt equi-volume impregnating load C o, requiring the mass fraction of Co in final catalyst is 10.0wt%.The preparation cobalt acetate aqueous solution, and be that 8 amount adds nitrilotriacetic acid, the incipient impregnation carrier in solution by the mol ratio of nitrilotriacetic acid: Co.The gained sample descended dry 12 hours at 100 ℃, in 700 ℃ of following roastings 4 hours, promptly got last catalyst.Catalyst is formed: the 10.0wt%Co/ mesoporous TiO 2.
The gained catalyst obtains 200-400 purpose catalyst granules after compressing tablet, screening.Adopting offline restore, catalyst to be reduced the back transfers in the reactor under indifferent gas (as Ar etc.) protection.Reducing condition: 500 ℃ of reduction temperatures, hydrogen gas space velocity are 1800h
-1, reduction pressure 0.5MPa.Reaction condition is as follows: 230 ℃ of reaction temperatures, reaction pressure 3.0MPa, gas space velocity 1500h
-1, unstripped gas hydrogen-carbon ratio H
2/ CO=2.0.Evaluating catalyst the results are shown in Table 1.
Embodiment 6:
Press incipient impregnation normal direction porous material loading metal Co.Select for use commercially available SAPO-11 molecular sieve as catalyst carrier.Account for the preparation cobalt nitrate solution of 35.0wt% by Co in the catalyst, in the mol ratio of ethylenediamine and Co is that 10: 1 ratio adds ethylenediamine to cobalt nitrate solution, incipient impregnation carrier then, the gained sample is after under 80 ℃ dry 20 hours, in 550 ℃ of following roastings 6 hours, get not metal-modified catalyst.
Press the not metal-modified catalyst of amount preparation zinc nitrate solution incipient impregnation of 20.0wt%Zn.The gained sample 70 ℃ dry 18 hours down, 600 ℃ of following roastings 5 hours make last catalyst.Catalyst is formed: the 35.0wt%Co/20.0wt%Zn/ mesoporous TiO 2.
The gained catalyst obtains 60-80 purpose catalyst granules after compressing tablet, screening, get 2ml and be filled in the single tube reactor.Adopt pure hydrogen in-situ reducing, 400 ℃ of reduction temperatures, hydrogen gas space velocity is 1200h
-1, reduction pressure 0.3MPa.Reaction condition: 190 ℃ of reaction temperatures, reaction pressure 2.0MPa, gas space velocity 2000h
-1, unstripped gas hydrogen-carbon ratio H
2/ CO=2.0.Evaluating catalyst the results are shown in Table 1.
Embodiment 7:
Press embodiment 1 preparation catalyst sample.Press incipient impregnation normal direction gained sample load Fe again.Press the amount preparation iron nitrate solution dipping gained sample of 5.0wt%Fe.The gained sample 60 ℃ dry 24 hours down, 600 ℃ of following roastings 2 hours make last catalyst.Catalyst is formed: 35.0wt%Co/5.0wt%Fe/SBA-15.
The gained catalyst obtains 200-400 purpose catalyst granules after compressing tablet, screening.Adopting offline restore, catalyst to be reduced the back transfers in the reactor under indifferent gas (as Ar etc.) protection.Reducing condition: 450 ℃ of reduction temperatures, hydrogen gas space velocity are 1500h
-1, reduction pressure 0.8MPa.Reaction condition is as follows: 220 ℃ of reaction temperatures, reaction pressure 4.0MPa, gas space velocity 2000h
-1, unstripped gas hydrogen-carbon ratio H
2/ CO=1.8.Evaluating catalyst the results are shown in Table 1.
Embodiment 8:
Press embodiment 2 preparation catalyst samples.Press incipient impregnation normal direction gained sample load Be again.Press the amount preparation beryllium nitrate solution impregnation gained sample of 7.0wt%Be.The gained sample 70 ℃ dry 24 hours down, 700 ℃ of following roastings 3 hours make last catalyst.Catalyst is formed: 35.0wt%Co/7.0wt%Be/HMS.
The gained catalyst obtains 60-80 purpose catalyst granules after compressing tablet, screening, get 2ml and be filled in the single tube reactor.Adopt pure hydrogen in-situ reducing, 500 ℃ of reduction temperatures, hydrogen gas space velocity is 2000h
-1, reduction pressure 0.3MPa.Reaction condition: 210 ℃ of reaction temperatures, reaction pressure 2.0MPa, gas space velocity 3500h
-1, unstripped gas hydrogen-carbon ratio H
2/ CO=2.5.Evaluating catalyst the results are shown in Table 1.
Embodiment 9:
Press embodiment 5 preparation catalyst samples.Press incipient impregnation normal direction gained sample load C e again.Press the amount preparation cerous nitrate solution incipient impregnation gained sample of 6.0wt%Ce.The gained sample 80 ℃ dry 20 hours down, 600 ℃ of following roastings 3 hours make last catalyst.Catalyst is formed: the 10.0wt%Co/6.0wt%Ce/ mesoporous TiO 2.
The gained catalyst obtains 200-400 purpose catalyst granules after compressing tablet, screening.Adopting offline restore, catalyst to be reduced the back transfers in the reactor under indifferent gas (as Ar etc.) protection.Reducing condition: 450 ℃ of reduction temperatures, hydrogen gas space velocity are 1500h
-1, reduction pressure 0.8MPa.Reaction condition is as follows: 220 ℃ of reaction temperatures, reaction pressure 4.0MPa, gas space velocity 2000h
-1, unstripped gas hydrogen-carbon ratio H
2/ CO=1.8.Evaluating catalyst the results are shown in Table 1.
Embodiment 10:
Press the load cobalt sample of embodiment 1 preparation, utilize the back grafting to prepare the target catalyst again.
It is stifling with 2ml MTES mixed solution to take by weighing 10.0g, and is aided with the ultrasonic wave that operating frequency is 30KHz, vibrates the solid collected by filtration sample 2 hours.Be medium difference extracting 24 hours with toluene and acetone then.The gained sample promptly made the target catalyst after under 60 ℃ dry 20 hours.Catalyst is formed: 35.0wt%Co/0.8wt% organic group/SBA-15.
The gained catalyst obtains 60-80 purpose catalyst granules after compressing tablet, screening, get 2ml and be filled in the single tube reactor.Adopt pure hydrogen in-situ reducing, 500 ℃ of reduction temperatures, hydrogen gas space velocity is 2000h
-1, reduction pressure 0.3MPa.Reaction condition: 210 ℃ of reaction temperatures, reaction pressure 2.0MPa, gas space velocity 3500h
-1, unstripped gas hydrogen-carbon ratio H
2/ CO=2.5.Evaluating catalyst the results are shown in Table 1.
Embodiment 11:
It is catalyst based to press embodiment 7 preparation Co, utilizes the back grafting to prepare the target catalyst again.
Take by weighing the above-mentioned load cobalt of 10.0g sample, sample is in the VTES environment.Be respectively extracting 24 hours of medium with sample with toluene and acetone after 8 hours.Through 80 ℃ times dry 16 hours, promptly make the target catalyst again.Catalyst is formed: 35.0wt%Co/5.0wt%Fe/2.1wt% organic group/SBA-15.
The gained catalyst obtains 200-400 purpose catalyst granules after compressing tablet, screening.Adopting offline restore, catalyst to be reduced the back transfers in the reactor under indifferent gas (as Ar etc.) protection.Reducing condition: 300 ℃ of reduction temperatures, hydrogen gas space velocity are 500h
-1, reduction pressure 1.0MPa.Reaction condition is as follows: 240 ℃ of reaction temperatures, reaction pressure 8.0MPa, gas space velocity 2000h
-1, unstripped gas hydrogen-carbon ratio H
2/ CO=3.0.Evaluating catalyst the results are shown in Table 1.
Embodiment 12:
It is catalyst based to press embodiment 2 preparation Co, utilizes the back grafting to prepare the target catalyst again.
Take by weighing the above-mentioned load cobalt of 10.0g sample, place under the enclosed system stifling with the 3ml VTES.Be respectively extracting 24 hours of medium with sample with toluene and acetone after 2 hours.Through 100 ℃ times dry 10 hours, promptly make the target catalyst again.Catalyst is formed: 35.0wt%Co/1.3wt% organic group/HMS.
The gained catalyst obtains 60-80 purpose catalyst granules after compressing tablet, screening, get 2ml and be filled in the single tube reactor.With pure hydrogen at 400 ℃, 0.3MPa, 1000h
-1After reducing under the condition, at 220 ℃, 3.0MPa, 1500h
-1, H
2React under the condition of/CO=2.0.Evaluating catalyst the results are shown in Table 1.
Embodiment 13:
Under 0 ℃, the amount that accounts for 10.0wt% according to Co is dissolved in cobalt nitrate in the ethanol, and the mol ratio of Co and ethanol is 1: 60.After treating the salt dissolving, add ethyl orthosilicate under well-beaten condition, the mol ratio of Co and ethyl orthosilicate is 1: 8.5.By Co and ethylenediamine mol ratio is that 1: 1 amount adds ethylenediamine.By the mol ratio of the water yield and support precursor is that 1: 1 amount adds entry.The turbid solution that continues to stir generation is after 24 hours, and 40 ℃ are aging down after 12 hours, oven dry, and baking temperature is 60 ℃, 450 ℃ of following roastings promptly got target sample in 6 hours.Catalyst is formed: 10.0wt%Co/3.1wt% organic group/porous silica.
The gained catalyst obtains 60-80 purpose catalyst granules after compressing tablet, screening, get 2ml and be filled in the single tube reactor.Adopt pure hydrogen in-situ reducing, 600 ℃ of reduction temperatures, hydrogen gas space velocity is 2000h
-1, reduction pressure 0.1MPa.Reaction condition: 170 ℃ of reaction temperatures, reaction pressure 1.0MPa, gas space velocity 500h
-1, unstripped gas hydrogen-carbon ratio H
2/ CO=3.0.Evaluating catalyst the results are shown in Table 1.
Embodiment 14:
Under 40 ℃, account for 15.0wt%, Mn according to Co and account for 5.0% amount cobalt nitrate, manganese nitrate are dissolved in the ethanol, the mol ratio of Co and ethanol is 1: 80.After treating the salt dissolving, add ethyl orthosilicate under well-beaten condition, the mol ratio of Co and ethyl orthosilicate is 1: 7.0.By Co and ethylenediamine mol ratio is that 1: 3 amount adds ethylenediamine.By the mol ratio of the water yield and support precursor is that 1: 5 amount adds entry.The turbid solution that continues to stir generation is after 12 hours, and 60 ℃ are aging down after 12 hours, oven dry, and baking temperature is 100 ℃, 300 ℃ of following roastings promptly got target sample in 4 hours.Catalyst is formed: 15.0wt%Co/5.0wt%Mn/4.3wt% organic group/porous silica.
The gained catalyst obtains 60-80 purpose catalyst granules after compressing tablet, screening, get 2ml and be filled in the single tube reactor.Adopt pure hydrogen in-situ reducing, 500 ℃ of reduction temperatures, hydrogen gas space velocity is 1500h
-1, reduction pressure 0.8MPa.Reaction condition: 230 ℃ of reaction temperatures, reaction pressure 4.0MPa, gas space velocity 3000h
-1, unstripped gas hydrogen-carbon ratio H
2/ CO=2.0.Evaluating catalyst the results are shown in Table 1.
Embodiment 15:
Under 40 ℃, account for the 35.0wt% amount according to Co cobalt nitrate is dissolved in the ethanol, the mol ratio of Co and ethanol is 1: 100.After treating the salt dissolving, add the support precursor of being made up of 2.5: 1 poly-methyl hydrogen-containing siloxane of mol ratio and ethyl orthosilicate mixture under well-beaten condition, the mol ratio of Co and ethyl orthosilicate is 1: 1.8.By the mol ratio of Co and ammoniacal liquor is that 1: 5 amount adds ethylenediamine.By the mol ratio of the water yield and support precursor is that 1: 5.1 amount adds entry.The turbid solution that continues to stir generation is after 36 hours, and 40 ℃ are aging down after 12 hours, oven dry, and baking temperature is 100 ℃, 600 ℃ of following roastings promptly got target sample in 5 hours.Catalyst is formed: the 35.0wt%Co/ porous silica.
The gained catalyst obtains 200-400 purpose catalyst granules after compressing tablet, screening.Adopting offline restore, catalyst to be reduced the back transfers in the reactor under indifferent gas (as Ar etc.) protection.Reducing condition: 300 ℃ of reduction temperatures, hydrogen gas space velocity are 500h
-1, reduction pressure 1.0MPa.Reaction condition is as follows: 240 ℃ of reaction temperatures, reaction pressure 8.0MPa, gas space velocity 2000h
-1, unstripped gas hydrogen-carbon ratio H
2/ CO=3.0.Evaluating catalyst the results are shown in Table 1.
Embodiment 16:
Under 40 ℃, account for the 15.0wt% amount according to Co cobalt nitrate is dissolved in the ethanol, the mol ratio of Co and ethanol is 1: 150.After treating the salt dissolving, under well-beaten condition, add the mixed type support precursor of forming by poly-methyl hydrogen-containing siloxane, ethyl orthosilicate and aminopropyl triethoxysilane, and guarantee that Co and aminopropyl triethoxysilane mol ratio are 1: 2, poly-methyl hydrogen-containing siloxane is 1.0 with the mol ratio of (ethyl orthosilicate+aminopropyl triethoxysilane), the mol ratio of Co and support precursor total amount is 1: 7.8, is that 1: 8.0 amount adds ethylenediamine by the mol ratio of Co and ammoniacal liquor.By the mol ratio of the water yield and support precursor is that 1: 10 amount adds entry.Stir after 10 hours, the muddy thing of gained was dried after under 25 ℃ aging 10 hours, and baking temperature is 60 ℃, and 800 ℃ of following roastings promptly got target sample in 10 hours.Catalyst is formed: the 15.0wt%Co/ porous silica.
The gained catalyst obtains 200-400 purpose catalyst granules after compressing tablet, screening.Adopting offline restore, catalyst to be reduced the back transfers in the reactor under indifferent gas (as Ar etc.) protection.Reducing condition: 400 ℃ of reduction temperatures, hydrogen gas space velocity are 1000h
-1, reduction pressure 0.2MPa.Reaction condition is as follows: 210 ℃ of reaction temperatures, reaction pressure 3.0MPa, gas space velocity 3000h
-1, unstripped gas hydrogen-carbon ratio H
2/ CO=2.0.Evaluating catalyst the results are shown in Table 1.
Embodiment 17:
Under 25 ℃, account for the amount that 25wt%, Cr account for 12.0wt% according to Co in the catalyst cobalt nitrate and chromic nitrate are dissolved in the ethanol, the mol ratio of Co and ethanol is 1: 100.After treating the salt dissolving, under well-beaten condition, add the mixed type support precursor of forming by poly-methyl hydrogen-containing siloxane, ethyl orthosilicate and aminopropyl triethoxysilane, and guarantee that Co and aminopropyl triethoxysilane mol ratio are 1: 1.5, poly-methyl hydrogen-containing siloxane is 1.0 with the mol ratio of (ethyl orthosilicate+aminopropyl triethoxysilane), the mol ratio of Co and support precursor total amount is 1: 4.2, is that 1: 6 amount adds ethylenediamine by the mol ratio of Co and ammoniacal liquor.By the mol ratio of the water yield and support precursor is that 1: 20 amount adds entry.Stir after 10 hours, the muddy thing of gained was dried after under 40 ℃ aging 10 hours, and baking temperature is 60 ℃, and 500 ℃ of following roastings promptly got target sample in 4 hours.Catalyst is formed: 15.0wt%Co/12.0wt%Cr/1.5wt% organic group/porous silica.
The gained catalyst obtains 60-80 purpose catalyst granules after compressing tablet, screening, get 2ml and be filled in the single tube reactor.Adopt pure hydrogen in-situ reducing, 450 ℃ of reduction temperatures, hydrogen gas space velocity is 1000h
-1, reduction pressure 0.5MPa.Reaction condition: 280 ℃ of reaction temperatures, reaction pressure 1.0MPa, gas space velocity 2000h
-1, unstripped gas hydrogen-carbon ratio H
2/ CO=2.0.Evaluating catalyst the results are shown in Table 1.
Embodiment 18:
Under 25 ℃, account for 18.0wt% according to Co, the amount that Ce accounts for 7.0wt% is dissolved in cobalt nitrate, cerous nitrate in the ethanol, and the mol ratio of Co and ethanol is 1: 60.After treating the salt dissolving, add the propyl alcohol zirconium under well-beaten condition, the mol ratio of Co and propyl alcohol zirconium is 1: 3.2.By Co and ethylenediamine mol ratio is that 1: 3 amount adds ethylenediamine.By the mol ratio of the water yield and propyl alcohol zirconium is that 1: 10 amount adds entry.The turbid solution that continues to stir generation is after 24 hours, and 50 ℃ are aging down after 12 hours, oven dry, and baking temperature is 60 ℃, 250 ℃ of following roastings promptly got target sample in 6 hours.Catalyst is formed: 18.0wt%Co/7.0wt%Ce/0.5wt% organic group/porous zirconium dioxide.
The gained catalyst obtains 60-80 purpose catalyst granules after compressing tablet, screening, get 2ml and be filled in the single tube reactor.Adopt pure hydrogen in-situ reducing, 600 ℃ of reduction temperatures, hydrogen gas space velocity is 2000h
-1, reduction pressure 0.1MPa.Reaction condition: 170 ℃ of reaction temperatures, reaction pressure 1.0MPa, gas space velocity 500h
-1, unstripped gas hydrogen-carbon ratio H
2/ CO=3.0.Evaluating catalyst the results are shown in Table 1.
Embodiment 19:
Under 40 ℃, account for 18wt% according to Co, the amount that Th accounts for 4.0wt% is dissolved in cobalt nitrate, thorium nitrate in the propyl alcohol, and the mol ratio of Co and propyl alcohol is 1: 50.After treating the salt dissolving, add the propyl alcohol zirconium under well-beaten condition, the mol ratio of Co and propyl alcohol zirconium is 1: 3.4.By Co and ethylenediamine mol ratio is that 1: 1.5 amount adds ethylenediamine.By the mol ratio of the water yield and propyl alcohol zirconium is that 1: 40 amount adds entry.The turbid solution that continues to stir generation is after 2 hours, and 40 ℃ are aging down after 24 hours, oven dry, and baking temperature is 60 ℃, 700 ℃ of following roastings promptly got target sample in 6 hours.Catalyst is formed: 18.0wt%Co/4.0wt%Th/ porous zirconium dioxide.
The gained catalyst obtains 60-80 purpose catalyst granules after compressing tablet, screening, get 2ml and be filled in the single tube reactor.Adopt pure hydrogen in-situ reducing, 600 ℃ of reduction temperatures, hydrogen gas space velocity is 2000h
-1, reduction pressure 0.1MPa.Reaction condition: 170 ℃ of reaction temperatures, reaction pressure 1.0MPa, gas space velocity 500h
-1, unstripped gas hydrogen-carbon ratio H
2/ CO=3.0.Evaluating catalyst the results are shown in Table 1.
Embodiment 20:
Under 40 ℃, account for 28wt% according to Co, the amount that Th accounts for 4.0wt% is dissolved in cobalt nitrate, thorium nitrate in the ethanol, and the mol ratio of Co and ethanol is 1: 100.After treating the salt dissolving, add butyl titanate under well-beaten condition, the mol ratio of Co and butyl titanate is 1: 4.2.By Co and ethylenediamine mol ratio is that 1: 3.0 amount adds ethylenediamine.By the mol ratio of the water yield and butyl titanate is that 1: 50 amount adds entry.The turbid solution that continues to stir generation is after 5 hours, and 40 ℃ are aging down after 24 hours, oven dry, and baking temperature is 60 ℃, 300 ℃ of following roastings promptly got target sample in 3 hours.Catalyst is formed: 28.0wt%Co/4.0wt%Th/ porous titanium dioxide.
The gained catalyst obtains 60-80 purpose catalyst granules after compressing tablet, screening, get 2ml and be filled in the single tube reactor.Adopt pure hydrogen in-situ reducing, 600 ℃ of reduction temperatures, hydrogen gas space velocity is 2000h
-1, reduction pressure 0.1MPa.Reaction condition: 170 ℃ of reaction temperatures, reaction pressure 1.0MPa, gas space velocity 500h
-1, unstripped gas hydrogen-carbon ratio H
2/ CO=3.0.Evaluating catalyst the results are shown in Table 1.
Table 1
Claims (20)
1, a kind of cobalt-base catalyst that becomes the synthetic intermediate oil of gas selectivity is characterized in that catalyst weight percentage consists of: Co:5-45wt%, porous carrier: 20-95wt%, metal promoter: 0-20wt%, organic group: 0-8wt%.
2, a kind of cobalt-base catalyst that becomes the synthetic intermediate oil of gas selectivity as claimed in claim 1 is characterized in that described metal promoter is one or more of IA family or transition metal.
3, a kind of cobalt-base catalyst that becomes the synthetic intermediate oil of gas selectivity as claimed in claim 2 is characterized in that described IA family metal is Be, Mg or Ca.
4, a kind of cobalt-base catalyst that becomes the synthetic intermediate oil of gas selectivity as claimed in claim 2 is characterized in that described transition metal is Cr, Mn, Fe, Ni, Cu, Zn, Ru, Rh, Pd, La, Ce or Th.
5, a kind of cobalt-base catalyst that becomes the synthetic intermediate oil of gas selectivity as claimed in claim 1, it is characterized in that described organic group is that the carrier organic precursor introduced remains in the organic group in the matrix after roasting in sol-gel process synthetic catalyst process, catalyst through after grafting methyl, methylene, dimethyl, trimethyl, ethyl, acetenyl or the phenyl organic group introduced.
6, a kind of cobalt-base catalyst that becomes the synthetic intermediate oil of gas selectivity as claimed in claim 1 is characterized in that described porous material is MCM-41, MCM-48, SBA-15, HMS, ZSM-5, ZSM-22, SAPO-11, SAPO-41, Y type or beta molecular sieve; And make template with three block polyoxyethylene-type non-ionic surface active agents according to Chinese patent CN1631796, with diglycol etc. is the complexing stabilizing agent, in suitable pH scope, make the mesoporous ZrO 2 of the slow hydrolysis in zirconium source, polycondensation preparation, Chinese patent CN1686821 with the titanium source with after triethanolamine mixes, with water or low-carbon alcohols is solvent, regulate pH and make mixture form homogeneous phase gel, after the sealing crystallization, with making mesoporous TiO 2 after alcoholic solution extraction or the roasting; Chinese patent CN1594102 adopts sol-gel process earlier, the titanium alkoxide is hydrolyzed into the nano particle of Detitanium-ore-type under uniform temperature, specific pH value, be bridging agent then with the surfactant, the titanium dioxide nano-particle of Detitanium-ore-type is assembled, through the Overheating Treatment typing, become the titanium dioxide mesoporous material that hole wall is the anatase phase.
7, as each described a kind of preparation method who becomes the cobalt-base catalyst of the synthetic intermediate oil of gas selectivity of claim 1-6, it is characterized in that comprising the steps:
(1) the solubility cobalt salt is a presoma preparation dipping solution, according to the mol ratio of complexing agent and Co at 0-10: 1 ratio adds complexing agent in dipping solution, with incipient impregnation normal direction porous carrier load C o, the gained sample descended dry 10-24 hour at 60-150 ℃, 300-800 ℃ following roasting 2-10 hour, unmodified catalyst;
(2) when the unmodified catalyst that makes with metal promoter modification procedure (1), with equi-volume impregnating, with soluble metal builder salts carried metal auxiliary agent on the unmodified catalyst of step (1), descended dry 10-24 hour at 60-150 ℃ again, 300-800 ℃ following roasting 2-10 hour, make the catalyst of metal promoter modification;
(3) when adding organic group modified catalyst, then adopt the back grafting to introduce the organic additive that contains organic group to the catalyst that step (1) or step (2) make: the catalyst that step (1) or step (2) are made is immersed in organic additive or its steam 2-10 hour, filter, after using organic solvent extracting 3-48 hour again, descended dry 8-48 hour at 40-150 ℃, it is catalyst based promptly to make organically-modified Co.
8, a kind of preparation method who becomes the cobalt-base catalyst of the synthetic intermediate oil of gas selectivity as claimed in claim 7 is characterized in that described solubility cobalt salt is cobalt nitrate, cobalt acetate or carbonyl cobalt.
9, a kind of preparation method who becomes the cobalt-base catalyst of the synthetic intermediate oil of gas selectivity as claimed in claim 7 is characterized in that described complexing agent is ethylenediamine, EDTA or nitrilotriacetic acid.
10, a kind of preparation method who becomes the cobalt-base catalyst of the synthetic intermediate oil of gas selectivity as claimed in claim 7 is characterized in that described soluble metal builder salts is nitrate or nitrite.
11, a kind of preparation method who becomes the cobalt-base catalyst of the synthetic intermediate oil of gas selectivity as claimed in claim 7 is characterized in that the described organic additive that contains organic group is MTES, dimethyldiethoxysilane, ethyl triethoxysilane, VTES, phenyl triethoxysilane, trim,ethylchlorosilane, vinyl trichlorosilane or HMDS.
12, a kind of preparation method who becomes the cobalt-base catalyst of the synthetic intermediate oil of gas selectivity as claimed in claim 7 is characterized in that the solvent that described extracting is used is acetone, benzene, toluene, ethanol, n-hexane or cyclohexane.
13, as each described a kind of preparation method who becomes the cobalt-base catalyst of the synthetic intermediate oil of gas selectivity of claim 1-6, it is characterized in that comprising the steps:
Under 0-60 ℃ preparation condition, the mixture of soluble cobalt salt or soluble cobalt salt and soluble metal builder salts composition is dissolved in the ethanol, wherein the mol ratio of Co and ethanol is 1: 30-200, after waiting to dissolve, under stirring condition, add the porous carrier presoma, the mol ratio of Co and porous carrier presoma is 1: 0.5-30, the amount of pressing the mol ratio 1 of Co and base catalyst: 0.1-10 adds base catalyst, mol ratio by the water yield and porous carrier presoma is 1: the amount of 1-50 adds entry, stir after 10-48 hour, 25-80 ℃ aging 0-48 hour down, be 40-150 ℃ of oven dry down at baking temperature, 200-800 ℃ following roasting 2-10 hour.
14, as a kind of preparation method who becomes the cobalt-base catalyst of the synthetic intermediate oil of gas selectivity as claimed in claim 13, it is characterized in that described porous carrier presoma is organosilicon source, organic zirconium source or organic titanium source.
15,, it is characterized in that described organosilicon source is poly-methyl hydrogen-containing siloxane, ethyl orthosilicate or aminopropyl triethoxysilane as a kind of preparation method who becomes the cobalt-base catalyst of the synthetic intermediate oil of gas selectivity as claimed in claim 14; The organic zirconium source is propyl alcohol zirconium or zirconium iso-propoxide; The organic titanium source is a butyl titanate.
16, as a kind of preparation method who becomes the cobalt-base catalyst of the synthetic intermediate oil of gas selectivity as claimed in claim 13, it is characterized in that described base catalyst is organic base and inorganic base.
17, as a kind of preparation method who becomes the cobalt-base catalyst of the synthetic intermediate oil of gas selectivity as claimed in claim 16, it is characterized in that described organic base is an ethylenediamine; Inorganic base is an ammoniacal liquor.
18, as a kind of preparation method who becomes the cobalt-base catalyst of the synthetic intermediate oil of gas selectivity as claimed in claim 13, it is characterized in that described solubility cobalt salt is cobalt nitrate, cobalt acetate or carbonyl cobalt.
19, as a kind of preparation method who becomes the cobalt-base catalyst of the synthetic intermediate oil of gas selectivity as claimed in claim 13, it is characterized in that described soluble metal builder salts is nitrate or nitrite.
20, as each described a kind of application that becomes the cobalt-base catalyst of the synthetic intermediate oil of gas selectivity of claim 1-6, it is characterized in that being used in fixed bed or paste state bed reactor, application conditions is: reaction temperature 170-350 ℃, and reaction pressure 0.5-8MPa, gas space velocity 500-5000h
-1, unstripped gas hydrogen-carbon ratio H
2/ CO=1.5-4.0.
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