CN102059119B - Mesoporous-macroporous cobalt-based catalyst and preparation method and application thereof - Google Patents
Mesoporous-macroporous cobalt-based catalyst and preparation method and application thereof Download PDFInfo
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- CN102059119B CN102059119B CN2010105393259A CN201010539325A CN102059119B CN 102059119 B CN102059119 B CN 102059119B CN 2010105393259 A CN2010105393259 A CN 2010105393259A CN 201010539325 A CN201010539325 A CN 201010539325A CN 102059119 B CN102059119 B CN 102059119B
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Abstract
The invention discloses a mesoporous-macroporous cobalt-based catalyst. The catalyst is characterized by consisting of the following components in percentage by weight: 5 to 35 percent of metal cobalt which serves as an active ingredient and 65 to 95 percent of silicon dioxide which serves as a carrier. The first pore diameter of a mesoporous-macroporous double pore-distributed catalyst is between 2.3 and 50 nanometers which accounts for 20 to 35 percent of the pore structure of the catalyst; and the second pore diameter of the catalyst is between 50 and 100 nanometers which accounts for 40 to 60 percent of the pore structure of the catalyst. The catalyst is prepared by an isometric immersion method. The catalyst has different mesoporous-macroporous pore cannel structures, so that problems such as diffusion limits of a reactant and a product and the like are solved. The two pore diameters of the catalyst are adjustable. The first pore diameter is between 2 and 50 nanometers, and the second pore diameter is between 50 and 100 nanometers, so that hydrocarbon compounds with different carbon numbers can be synthesized selectively.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method and application, a kind of specifically preparation method of mesopore-macropore material load cobalt catalyst and the application in Fischer-Tropsch is synthetic.
Technical background
With natural gas, coal bed gas or living beings are converted into power fuel and high quality chemical article under catalyst action technology (Fischer-Tropsch is synthetic) is the emphasis of present international C-1 chemistry research.And cobalt-base catalyst has active height, and methane selectively is low, C
5Advantages such as+selectivity height and water gas reaction selectivity are low are catalyst commonly used during Fischer-Tropsch synthesizes.At present, be main mainly based on the FT product with heavy hydrocarbon (wax), intermediate oil C
5-C
18Productive rate is low.The two-stage method or the multiple process technology that adopt in the industry become intermediate oil to have complex process heavy hydrocarbon hydrocracking; Therefore shortcoming such as involve great expense adopts synthetic intermediate oil Preparation of catalysts of Fischer-Tropsch synthesis method selectivity and application to have meaning of crucial importance.
At present, novel mesoporous material at bulky molecular catalysis, very tempting prospect has been showed in aspects such as adsorbing separation.Different mesopore molecular sieves are used as the preparing carriers cobalt-base catalyst, and mesopore-macropore bimodal pore distribution catalyst becomes the focus of current research gradually owing to its specific structure and excellent performance.The influence that the space facilitation of double-pore structure reaches the adsorption and diffusion behavior of reactant and product makes the bimodal pore distribution load type cobalt-base catalyst have good reaction rate and low CH
4Selectivity.
The mesopore-macropore material can not only provide enough specific areas for reaction; Have enough mesoporous and macropores simultaneously; Avoided problems such as diffusion restriction,, made it become carrier important in the catalytic reaction and catalyst for reactant and product provide the passage of quick transmission.Shinoda etc. are with SiO
2Or ZrO
2Colloidal sol joins macro-pore SiO
2Obtain the bimodal pore distribution load type cobalt-base catalyst in the gel, and demonstrate good reaction rate and low CH
4Selectivity.WO 02/00338A has published a kind of Co/SiO with double hole channel
2Catalyst.This invention impregnated in the commercial macropore Ludox with Ludox, obtains dipping cobalt nitrate behind the silicon carrier that diplopore distributes and makes catalyst.This catalyst is used for fischer-tropsch reaction and has showed high activity and low methane selectively.But the porous that adopts this method to obtain not is to be that self assembly forms, and regularity is poor, and still there is certain restrictive function in the transmission of material.Thereby use mesopore-macropore diplopore distribution fischer-tropsch synthetic catalyst and have important learning value and realistic meaning with regular passage.
Summary of the invention
The purpose of this invention is to provide a kind of mesopore-macropore material load cobalt catalyst and preparation method and the application in Fischer-Tropsch is synthetic.
Catalyst of the present invention is made up of active component and carrier, and its percentage by weight consists of: metallic cobalt: 5-35%, silica are 65-95%.
Aforesaid mesopore-macropore diplopore distribution catalyst first aperture is 2.3-50nm, accounts for the 20-35% of catalyst pores structure, and second aperture is 50-100nm, accounts for the 40-60% of catalyst pores structure.
Preparation of catalysts method of the present invention is following:
The preparation of mesopore-macropore silica supports:
Softex kw (CTAB) is dissolved in the NaOH aqueous solution of 0.01-0.05mol/L; Add expanding agent 1,3,5-trimethylbenzene (TMB) after stirring 30-60min; Speed with 1-2ml/min adds ethyl orthosilicate (TEOS) again; After continuing to stir 30-60min, leave standstill 3-8h, then 60-100 ℃ of aging 36-72h.Material dries by the fire 24-30h down at 60-90 ℃, is warming up at 500-650 ℃ of roasting 6-10h with 1-3 ℃/min, obtains the silica supports that the mesopore-macropore diplopore distributes;
Each material molar ratio of synthetic different apertures mesopore-macropore carrier is softex kw: 1,3, and 5-trimethylbenzene: NaOH: ethyl orthosilicate=0.1-5: 1: 0.1-0.6: 10.
Ratio through changing expanding agent TMB and catalyst n aOH and Surfactant CTAB is with regard to the pore-size distribution of adjustable carrier.
The mesopore-macropore Preparation of catalysts:
Adopt ammoniacal liquor gas phase revulsion to prepare required catalyst.With putting into the internal layer of the double-deck autoclave of top UNICOM without the catalyst of oven dry behind the solubility cobalt salt incipient impregnation 20-30h; Ammonia spirit with 10-20wt% places skin again; Seal and be placed on 60-90 ℃ of reaction 0.5-2h, naturally cool to room temperature, then at 60-80 ℃ of baking 12-48h; At 400-550 ℃ of roasting 1-3h, promptly get required catalyst at last.
Aforesaid solubility cobalt salt is a cobalt nitrate, cobalt acetate etc.
The prepared catalyst of the present invention both can be used for fixed bed Fischer-Tropsch synthesis device, can be used for again starching in the attitude bed.The application operating condition is: reducing condition does, pure hydrogen atmosphere, and 250～500 ℃, 0.1～1.20MPa, volume space velocity are 500-2000h
-1(V/V), recovery time 6-24h.
Reaction condition is that 190～300 ℃, 0.5～5.0MPa, volume space velocity are 500～2000h
-1(V/V), H
2/ CO=1/1～3/1 (Mol ratio)
The catalyst of the present invention's preparation has following characteristics: have abundant mesopore-macropore structure, for reaction provides enough specific surfaces, the cobalt-base catalyst that utilizes the acquisition high dispersive is being arranged; Simultaneously, catalyst has different mesopore-macropore pore passage structures, has avoided the problems such as diffusion restriction of reactant and product.Two kinds of pore sizes of catalyst are adjustable, first kind of pore diameter range 2-50nm, and second kind of pore diameter range 50-100nm helps the hydrocarbon compound that selectivity is synthesized different carbon numbers.
The specific embodiment
Embodiment 1
1g CTAB is dissolved in the NaOH aqueous solution of 500ml 0.01mol/L, behind the stirring 30min, adds 0.35g TMB, and the speed with 1ml/min adds 5.62mlTEOS then, after continuing to stir 30min, leaves standstill 3h, then 60 ℃ of aging 72h.Material at 500 ℃ of roasting 6h, obtains mesopore-macropore diplopore distribution silica supports with the heating rate of 1 ℃/min behind 60 ℃ of baking 30h.
The 3g carrier is carried out incipient impregnation with being dissolved in the solution that 9ml contains the 0.499g cobalt nitrate.With putting into the internal layer of the double-deck autoclave of top UNICOM without the catalyst of oven dry behind the incipient impregnation 20h; Ammonia spirit with 10wt% places the autoclave skin again; Seal to be placed in 60 ℃ of baking ovens and react 0.5h, naturally cool to room temperature, then 60 ℃ of baking 12h in baking oven; 500 ℃ of roasting 1h in Muffle furnace promptly get required catalyst at last.Metallic cobalt is 5wt% in the catalyst.Mesoporous 20% of the pore structure that accounts in the catalyst, macropore accounts for 40% of pore structure.
(the above-mentioned catalyst of φ 10 * 500nm) filling 2ml 60-80 purposes, temperature programmed reduction in pure hydrogen atmosphere in pressurization static bed reactor.Reducing condition is that 400 ℃, 0.1MPa, volume space velocity are 500h
-1(V/V), reduction 6h.Reaction condition is that 190 ℃, 1Mpa, volume space velocity are 1000h
-1(V/V), H
2/ CO=2/1 (Mol ratio).Reaction result is seen table 1.
Get the slurry attitude stirred tank that the above above-mentioned catalyst 15ml of 100 orders puts into 1L, add the 500ml atoleine then, temperature programmed reduction in pure hydrogen.Reducing condition does, 400 ℃, and 0.1MPa, 500h
-1(V/V), 6h.After the reduction, cooling switches to synthesis gas and reacts, and reaction condition is 190 ℃, 1MPa, 1000h
-1(V/V),, H
2/ CO=2/1 (Mol ratio).Reaction result is seen table 1.
Embodiment 2
1g CTAB is dissolved in the NaOH aqueous solution of 50ml 0.02mol/L, behind the stirring 30min, adds 0.50g TMB, and the speed with 1ml/min adds 5.62mlTEOS then, after continuing to stir 30min, leaves standstill 3h, then 60 ℃ of aging 40h.Material at 650 ℃ of roasting 6h, obtains mesopore-macropore diplopore distribution carrier with the heating rate of 1 ℃/min behind 60 ℃ of baking 30h.
The 3g carrier is carried out incipient impregnation with being dissolved in the solution that 11ml contains the 6.22g cobalt nitrate.With putting into the internal layer of the double-deck autoclave of top UNICOM without the catalyst of oven dry behind the incipient impregnation 30h; Again the ammonia spirit of 15wt% is placed the skin of autoclave; Seal to be placed in 60 ℃ of baking ovens and react 1h, naturally cool to room temperature, then 60 ℃ of baking 36h in baking oven; 550 ℃ of roasting 1h in Muffle furnace promptly get required catalyst at last.The containing metal cobalt is 35wt% in the catalyst.Mesoporous 35% of the pore structure that accounts in the catalyst, macropore accounts for 60% of pore structure.
(the above-mentioned catalyst of φ 10 * 500nm) filling 2ml 60-80 purposes, temperature programmed reduction in pure hydrogen atmosphere in pressurization static bed reactor.Reducing condition is that 500 ℃, 0.5Mpa, volume space velocity are 500h
-1(V/V), reduction 6h.Reaction condition is that 210 ℃, 1MPa, volume space velocity are 1000h
-1(V/V), H
2/ CO=2/1 (Mol ratio).Reaction result is seen table 1.
Get the slurry attitude stirred tank that the above above-mentioned catalyst 15ml of 100 orders puts into 1L, add the 500ml atoleine then, temperature programmed reduction in pure hydrogen.Reducing condition does, 500 ℃, and 0.5MPa, 500h
-1(V/V), 6h.After the reduction, cooling switches to synthesis gas and reacts, and reaction condition is 210 ℃, 1MPa, 1000h
-1(V/V), H
2/ CO=2/1 (Mol ratio).Reaction result is seen table 1.
Embodiment 3
1g CTAB is dissolved in the NaOH aqueous solution of 10ml 0.03mol/L, behind the stirring 30min, adds 0.80g TMB, and the speed with 1ml/min adds 5.62mlTEOS then, after continuing to stir 30min, leaves standstill 8h, then 100 ℃ of aging 72h.Material at 650 ℃ of roasting 8h, obtains mesopore-macropore diplopore distribution carrier with the heating rate of 1 ℃/min behind 90 ℃ of baking 25h.
The 3g carrier is carried out incipient impregnation with being dissolved in the solution that 8ml contains the 3.527g cobalt nitrate.With putting into the internal layer of the double-deck autoclave of top UNICOM without the catalyst of oven dry behind the incipient impregnation 25h; Again the ammonia spirit of 20wt% is placed the skin of agitated reactor; Seal to be placed in 90 ℃ of baking ovens and react 1h, naturally cool to room temperature, then 60 ℃ of baking 48h in baking oven; 400 ℃ of roasting 3h in Muffle furnace promptly get required catalyst at last.The containing metal cobalt is 25wt% in the catalyst.Mesoporous 20% of the pore structure that accounts in the catalyst, macropore accounts for 60% of pore structure.
(the above-mentioned catalyst of φ 10 * 500nm) filling 2ml 60-80 purposes, temperature programmed reduction in pure hydrogen atmosphere in pressurization static bed reactor.Reducing condition is that 500 ℃, 0.5Mpa, volume space velocity are 500h
-1(V/V), reduction 6h.Reaction condition is that 200 ℃, 2MPa, volume space velocity are 1000h
-1(V/V), H
2/ CO=2/1 (Mol ratio).Reaction result is seen table 1.
Get the slurry attitude stirred tank that the above above-mentioned catalyst 15ml of 100 orders puts into 1L, add the 500ml atoleine then, temperature programmed reduction in pure hydrogen.Reducing condition does, 500 ℃, and 0.5MPa, 500h
-1(V/V), 6h.After the reduction, cooling switches to synthesis gas and reacts, and reaction condition is 200 ℃, 2MPa, 1000h
-1(V/V), H
2/ CO=2/1 (Mol ratio).Reaction result is seen table 1.
Embodiment 4
1g CTAB is dissolved in the NaOH aqueous solution of 50ml 0.02mol/L, behind the stirring 30min, adds 1g TMB, and the speed with 1ml/min adds 5.62mlTEOS then, after continuing to stir 30min, leaves standstill 5h, then 80 ℃ of aging 48h.Material at 550 ℃ of roasting 6h, obtains mesopore-macropore diplopore distribution carrier with the heating rate of 2 ℃/min behind 80 ℃ of baking 28h.
The 3g carrier is carried out incipient impregnation with being dissolved in the solution that 6.8ml contains the 1.754g cobalt nitrate.With putting into the internal layer of the double-deck autoclave of top UNICOM without the catalyst of oven dry behind the incipient impregnation 25h; Again the ammonia spirit of 10wt% is placed the skin of agitated reactor; Seal to be placed in 90 ℃ of baking ovens and react 0.5h, naturally cool to room temperature, then 60 ℃ of baking 48h in baking oven; 400 ℃ of roasting 3h in Muffle furnace promptly get required catalyst at last.The containing metal cobalt is 15wt% in the catalyst.Mesoporous 35% of the pore structure that accounts in the catalyst, macropore accounts for 40% of pore structure.
(the above-mentioned catalyst of φ 10 * 500nm) filling 2ml 60-80 purposes, temperature programmed reduction in pure hydrogen atmosphere in pressurization static bed reactor.Reducing condition is that 400 ℃, 0.5Mpa, volume space velocity are 500h
-1(V/V), reduction 6h.Reaction condition is that 230 ℃, 2MPa, volume space velocity are 2000h
-1(V/V), H
2/ CO=2/1 (Mol ratio).Reaction result is seen table 1.
Get the slurry attitude stirred tank that the above above-mentioned catalyst 15ml of 100 orders puts into 1L, add the 500ml atoleine then, temperature programmed reduction in pure hydrogen.Reducing condition does, 400 ℃, and 0.5MPa, 500h
-1(V/V), 6h.After the reduction, cooling switches to synthesis gas and reacts, and reaction condition is 230 ℃, 2MPa, 2000h
-1(V/V), H
2/ CO=2/1 (Mol ratio).Reaction result is seen table 1.
Embodiment 5
1g CTAB is dissolved in the NaOH aqueous solution of 50ml 0.02mol/L, behind the stirring 30min, adds 1gTMB, and the speed with 2ml/min adds 5.62mlTEOS then, after continuing to stir 40min, leaves standstill 6h, then 70 ℃ of aging 68h.Material at 600 ℃ of roasting 6h, obtains mesopore-macropore diplopore distribution carrier with the heating rate of 1 ℃/min behind 685 ℃ of baking 24h.
The 3g carrier is carried out incipient impregnation with being dissolved in the solution that 11ml contains the 4.719g cobalt nitrate.With putting into the internal layer of the double-deck autoclave of top UNICOM without the catalyst of oven dry behind the incipient impregnation 30h; Ammonia spirit with 15wt% places autoclave outer again; Seal to be placed in 60 ℃ of baking ovens and react 2h, naturally cool to room temperature, then 80 ℃ of baking 12h in baking oven; 550 ℃ of roasting 2h in Muffle furnace promptly get required catalyst at last.The containing metal cobalt is 30wt% in the catalyst.Mesoporous 30% of the pore structure that accounts in the catalyst, macropore accounts for 50% of pore structure.
(the above-mentioned catalyst of φ 10 * 500nm) filling 2ml 60-80 purposes, temperature programmed reduction in pure hydrogen atmosphere in pressurization static bed reactor.Reducing condition is that 250 ℃, 1.2Mpa, volume space velocity are 2000h
-1(V/V), reductase 12 4h.Reaction condition is that 300 ℃, 2MPa, volume space velocity are 2000h
-1(V/V), H
2/ CO=2/1 (Mol ratio).Reaction result is seen table 1.
Get the slurry attitude stirred tank that the above above-mentioned catalyst 15ml of 100 orders puts into 1L, add the 500ml atoleine then, temperature programmed reduction in pure hydrogen.Reducing condition is that 250 ℃, 1.2Mpa, volume space velocity are 2000h
-1(V/V), reductase 12 4h.After the reduction, cooling switches to synthesis gas and reacts, and reaction condition is 300 ℃, 2MPa, 2000h
-1(V/V), H
2/ CO=2/1 (Mol ratio).Reaction result is seen table 1.
Embodiment 6
1g CTAB is dissolved in the NaOH aqueous solution of 10ml 0.03mol/L, behind the stirring 30min, adds 0.80g TMB, and the speed with 1ml/min adds 5.62mlTEOS then, after continuing to stir 50min, leaves standstill 6h, then 80 ℃ of aging 40h.Material at 600 ℃ of roasting 8h, obtains mesopore-macropore diplopore distribution carrier with the heating rate of 2 ℃/min behind 60 ℃ of baking 30h.
The 3g carrier is carried out incipient impregnation with being dissolved in the solution that 7.4ml contains the 2.557g cobalt nitrate.With putting into the internal layer of the double-deck autoclave of top UNICOM without the catalyst of oven dry behind the incipient impregnation 30h; Ammonia spirit with 15wt% places skin again; Seal to be placed in 80 ℃ of baking ovens and react 2h, naturally cool to room temperature, then 80 ℃ of baking 24h in baking oven; 550 ℃ of roasting 2h in Muffle furnace promptly get required catalyst at last.The containing metal cobalt is 20wt% in the catalyst.Mesoporous 25% of the pore structure that accounts in the catalyst, macropore accounts for 55% of pore structure.
(the above-mentioned catalyst of φ 10 * 500nm) filling 2ml 60-80 purposes, temperature programmed reduction in pure hydrogen atmosphere in pressurization static bed reactor.Reducing condition is that 400 ℃, 1Mpa, volume space velocity are 1500h
-1(V/V), reduction 6h.Reaction condition is that 240 ℃, 2MPa, volume space velocity are 1500h
-1(V/V), H
2/ CO=2/1 (Mol ratio).Reaction result is seen table 1.
Get the slurry attitude stirred tank that the above above-mentioned catalyst 15ml of 100 orders puts into 1L, add the 500ml atoleine then, temperature programmed reduction in pure hydrogen.Reducing condition does, 400 ℃, and 1MPa, 1500h
-1(V/V), 6h.After the reduction, cooling switches to synthesis gas and reacts, and reaction condition is 240 ℃, 5MPa, 1500h
-1(V/V), H
2/ CO=2/1 (Mol ratio).Reaction result is seen table 1.
Embodiment 7
1g CTAB is dissolved in the NaOH aqueous solution of 10ml 0.02mol/L, behind the stirring 50min, adds 0.50g TMB, and the speed with 1ml/min adds 5.62mlTEOS then, after continuing to stir 40min, leaves standstill 5h, then 80 ℃ of aging 40h.At 600 ℃ of roasting 8h, obtain mesopore-macropore diplopore distribution carrier with the heating rate of 2 ℃/min.
The 3g carrier is carried out incipient impregnation with being dissolved in the solution that 8.3ml contains the 4.211g cobalt nitrate.With putting into the internal layer of the double-deck autoclave of top UNICOM without the catalyst of oven dry behind the incipient impregnation 30h; Again the ammonia spirit of 15wt% is placed the skin of autoclave; Seal to be placed in 80 ℃ of baking ovens and react 2h, naturally cool to room temperature, then 80 ℃ of baking 24h in baking oven; 550 ℃ of roasting 2h in Muffle furnace promptly get required catalyst at last.The containing metal cobalt is 28wt% in the catalyst.Mesoporous 25% of the pore structure that accounts in the catalyst, macropore accounts for 55% of pore structure.
(the above-mentioned catalyst of φ 10 * 500nm) filling 2ml 60-80 purposes, temperature programmed reduction in pure hydrogen atmosphere in pressurization static bed reactor.Reducing condition is that 250 ℃, 1Mpa, volume space velocity are 1500h
-1(V/V), reduction 6h.Reaction condition is that 220 ℃, 2MPa, volume space velocity are 1500h
-1(V/V), H
2/ CO=2/1 (Mol ratio).Reaction result is seen table 1.
Get the slurry attitude stirred tank that the above above-mentioned catalyst 15ml of 100 orders puts into 1L, add the 500ml atoleine then, temperature programmed reduction in pure hydrogen.Reducing condition does, 250 ℃, and 1MPa, 1500h
-1(V/V), 6h.After the reduction, cooling switches to synthesis gas and reacts, and reaction condition is 220 ℃, 5MPa, 1500h
-1(V/V),, H
2/ CO=2/1 (Mol ratio).Reaction result is seen table 1.
Table 1 catalyst applications condition and reaction result
Claims (4)
1. mesopore-macropore cobalt-base catalyst is characterized in that catalyst is made up of active component and carrier, and percentage by weight consists of: metallic cobalt: 5-35%, silica are 65-95%;
Described mesopore-macropore cobalt-base catalyst is diplopore and distributes, and first aperture is 2.3-50nm, accounts for the 20-35% of catalyst pores structure, and second aperture is 50-100nm, does not comprise 50nm, accounts for the 40-60% of catalyst pores structure;
And by the preparation of following method:
(1) preparation of mesopore-macropore silica supports:
Softex kw is dissolved in the NaOH aqueous solution of 0.01-0.05mol/L; Add expanding agent 1,3, the 5-trimethylbenzene after stirring 30-60min; Speed with 1-2mL/min adds ethyl orthosilicate again; After continuing to stir 30-60min, leave standstill 3-8h, then 60-100 ℃ of aging 36-72h; Material dries by the fire 24-30h down at 60-90 ℃, is warming up at 500-650 ℃ of roasting 6-10h with 1-3 ℃/min, obtains the silica supports that the mesopore-macropore diplopore distributes;
Each material molar ratio is softex kw: 1,3, and 5-trimethylbenzene: NaOH: ethyl orthosilicate=0.1-5: 1: 0.1-0.6: 10;
(2) mesopore-macropore Preparation of catalysts:
With putting into the internal layer of the double-deck autoclave of top UNICOM without the catalyst of oven dry behind the solubility cobalt salt incipient impregnation 20-30h; Ammonia spirit with 10-20wt% places skin again; Seal and be placed on 60-90 ℃ of reaction 0.5-2h, naturally cool to room temperature, then at 60-80 ℃ of baking 12-48h; At 400-550 ℃ of roasting 1-3h, promptly get required catalyst at last.
2. the preparation method of mesopore-macropore cobalt-base catalyst as claimed in claim 1 is characterized in that comprising the steps:
(1) preparation of mesopore-macropore silica supports:
Softex kw is dissolved in the NaOH aqueous solution of 0.01-0.05mol/L; Add expanding agent 1,3, the 5-trimethylbenzene after stirring 30-60min; Speed with 1-2mL/min adds ethyl orthosilicate again; After continuing to stir 30-60min, leave standstill 3-8h, then 60-100 ℃ of aging 36-72h; Material dries by the fire 24-30h down at 60-90 ℃, is warming up at 500-650 ℃ of roasting 6-10h with 1-3 ℃/min, obtains the silica supports that the mesopore-macropore diplopore distributes;
Each material molar ratio is softex kw: 1,3, and 5-trimethylbenzene: NaOH: ethyl orthosilicate=0.1-5: 1: 0.1-0.6: 10;
(2) mesopore-macropore Preparation of catalysts:
With putting into the internal layer of the double-deck autoclave of top UNICOM without the catalyst of oven dry behind the solubility cobalt salt incipient impregnation 20-30h; Ammonia spirit with 10-20wt% places skin again; Seal and be placed on 60-90 ℃ of reaction 0.5-2h, naturally cool to room temperature, then at 60-80 ℃ of baking 12-48h; At 400-550 ℃ of roasting 1-3h, promptly get required catalyst at last.
3. the preparation method of mesopore-macropore cobalt-base catalyst as claimed in claim 2 is characterized in that described solubility cobalt salt is cobalt nitrate or cobalt acetate.
4. the application of mesopore-macropore cobalt-base catalyst as claimed in claim 1 is characterized in that both being used for fixing a Fischer-Tropsch synthesis device, is used for starching the attitude bed again;
Reducing condition is: pure hydrogen atmosphere, and 250～500 ℃, 0.1～1.20MPa, volume space velocity are 500-2000h-1, recovery time 6-24h;
Reaction condition is: 190～300 ℃, 0.5～5.0MPa, volume space velocity are 500～2000h
-1, H
2/ CO mol ratio is 1～3: 1.
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| CN101224425A (en) * | 2008-01-30 | 2008-07-23 | 中国科学院山西煤炭化学研究所 | Co catalyst with controllable Fischer-Tropsch product distribution, preparing and applications thereof |
| CN101224430A (en) * | 2008-01-30 | 2008-07-23 | 中国科学院山西煤炭化学研究所 | Hydrophobic organic modification of Co group Fischer-Tropsch synthesized catalyst, preparing and applications thereof |
| CN101269329A (en) * | 2008-05-19 | 2008-09-24 | 中国科学院山西煤炭化学研究所 | Cobalt group catalyst synthesized with fischer tropsch process, production method and application thereof |
| CN101411989A (en) * | 2008-11-25 | 2009-04-22 | 福州大学 | Preparation of Co-based Fischer-Tropsch synthetic catalyst using silicon based molecular sieve with mixed macropore and mesopore as vector, and uses thereof |
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