CN101698152A - Cobalt-based compounded catalyst and preparing method and application thereof - Google Patents
Cobalt-based compounded catalyst and preparing method and application thereof Download PDFInfo
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- CN101698152A CN101698152A CN200910272466A CN200910272466A CN101698152A CN 101698152 A CN101698152 A CN 101698152A CN 200910272466 A CN200910272466 A CN 200910272466A CN 200910272466 A CN200910272466 A CN 200910272466A CN 101698152 A CN101698152 A CN 101698152A
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Abstract
The invention provides a cobalt-based compounded catalyst and preparing method and application thereof, comprising a carrier component and a metal component; the carrier uses spherical powder Al2O3; the metal component comprises a first metal component Co; a second metal component is one of Ce, La and Zr; a third metal component is one of Pt, Ru, Rh and Re; the weight percentage of each metal component in the finished catalyst is as follows: the first metal component is 10-35%; the second metal component is 0.5-10%; the third metal component is 0.05-3%; and the rest is aluminum oxide carrier. The invention is cobalt-based compounded catalyst with the diesel oil and paraffin as the main products; and the catalyst is applied for slurry bubble column reactor or continuous-stirring reactor with simple preparing method, less selectivity in methane, high reacting activity and good selectivity in C5+.
Description
Technical field
The present invention relates to a kind of Co based Fischer-Tropsch synthesis catalyst and its production and application, relate to a kind of preparation method and application that is used for the Co based Fischer-Tropsch synthesis catalyst of paste state bed reactor specifically.
Background technology
Synthetic synthesis gas (the CO+H that is meant of Fischer-Tropsch
2) on catalyst, transforming the reaction that generates hydro carbons, product comprises various alkane and alkene, and by-product CO
2, H
2Organic oxygen-containing things such as O and alcohol, aldehyde, ketone, acid and ester can get high-quality liquid fuel such as gasoline, diesel oil, aviation kerosine etc. through deep processing.Be that nineteen twenty-three is by Germany scientist Frans Fischer and Hans Tropsch invention, so the abbreviation Fischer-Tropsch is synthetic or F-T is synthetic.
In recent years, along with the shortage day by day of world's crude resources and the fluctuation of crude oil price rise and fall, develop multiple liquid fuel source and be subject to people's attention day by day.Carbonaceous materials such as natural gas, coal, living beings all can be converted into synthesis gas through gasification, synthesis gas can be converted into liquid fuel through the Fischer-Tropsch building-up process again, owing to this liquid fuel comes through synthetic cyclostrophicization, be also referred to as artificial oil, be a kind of no sulphur, no nitrogen, the super clean fuel that nitrogen oxide emission is low, can be applied to existing automobile engine system fully and do not need engine system is carried out any improvement, be the regenerative resource of clean environment firendly, have important economic implications and commercial value.
The main metal of fischer-tropsch synthetic catalyst is based on the 8th family's element of Fe, Co, Ni and Ru, and Fe, Co are the comparatively desirable fischer-tropsch synthetic catalysts through the industry checking.Wherein the Ru catalytic activity is the highest, the chain growth ability excellence of product, but because of its resource-constrained, cost an arm and a leg, so the general auxiliary agent that only is used as improves activity of such catalysts and selectivity.When making catalyst, Ni is easy to generate methane, and should not be as the catalyst of synthetic long chain hydrocarbon.Activity is higher during Fe catalysis CO hydrogenation reaction, but under reaction condition, easy oxidation of Fe and carbon deposit, active high to water gas shift reaction in addition, the chain growth ability of synthetic hydrocarbon.Co is insensitive to water gas reaction, the catalytic hydrogenation activity height, and reaction rate is not subjected to the influence of water partial pressure, is difficult for carbon deposit and poisoning, and generates CO
2Selectivity low, the selectivity height of long chain hydrocarbon, oxygenatedchemicals is less in the product, is synthetic at present long chain hydrocarbon catalyst system preferably.
The molecular weight distribution of Fischer-Tropsch Synthin product is very wide, can only obtain the hydrocarbon mixture product, and poor selectivity is a synthetic notable feature of Fischer-Tropsch.Therefore, research and development high activity, high selectivity, catalyst with good engineering characteristic are the contents of core the most in the research of Fischer-Tropsch synthetic technology.
For the load type cobalt-base fischer-tropsch synthetic catalyst, there have been considerable patent and article that the adding method of kind of carrier, the kind of adding other metal components and other metal components is studied.As European patent EP 0358811B1 respectively with Al
2O
3With molecular sieve TC-123 be carrier, except that main active component Co, added second kind of metal component Mn, improved the selectivity of product and the stability of catalyst.U.S. Pat 4822824 is with TiO
2Be carrier, added ruthenium, adopt coprecipitation to prepare Co-Ru/TiO as co-catalyst
2Catalyst can reduce methane selectively, improves the C5+ selectivity, and has prolonged the service life of catalyst.
Patent CN 10129329A adopts reduction-deactivation method to prepare Co based Fischer-Tropsch synthesis catalyst, and the metallic cobalt percetage by weight is 5～35%, does not add other metal components.Whole process of preparation is comparatively complicated, and catalyst still needs activation once more before using behind reduction and passivating process, the catalyst cost is significantly improved.And method therefor of the present invention is simple, has omitted reduction and the passivation step in the preparation process, and the catalyst cost is significantly reduced, and resulting catalyst activity is higher by comparison, and the C5+ selectivity is also better.
Patent CN 1386821A provides a kind of Ln0-Co catalyst based, and this catalyst is active component with the cobalt, has wherein added a kind of co-catalyst, and this co-catalyst is La, Ce, and Mg, Mn, Zr, a kind of in the elements such as K is with SiO
2Or Al
2O
3Be carrier, catalyst reacts in fixed bed reactors.And the catalyst that the present invention relates to uses Al
2O
3Be carrier, except that the active component cobalt, added the two kind metal components different in addition with patent CN1386821A, catalyst activity is higher, methane selectively is lower, and product is based on diesel oil and paraffin, and catalyst is applicable to bubbling paste state bed reactor or continuous stirring paste state bed reactor.
Summary of the invention
The object of the present invention is to provide a kind of preparation simple, methane selectively is low, the catalytic reaction activity height, the C5+ selectivity is good, with diesel oil and paraffin is Co based Fischer-Tropsch synthesis catalyst of primary product and its production and application, and this catalyst is applicable to bubbling slurry attitude bed or continuous stirring paste state bed reactor.
Technical scheme of the present invention: Co based Fischer-Tropsch synthesis catalyst of the present invention comprises carrier and metal component, and its carrier adopts spherical powder Al
2O
3Metal component comprises that first kind of metal component is Co, and second kind of metal component is Ce, La, and a kind of among the Zr, the third metal component is a kind of among Pt, Ru, Rh, the Re; In finished catalyst, the percentage by weight of each metal component is: first kind of metal component: 10～35%, second kind of metal component: 0.5%～10%; The third metal component: 0.05%～3%, surplus is an alumina support.
Described Co based Fischer-Tropsch synthesis catalyst, its metal component percentage by weight is: first kind of metal component: 15～35%, second kind of metal component: 1%～5%; The third metal component: 0.1%～1%, surplus is an alumina support.
Described spherical powder Al
2O
3Be γ-Al
2O
3, the average grain scope is 20～120 microns, and the part that is lower than 25 microns is no more than 3%, and specific area is 130～180m
2/ g, the aperture is 5～12nm, pore volume is 0.3～0.5cm
3/ g.
The preparation method of described Co based Fischer-Tropsch synthesis catalyst is as follows:
Step (1) is with the Al of predetermined volume
2O
3Carrier is put into Muffle furnace, and at 350～550 ℃ of roasting 4～10h, taking-up places drier standby;
Step (2) takes by weighing the nitrate of the cobalt nitrate, second kind of metal component and the third metal component that calculate consumption, is dissolved in jointly in the deionized water, makes it fully to dissolve and mix;
Step (3) adopts full hole infusion process, on rotary evaporator with step (2) solution impregnation at Al
2O
3On the carrier, vacuumize drying at 70～110 ℃;
Step (4) is with the at room temperature aging 4～24h of dried catalyst, and at 100～120 ℃ of down dry 6～24h, roasting 2～24h between 300～500 ℃ makes finished catalyst then.
The preparation method of described Co based Fischer-Tropsch synthesis catalyst is as follows:
Step (1) is with the Al of predetermined volume
2O
3Carrier is put into Muffle furnace, 400～500 ℃ of roasting 6～10h the bests;
Step (3) adopts full hole infusion process, on rotary evaporator with step (2) solution impregnation at Al
2O
3On the carrier, vacuumize dry best at 70～90 ℃;
Step (4) is with the at room temperature aging 6～16h of dried catalyst, then in 100～120 ℃ of down dry 6～16h, roasting 2～12h the best between 300～450 ℃.
The preparation method of described Co based Fischer-Tropsch synthesis catalyst, during obtain solution, the salt of first kind of used active metal component cobalt is cobalt nitrate, cobalt acetate or carbonyl cobalt; The salt of second kind of metal component is the nitrate of selected metal; The salt of the third metal component is the nitrate of selected metal, also can be the nitrosyl radical nitrate of these metals.
Described full hole infusion process is meant that the solution amount of dipping is enough to fill the hole of carrier and make the carrier granular outer surface fully wetting just, and the while catalyst surface does not exist can free-pouring liquid.
The catalyst granules diameter range of preparation moulding is 10～180 microns, and specific area is 80～160m
2/ g, the aperture is 5～12nm, pore volume is 0.3～0.5cm
3/ g.This catalyst mainly is applicable to bubbling paste state bed reactor or continuous stirring paste state bed reactor.
Application process of the present invention is as follows:
Catalyst needed before using through reduction in advance, and the present invention adopts pure H
2(purity＞99.9%) is reducing gas, can carry out on fixed bed reactors or fluidized-bed reactor.Catalyst reduction finishes, and needs to transfer in the paste state bed reactor under the condition of anhydrous and oxygen-free, carries out Fischer-Tropsch synthesis in paste state bed reactor, and reacting gas is a synthesis gas.
The condition that catalyst activates on fixed reactor is: the reducing gas volume space velocity is 1000～5000h
-1, heating rate is 1～3 ℃/min, and activation temperature is 300～500 ℃, and activation pressure is 0.1～0.5MPa, and soak time is 2～16h.
The condition that catalyst activates on fluidized-bed reactor is: the reducing gas volume space velocity is 1000～5000h
-1, heating rate is 1～3 ℃/min, and activation temperature is 300～500 ℃, and activation pressure is 0.5～2MPa, and soak time is 2～16h.
Catalyst carries out Fischer-Tropsch synthesis in paste state bed reactor condition is: H in the synthesis gas
2: CO=1～3, synthesis gas volume air speed is 1000～10000h
-1, reaction temperature is 200～240 ℃, reaction pressure is 1.0～3.0MPa.
The application of described Co based Fischer-Tropsch synthesis catalyst, the fixed bed reactors activation condition is: reducing gases volume air speed is 1500～3000h
-1The best, heating rate are 1～2 ℃/min the best, and activation temperature is 350～450 ℃ of the bests, and activation pressure is 0.3～0.5MPa the best, and soak time is 6～12h the best.
The condition that the application of described Co based Fischer-Tropsch synthesis catalyst, catalyst activate on fluidized-bed reactor is: reducing gases volume air speed is 1000～3000h
-1The best, heating rate are 1～2 ℃/min the best, and activation temperature is 350～450 ℃ of the bests, and activation pressure is 1.0～2.0MPa the best, and soak time is 6～12h the best.
Fischer-Tropsch synthesis is carried out in the application of described Co based Fischer-Tropsch synthesis catalyst, catalyst in paste state bed reactor condition is: H in the synthesis gas
2: CO=1.5～2.5 the bests, synthesis gas volume air speed is 2000～6000h
-1The best, reaction temperature are 210～230 ℃ of the bests, and reaction pressure is 2.0～3.0MPa the best.
The present invention has the following advantages:
1, the Co based Fischer-Tropsch synthesis catalyst that the present invention relates to has high reactivity, and methane selectively is low, C5+ long chain hydrocarbon selectivity height.In the fischer-tropsch synthetic catalyst, the reactive metal that plays main catalytic action is Co, in theory, under the identical situation of decentralization, the content of Co is high more, and activity of such catalysts is just high more, but in fact the content of Co is subjected to the restriction of used carrier, the specific area of carrier, character such as aperture and pore volume have limited the ultimate load of Co; If simultaneously the load capacity of Co is excessive, then be easy to assemble agglomerating, can reduce catalyst activity on the contrary.So, need to add auxiliary agent improving the dispersion of Co on catalyst carrier, thereby bring into play the catalytic action of Co as much as possible.Among the present invention, second kind of metal component Ce, La, Zr exist mainly as structural promoter, can effectively promote the dispersion of Co, form more catalytic active center.The third metal component Ru, Pt, Rh and Re mainly promote H
2In the absorption and the disassociation of catalyst surface, thereby promote CO and H indirectly
2Reaction, improve whole catalyst activity.Simultaneously, second kind is not The more the better with the third metal component, and its optimum value is arranged within the specific limits.In the formula range of the best, to compare with adding assistant not or the catalyst that only adds a kind of auxiliary agent, the catalyst activity that adds two kinds of auxiliary agents is significantly improved, and methane selectively is lower simultaneously, and the above hydrocarbon selective of C5 is higher.
2, the present invention is by selecting the Al of special pore size distribution and specific area for use
2O
3Carrier can be regulated the synthetic product of Fischer-Tropsch and distribute the selectivity height of diesel oil and paraffinic components in the product of generation.Fischer-Tropsch synthetic distributes wide, and up to the very big paraffin of molecular weight, poor selectivity is a shortcoming of this reaction to synthetic product from methane.Some patents are selected more novel carrier such as TC-123 molecular sieve for use, and MCM-41 molecular sieve, HSM molecular sieve wait and improve selectivity of product, but a lot of manufacturing cost of molecular sieve own is higher, have significantly increased the cost of catalyst.In addition, adopt the method for in dipping process, adding complexing agent to control the distribution of cobalt granule as patent CN101224425A, thereby the control Fischer-Tropsch product distribute at carrier surface.We adopt the Al of different apertures and specific area by discovering
2O
3Carrier also can obviously improve product selectivity, when the carrier specific area at 130～180m
2/ g when the aperture is 5～12nm, more helps generating diesel oil and paraffinic components.Used Al
2O
3Carrier has ripe industrialization supply, greatly reduces the catalyst manufacturing cost.
3, the cobalt-base catalyst preparation technology who the present invention relates to is simple, and the good prospect of large-scale industrial production is arranged.In order to improve catalyst performance, some patents such as CN10129329A adopt the method for reduction post-passivation earlier, preparation process complexity.And the present invention adopts the method for adding auxiliary agent, and the mixed solution co-impregnation is adopted in the interpolation of auxiliary agent, and flow process is simple, is convenient to operation, is more suitable for suitability for industrialized production.
The specific embodiment
The Co based Fischer-Tropsch synthesis catalyst that is used for paste state bed reactor of the present invention comprises carrier and metal component, and its carrier adopts spherical powder Al
2O
3Metal component comprises that first kind of metal component is Co, and second kind of metal component is Ce, La, and a kind of among the Zr, the third metal component is a kind of among Pt, Ru, Rh, the Re; In finished catalyst, the percentage by weight of each metal component is: first kind of metal component: 10～35%, second kind of metal component: 0.5%～10%; The third metal component: 0.05%～3%, surplus is an alumina support.
The described Co based Fischer-Tropsch synthesis catalyst that is used for paste state bed reactor is characterized in that: the metal component percentage by weight is: first kind of metal component: 15～35%, second kind of metal component: 1%～5%; The third metal component: 0.1%～1%, surplus is an alumina support.
Described spherical powder Al
2O
3Be γ-Al
2O
3, the average grain scope is 20～120 microns, and the part that is lower than 25 microns is no more than 3%, and specific area is 130～180m
2/ g, the aperture is 5～12nm, pore volume is 0.3～0.5cm
3/ g.
The preparation method of described Co based Fischer-Tropsch synthesis catalyst is as follows:
Step (1) is with the Al of predetermined volume
2O
3Carrier is put into Muffle furnace, and at 350～550 ℃ of roasting 4～10h, taking-up places drier standby;
Step (2) takes by weighing the nitrate of the cobalt nitrate, second kind of metal component and the third metal component that calculate consumption, is dissolved in jointly in the deionized water, makes it fully to dissolve and mix;
Step (3) adopts full hole infusion process, on rotary evaporator with step (2) solution impregnation at Al
2O
3On the carrier, vacuumize drying at 70～110 ℃;
Step (4) is with the at room temperature aging 4～24h of dried catalyst, and at 100～120 ℃ of down dry 6～24h, roasting 2～24h between 300～500 ℃ makes finished catalyst then.
The preparation method of the described Co based Fischer-Tropsch synthesis catalyst that is used for paste state bed reactor is as follows:
Step (1) is with the Al of predetermined volume
2O
3Carrier is put into Muffle furnace, 400～500 ℃ of roasting 6～10h the bests;
Step (3) adopts full hole infusion process, on rotary evaporator with step (2) solution impregnation at Al
2O
3On the carrier, vacuumize dry best at 70～90 ℃;
Step (4) is with the at room temperature aging 6～16h of dried catalyst, then in 100～120 ℃ of down dry 6～16h, roasting 2～12h the best between 300～450 ℃.
The described preparation method who is used for the Co based Fischer-Tropsch synthesis catalyst of paste state bed reactor, during obtain solution, the salt of first kind of used active metal component cobalt is cobalt nitrate, cobalt acetate or carbonyl cobalt; The salt of second kind of metal component is the nitrate of selected metal; The salt of the third metal component is the nitrate of selected metal, also can be the nitrosyl radical nitrate of these metals.
The catalyst granules diameter range of preparation moulding is 10～180 microns, and specific area is 80～160m
2/ g, the aperture is 5～12nm, pore volume is 0.3～0.5cm
3/ g.
The condition that the application of described Co based Fischer-Tropsch synthesis catalyst, catalyst activate on fixed bed reactors is: reducing gas is pure H
2(purity＞99.9%), its volume space velocity are 1000～5000h
-1, heating rate is 1～3 ℃/min, and activation temperature is 300～500 ℃, and activation pressure is 0.1～0.5MPa, and soak time is 2～16h; Catalyst is applied to paste state bed reactor to carry out the reaction condition of Fischer-Tropsch when synthetic and be: reacting gas is a synthesis gas, and its volume space velocity is 1000～10000h
-1, H in the synthesis gas
2: CO=1～3, reaction temperature are 200～240 ℃, and reaction pressure is 1.0～3.0MPa.
The application of described Co based Fischer-Tropsch synthesis catalyst, the fixed bed reactors activation condition is: the reducing gas volume space velocity is 1500～3000h
-1The best, heating rate are 1～2 ℃/min the best, and activation temperature is 350～450 ℃ of the bests, and activation pressure is 0.3～0.5MPa the best, and soak time is 6～12h the best; Catalyst is applied to paste state bed reactor to carry out the reaction condition of Fischer-Tropsch when synthetic and be: synthesis gas volume air speed is 2000～6000h
-1The best, H in the synthesis gas
2: CO=1.5～2.5 the bests, reaction temperature is 210～230 ℃ of the bests, reaction pressure is 2.0～3.0MPa the best.
The condition that the application of described Co based Fischer-Tropsch synthesis catalyst, catalyst activate on fluidized-bed reactor is: reducing gases is pure H
2(purity＞99.9%), its volume space velocity are 1000～5000h
-1, heating rate is 1～3 ℃/min, and activation temperature is 300～500 ℃, and activation pressure is 0.5～2.0MPa, and soak time is 2～16h; Catalyst is applied to paste state bed reactor to carry out the reaction condition of Fischer-Tropsch when synthetic and be: reacting gas is a synthesis gas, and volume space velocity is 1000～10000h
-1, H in the synthesis gas
2: CO=1～3, reaction temperature are 200～240 ℃, and reaction pressure is 1.0～3.0MPa.
The application of described Co based Fischer-Tropsch synthesis catalyst, the condition that its catalyst activates on fluidized-bed reactor is: the reducing gas volume space velocity is 1000～3000h
-1The best, heating rate are 1～2 ℃/min the best, and activation temperature is 350～450 ℃ of the bests, and activation pressure is 1.0～2.0MPa the best, and soak time is 6～12h the best; Catalyst is applied to paste state bed reactor to carry out the reaction condition of Fischer-Tropsch when synthetic and be: the reacting gas air speed is 2000～6000h
-1The best, H in the synthesis gas
2: CO=1.5～2.5 the bests, reaction temperature is 210～230 ℃ of the bests, reaction pressure is 2.0～3.0MPa the best.
The following examples will the present invention is described further, and protection scope of the present invention is not subjected to the restriction of these embodiment.
Embodiment one:
Take by weighing an amount of Al
2O
3Carrier, the 100g that gets wherein behind 550 ℃ of roasting 4h in Muffle furnace is standby in advance.Take by weighing the 53.6g cabaltous nitrate hexahydrate, 1.7g six nitric hydrate ceriums, 11.8g nitrosyl radical nitric acid ruthenium is dissolved in the deionized water, stirs to make it fully to dissolve and mix, and liquor capacity is diluted to 110ml.Adopt full hole infusion process, solution impregnation is arrived 100g Al
2O
3On the carrier.The catalyst that dipping is good vacuumizes drying 80 ℃ of following water-baths, places at room temperature aging 24h then.Be placed on after aging and slowly be warming up to 120 ℃ in the Muffle furnace, dry 6h under 120 ℃ is warming up to 500 ℃ of roasting 8h then.The catalyst that makes consists of: Co: Ce: Ru: Al
2O
3=10: 0.5: 3: 86.5.
The catalyst activation is carried out on pressurization static bed reactor: get the catalyst 20ml for preparing, in the reactor of packing into, with pure H
2(purity＞99%) is reducing gas, and volume space velocity is 1000h
-1, heating rate is 3 ℃/min, and activation temperature is 500 ℃, and activation pressure is 0.5MPa, and soak time is 10h.
Catalytic reaction is being carried out on the paste state bed reactor: getting under the good condition of catalyst 10ml at anhydrous and oxygen-free of activation and be transferred in the paste state bed reactor, is reaction medium with the polyolefin, feeds synthesis gas, and regulating flow, to make air speed be 1000h
-1, H in the synthesis gas
2: CO=2, conditioned reaction device internal pressure is 1.0MPa.Set heating schedule, make reaction temperature rise to 150 ℃ with the speed of 5 ℃/min from room temperature, the speed with 2 ℃/min is warming up to 230 ℃ then, reacts at 230 ℃.Reaction evaluating the results are shown in the subordinate list.
Embodiment two:
Take by weighing an amount of Al
2O
3Carrier, the 100g that gets wherein behind 350 ℃ of roasting 10h in Muffle furnace is standby in advance.Take by weighing the 93.8g cabaltous nitrate hexahydrate, the 39.1g lanthanum nitrate hexahydrate, the 4.65g platinum nitrate is dissolved in the deionized water, stirs to make it fully to dissolve and mix, and liquor capacity is diluted to 90ml.Adopt full hole infusion process, solution impregnation is arrived 95g Al
2O
3On the carrier.The catalyst that dipping is good vacuumizes drying 90 ℃ of following water-baths, places at room temperature aging 4h then.Be placed on after aging and slowly be warming up to 110 ℃ in the Muffle furnace, dry 6h under 110 ℃ is warming up to 400 ℃ of roasting 16h then.The catalyst that makes consists of: Co: La: Pt: Al
2O
3=15: 10: 1: 74.
The catalyst activation is carried out on pressurization static bed reactor: get the catalyst 20ml for preparing, and in the reactor of packing into, pure H
2(purity＞99.9%) is reducing gas, and volume space velocity is 3000h
-1, heating rate is 2 ℃/min, and activation temperature is 350 ℃, and activation pressure is 1.5MPa, and soak time is 4h.
Catalytic reaction is being carried out on the paste state bed reactor: getting under the good condition of catalyst 10ml at anhydrous and oxygen-free of activation and be transferred in the paste state bed reactor, is reaction medium with the polyolefin, feeds synthesis gas, H in the synthesis gas
2: CO=1.5, it is 3000h that the adjusting flow makes air speed
-1, conditioned reaction device internal pressure is 3.0MPa.Set heating schedule, make reaction temperature rise to 150 ℃ with the speed of 3 ℃/min from room temperature, the speed with 2 ℃/min is warming up to 220 ℃ then, reacts at 220 ℃.Reaction evaluating the results are shown in the subordinate list.
Embodiment three:
Take by weighing an amount of Al
2O
3Carrier, the 100g that gets wherein behind 550 ℃ of roasting 6h in Muffle furnace is standby in advance.Take by weighing the 169.4g cabaltous nitrate hexahydrate, the 8.55g zirconium nitrate, 0.26g nitric acid rhenium is dissolved in the deionized water, stirs to make it fully to dissolve and mix, and liquor capacity is diluted to 100ml.Adopt full hole infusion process, solution impregnation is arrived 100g Al
2O
3On the carrier.The catalyst that dipping is good vacuumizes drying 80 ℃ of following water-baths, places at room temperature aging 12h then.Be placed on after aging and slowly be warming up to 120 ℃ in the Muffle furnace, dry 24h under 110 ℃ is warming up to 450 ℃ of roasting 10h then.The catalyst that makes consists of: Co: Zr: Re: Al
2O
3=25: 2: 0.05: 72.9.
The catalyst activation is carried out on fluidized-bed reactor: get the catalyst 20ml for preparing, and in the reactor of packing into, pure H
2(purity＞99%) is reducing gas, and volume space velocity is 5000h
-1, heating rate is 1 ℃/min, and activation temperature is 400 ℃, and activation pressure is 2MPa, and soak time is 16h.
Catalytic reaction is being carried out on the paste state bed reactor: getting under the good condition of catalyst 10ml at anhydrous and oxygen-free of activation and be transferred in the paste state bed reactor, is reaction medium with the polyolefin, feeds synthesis gas, and regulating flow, to make air speed be 10000h
-1, H in the synthesis gas
2: CO=1.5, conditioned reaction device internal pressure is 3.0MPa.Set heating schedule, make reaction temperature rise to 150 ℃ with the speed of 5 ℃/min from room temperature, the speed with 1 ℃/min is warming up to 220 ℃ then, reacts at 220 ℃.Reaction evaluating the results are shown in the subordinate list.
Embodiment four:
Take by weighing an amount of Al
2O
3Carrier, the 100g that gets wherein behind 350 ℃ of roasting 4h in Muffle furnace is standby in advance.Take by weighing the 288.1g cabaltous nitrate hexahydrate, the 15.7g lanthanum nitrate hexahydrate, 10.7g nitrosyl radical nitric acid ruthenium is dissolved in the deionized water, stirs to make it fully to dissolve and mix, and liquor capacity is diluted to 110ml.Adopt full hole infusion process, solution impregnation is arrived 100g Al
2O
3On the carrier.The catalyst that dipping is good vacuumizes drying 80 ℃ of following water-baths, places at room temperature aging 12h then.Be placed on after aging and slowly be warming up to 120 ℃ in the Muffle furnace, dry 24h under 110 ℃ is warming up to 450 ℃ of roasting 10h then.The catalyst that makes consists of: Co: La: Ru: Al
2O
3=35: 3: 2: 60.
The catalyst activation is carried out on fluidized-bed reactor: get the catalyst 80ml for preparing, in the reactor of packing into, with pure H
2(purity＞99%) is reducing gas, and volume space velocity is 5000h
-1, heating rate is 2 ℃/min, and activation temperature is 400 ℃, and activation pressure is 1.5MPa, and soak time is 10h.
Catalytic reaction is being carried out on the paste state bed reactor: getting under the good condition of catalyst 10ml at anhydrous and oxygen-free of activation and be transferred in the paste state bed reactor, is reaction medium with the polyolefin, feeds synthesis gas, and regulating flow, to make air speed be 8000h
-1, H in the synthesis gas
2: CO=2, conditioned reaction device internal pressure is 2.0MPa.Set heating schedule, make reaction temperature rise to 150 ℃ with the speed of 5 ℃/min from room temperature, the speed with 2 ℃/min is warming up to 215 ℃ then, reacts at 215 ℃.Reaction evaluating the results are shown in the subordinate list.
Embodiment five:
Take by weighing an amount of Al
2O
3Carrier, the 100g that gets wherein behind 500 ℃ of roasting 10h in Muffle furnace is standby in advance.Take by weighing the 132.3g cabaltous nitrate hexahydrate, the 20.9g lanthanum nitrate hexahydrate, the 1.3g rhodium nitrate is dissolved in the deionized water, stirs to make it fully to dissolve and mix, and liquor capacity is diluted to 130ml.Adopt full hole infusion process, solution impregnation is arrived 100g Al
2O
3On the carrier.The catalyst that dipping is good vacuumizes drying 70 ℃ of following water-baths, places at room temperature aging 12h then.Be placed on after aging and slowly be warming up to 120 ℃ in the Muffle furnace, dry 24h under 110 ℃ is warming up to 450 ℃ of roasting 10h then.The catalyst that makes consists of: Co: La: Rh: Al
2O
3=20: 5: 0.3: 74.7.
The catalyst activation is carried out on fluidized-bed reactor: get the catalyst 80ml for preparing, in the reactor of packing into, with pure H
2(purity＞99%) is reducing gas, and volume space velocity is 2000h
-1, heating rate is 2 ℃/min, and activation temperature is 400 ℃, and activation pressure is 1.0MPa, and soak time is 8h.
Catalytic reaction is being carried out on the paste state bed reactor: getting under the good condition of catalyst 10ml at anhydrous and oxygen-free of activation and be transferred in the paste state bed reactor, is reaction medium with the polyolefin, feeds synthesis gas, and regulating flow, to make air speed be 6000h
-1, H in the synthesis gas
2: CO=2, conditioned reaction device internal pressure is 3.0MPa.Set heating schedule, make reaction temperature rise to 150 ℃ with the speed of 3 ℃/min from room temperature, the speed with 1 ℃/min is warming up to 220 ℃ then, reacts at 220 ℃.Reaction evaluating the results are shown in the subordinate list.
Subordinate list: the Fischer-Tropsch synthesis result of catalyst
As can be seen from the above table, catalyst activity of the present invention is higher, is 1000h in the synthesis gas air speed
-1Condition under, even Co content has only 10% (embodiment one), the CO conversion ratio still can reach more than 80%, illustrates that the effect of adding second kind and the third metal component is obvious.In illustrated embodiment, methane selectively all is lower than 10%, and the above product selectivity of C5 all can reach more than 80%, and especially above diesel oil and the paraffinic components of C12 all can reach 50～60%.
The volume space velocity relation of activity of such catalysts and synthesis gas is very big, and as can be seen from the above table, the CO conversion ratio raises with the synthesis gas air speed and descends, when the synthesis gas air speed is 10000h
-1The time, the CO conversion per pass is 49.2%, the circulation that need to increase reaction end gas this moment just can make full use of synthesis gas.Take all factors into consideration, the synthesis gas air speed is selected 2000～6000h for use
-1Be the best.
Claims (10)
1. a Co based Fischer-Tropsch synthesis catalyst comprises carrier and metal component, it is characterized in that: carrier adopts spherical powder Al
2O
3Metal component comprises that first kind of metal component is Co, and second kind of metal component is Ce, La, and a kind of among the Zr, the third metal component is a kind of among Pt, Ru, Rh, the Re; In finished catalyst, the percentage by weight of each metal component is: first kind of metal component: 10～35%, second kind of metal component: 0.5%～10%; The third metal component: 0.05%～3%, surplus is an alumina support.
2. Co based Fischer-Tropsch synthesis catalyst according to claim 1 is characterized in that: the metal component percentage by weight is: first kind of metal component: 15～35%, second kind of metal component: 1%～5%; The third metal component: 0.1%～1%, surplus is an alumina support.
3. Co based Fischer-Tropsch synthesis catalyst according to claim 1 and 2 is characterized in that: described spherical powder Al
2O
3Be γ-Al
2O
3, the average grain scope is 20～120 microns, and the part that is lower than 25 microns is no more than 3%, and specific area is 130～180m
2/ g, the aperture is 5～12nm, pore volume is 0.3～0.5cm
3/ g.
4. the preparation method of the described Co based Fischer-Tropsch synthesis catalyst that is used for paste state bed reactor of one of claim 1～3 is as follows:
Step (1) is with the Al of predetermined volume
2O
3Carrier is put into Muffle furnace, and at 350～550 ℃ of roasting 4～10h, taking-up places drier standby;
Step (2) takes by weighing the nitrate of the cobalt nitrate, second kind of metal component and the third metal component that calculate consumption, is dissolved in jointly in the deionized water, makes it fully to dissolve and mix;
Step (3) adopts full hole infusion process, on rotary evaporator with step (2) solution impregnation at Al
2O
3On the carrier, vacuumize drying at 70～110 ℃;
Step (4) is with the at room temperature aging 4～24h of dried catalyst, and at 100～120 ℃ of down dry 6～24h, roasting 2～24h between 300～500 ℃ makes finished catalyst then.
5. the preparation method of the described Co based Fischer-Tropsch synthesis catalyst of claim 4 is as follows:
Step (1) is with the Al of predetermined volume
2O
3Carrier is put into Muffle furnace, at 400～500 ℃ of roasting 6～10h;
Step (3) adopts full hole infusion process, on rotary evaporator with step (2) solution impregnation at Al
2O
3On the carrier, vacuumize drying at 70～90 ℃;
Step (4) is with the at room temperature aging 6～16h of dried catalyst, then at 100～120 ℃ of down dry 6～16h, roasting 2～12h between 300～450.
6. according to claim 4 or the 5 described preparation methods that are used for the Co based Fischer-Tropsch synthesis catalyst of paste state bed reactor, it is characterized in that: during obtain solution, the salt of first kind of used active metal component cobalt is cobalt nitrate, cobalt acetate or carbonyl cobalt; The salt of second kind of metal component is the nitrate of selected metal; The salt of the third metal component is the nitrate of selected metal, also can be the nitrosyl radical nitrate of these metals.
7. as the application of the described Co based Fischer-Tropsch synthesis catalyst of claim 1～3, it is characterized in that: the condition that catalyst activates on fixed bed reactors is: reducing gases is pure H
2, purity＞99.9%, its volume space velocity are 1000～5000h
-1, heating rate is 1～3 ℃/min, and activation temperature is 300～500 ℃, and activation pressure is 0.1～0.5MPa, and soak time is 2～16h; Catalyst is applied to paste state bed reactor to carry out the reaction condition of Fischer-Tropsch when synthetic and be: reacting gas is a synthesis gas, and its volume space velocity is 1000～10000h
-1, H in the synthesis gas
2: CO=1～3, reaction temperature are 200～240 ℃, and reaction pressure is 1.0～3.0MPa.
8. the application of Co based Fischer-Tropsch synthesis catalyst as claimed in claim 7 is characterized in that: catalyst at the fixed bed reactors activation condition is: reducing gases is pure H
2, purity＞99.9%, its volume space velocity are 1500～3000h
-1, heating rate is 1～2 ℃/min, and activation temperature is 350～450 ℃, and activation pressure is 0.3～0.5MPa, and soak time is 6～12h; Catalyst is applied to paste state bed reactor to carry out the reaction condition of Fischer-Tropsch when synthetic and be: reacting gas is a synthesis gas, and its volume space velocity is 2000～6000h
-1, H in the synthesis gas
2: CO=1.5～2.5, reaction temperature are 210～230 ℃, and reaction pressure is 2.0～3.0MPa.
9. as the application of the described Co based Fischer-Tropsch synthesis catalyst of claim 1～3, it is characterized in that: the condition that catalyst activates on fluidized-bed reactor is: reducing gases is pure H
2, purity＞99.9%, its volume space velocity are 1000～5000h
-1, heating rate is 1～3 ℃/min, and activation temperature is 300～500 ℃, and activation pressure is 0.5～2.0MPa, and soak time is 2～16h; Catalyst is applied to paste state bed reactor to carry out the reaction condition of Fischer-Tropsch when synthetic and be: reacting gas is a synthesis gas, and its volume space velocity is 1000～10000h
-1, H in the synthesis gas
2: CO=1～3, reaction temperature are 200～240 ℃, and reaction pressure is 1.0～3.0MPa.
10. the application of Co based Fischer-Tropsch synthesis catalyst as claimed in claim 9 is characterized in that: the condition that catalyst activates on fluidized-bed reactor is: reducing gases is pure H
2, purity＞99.9%, its volume space velocity are 1000～3000h
-1, heating rate is 1～2 ℃/min, and activation temperature is 350～450 ℃, and activation pressure is 1.0～2.0MPa, and soak time is 6～12h; Catalyst is applied to paste state bed reactor, carries out the reaction condition of Fischer-Tropsch when synthetic to be: reacting gas is a synthesis gas, and its volume space velocity is 2000～6000h
-1, H in the synthesis gas
2: CO=1.5～2.5, reaction temperature are 210～230 ℃, and reaction pressure is 2.0～3.0MPa.
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