CN105771993A - Fischer-Tropsch synthesis catalyst for preparing liquid hydrocarbon from syngas and preparation method of Fischer-Tropsch synthesis catalyst - Google Patents
Fischer-Tropsch synthesis catalyst for preparing liquid hydrocarbon from syngas and preparation method of Fischer-Tropsch synthesis catalyst Download PDFInfo
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- CN105771993A CN105771993A CN201610283024.1A CN201610283024A CN105771993A CN 105771993 A CN105771993 A CN 105771993A CN 201610283024 A CN201610283024 A CN 201610283024A CN 105771993 A CN105771993 A CN 105771993A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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Abstract
The invention discloses a Fischer-Tropsch synthesis catalyst for preparing liquid hydrocarbon from syngas. According to preparation of the catalyst, by mass, 100 pbw of silicon dioxide or aluminium oxide is taken as a catalyst carrier, 10-60 pbw of cobalt nitrate is taken as an active component, and 1.5-20 pbw of titanium, zirconium, cerium, lanthanum and calcium oxides are taken as carrier modified additives. The preparation method includes the steps of (1) preparation of raw materials; (2) catalyst carrier pretreatment; (3), modification of the catalyst carrier; (4), drying; (5), roasting; and (6) catalyst preparation to obtain the Fischer-Tropsch synthesis catalyst. The Fischer-Tropsch synthesis catalyst has important significance in application, has high value-added products, and has the advantages of high selectivity, high stability, long service life and low cost. According to the preparation method of the catalyst, selectivity and stability of the catalyst can be improved while production cost can be reduced by regulating roasting and reduction conditions.
Description
Technical field
The present invention relates to the technical field of catalyst preparing, relate to the technology of fischer-tropsch synthetic catalyst reduction treatment, specifically, be for synthesis gas fischer-tropsch synthetic catalyst producing liquid hydrocarbon and preparation method thereof.
Background technology
F-T synthesis (Fischer-TropschSynthesis) be nineteen twenty-three by Germany scientist F.Fischer and H.Tropsch find by synthesis gas (H2/ CO) technology of catalyzed synthesis higher hydrocarbon.The raw materials such as coal, natural gas, coal bed gas, biomass can be converted into clean fuel and other high added value industrial chemicals and product by F-T synthesis technology and follow-up product purification processing procedure on a large scale, thus obtains giving more sustained attention of world energy sources and chemical industry.
Transition metal iron (Fe), cobalt (Co), nickel (Ni) and ruthenium (Ru) are studied for Fischer-Tropsch synthesis because having good hydrogenation reaction activity, wherein count catalysis activity catalyst based for Ru the highest, product chain growing ability is the most excellent, but, due to ruthenium resource-constrained, expensive, which has limited its application as industrial catalyst.Additionally, Ni is catalyst based due to methanation seriously, it is not suitable for use in the catalyst of synthesis high-carbon heavy hydrocarbon.Therefore, F-T synthesis generally uses Fe and Co as catalyst activity component.At present, representative fischer-tropsch synthetic catalyst has two kinds, and one is that Fe is catalyst based, and one is that Co is catalyst based.Wherein, the catalyst based hydrogenation activity of Fe is higher, easy-sintering, carbon deposit under certain reaction condition and inactivate, water gas shift reaction activity is high, and the chain growth ability relatively Co of synthesis hydrocarbon is poor.Co is catalyst based has good hydrogenation activity, relatively low water gas shift reaction activity and the price of relative moderate, has significantly high application potential.Adopt fixing bed Fischer-Tropsch synthesis catalyst based for Co simple to operate, elastic greatly.Additionally, the advantage such as Co catalyst based also has that not easily carbon deposit is poisoning, service life is longer, carbochain growing ability is higher, oxygenatedchemicals is less in product, therefore, Co is catalyst based is considered as the fischer-tropsch synthetic catalyst of extensive synthesis of heavy hydrocarbon most competitiveness.
The preparation method of the catalyst based routine of Co is mainly infusion process.Its preparation process is: first prepare the carrier (silicon oxide, aluminium oxide or the complex of the two) with loose structure, then to carrier molding, it is impregnated on carrier by infusion process presoma one step by Co or other auxiliary agents (Ca, Mn, Ti, V, Zr, La, Ce, Ga) or distribution；Subsequent step includes: dry removing water or organic solvent, and in air, roasting forms oxide catalyst, and then catalyst is through reducing atmosphere (H2、H2/CO、H2/N2) process reduction, it is packaged after catalyzed dose of passivation, or oxide catalyst is directly encapsulated, carry out on-the-spot reduction: the temperature of catalyst reduction is at 200～450 ° of C, generally reducing with steam heating, after reduction, temperature drops to below reaction temperature, passes into synthesis gas and reacts.At present, composition catalyst based for Co is originally determined elementary composition through substantial amounts of screening hexyl by the art, but, follow-up roasting and reduction process in preparation are not also obtained enough attention, reduction process is also bigger on the impact of reactivity worth.And the oxidized state of active component in catalyst is mainly metallic state by the catalyst based reduction process of Co by catalyst under reducing atmosphere condition, it is generally at H2Complete under constant-pressure and high-temperature under condition, owing to this reaction is more violent, it is easy to cause catalyst granules to grow up, can cause that catalyst activity bit quantity reduces, catalysis activity decrease.
First the product that fischer-tropsch synthetic catalyst is obtained by reacting has the following characteristics that, the fuel oil purity of generation is high, and aromatic hydrocarbons, olefin(e) centent are few, antioxygenic property is excellent, can as high-quality power fuel, and in the tail gas of post combustion emission, nuisance is few, is environmentally friendly fuel；Secondly, the high value added products such as top-grade lubricating oil can be produced by hydroisomerizing further, there is higher economic worth；3rd, wax phase product as fine chemical product, can have purity height, the advantage of not nitrogenous, sulfur.But, fischer-tropsch synthetic catalyst relatively costly, therefore, develop high selectivity, high stability, long-life, lower-cost fischer-tropsch synthetic catalyst just seem particularly significant.
Summary of the invention
It is an object of the invention to improve the deficiencies in the prior art, a kind of fischer-tropsch synthetic catalyst producing liquid hydrocarbon for synthesis gas is provided, it adopts unformed aluminium oxide, silicon oxide or the complex of the two as carrier, with cobalt for active component, add appropriate modified additive titanium, zirconium, cerium, lanthanum, calcium, can be used for preparing heavy hydrocarbon with synthesis gas for raw material；The preparation method that second purpose of the present invention is to provide described fischer-tropsch synthetic catalyst, by adjusting catalyst roasting condition and reducing condition, improves selectivity of catalyst, stability further, reduces Catalyst Production cost, can improve C in liquid hydrocarbon simultaneously19 +The selectivity of hydrocarbon.
For achieving the above object, this invention takes techniques below scheme.
A kind of fischer-tropsch synthetic catalyst producing liquid hydrocarbon for synthesis gas, with silicon dioxide (SiO2) or aluminium oxide (Al2O3) as catalyst carrier, using cobalt nitrate (Co) as active component, using titanium (Ti), zirconium (Zr), cerium (Ce), lanthanum (La), calcium (Ca) oxide as support modification auxiliary agent, it is characterised in that the mass fraction (pbw) of described fischer-tropsch synthetic catalyst composition is:
Catalyst carrier 100pbw；
Active component 10～60pbw；
Support modification auxiliary agent 1.5～20pbw.
Further, the mass fraction of described fischer-tropsch synthetic catalyst composition is:
Catalyst carrier 100pbw；
Active component 15～45pbw；
Support modification auxiliary agent 1.5～20pbw.
Optionally, described silica supports is diameter 0.20mm～3.35mm(6～60 order) silicon oxide bead.
Optionally, described alumina support is the cartwheel pattern carrier of diameter 3～5mm.
Optionally, described support modification auxiliary agent be titanium, zirconium, cerium, lanthanum, calcium nitrate one or more.
For achieving the above object, this invention takes techniques below scheme.
The preparation method of the described fischer-tropsch synthetic catalyst producing liquid hydrocarbon for synthesis gas, it is characterised in that comprise the steps of
(1) raw material prepares
With silicon dioxide (SiO2) or aluminium oxide (Al2O3) as catalyst carrier, using cobalt (Co) as active component, using titanium (Ti), zirconium (Zr), cerium (Ce), lanthanum (La), calcium (Ca) oxide as support modification auxiliary agent, the mass fraction of fischer-tropsch synthetic catalyst composition is:
Catalyst carrier 100pbw,
Active component 15～45pbw,
Support modification auxiliary agent 1.5～20pbw；
(2) catalyst carrier pretreatment
The catalyst carrier of step (1) mass fraction is put in Muffle furnace, in Muffle furnace, is warmed up to 350～800 DEG C of roastings 6 hours with the speed of 2 DEG C/min, after Temperature fall, obtains catalyst carrier, put it in exsiccator with standby；
(3) modified catalyst supports
Weigh one or more support modification auxiliary agents by the mass fraction of step (1) and step (2) processes the catalyst carrier obtained, be configured to certain density auxiliary agent nitrate solution；By equi-volume impregnating, catalyst carrier is carried out impregnation process, stand 12～24 hours under room temperature；
(4) dry
The impregnated catalyst carrier that step (3) processes is put in the baking oven that temperature is 90～120 DEG C and dry 12～24 hours；
(5) roasting
Step (4) dried catalyst carrier is carried out roasting by the method for step (2) again, obtains the catalyst carrier modifiied, put it in exsiccator with standby；
(6) catalyst preparing
The modified catalyst carrier cobalt of step (1) mass fraction and step (5) prepared prepares certain density cobalt nitrate solution, repeat the roasting of the dry and step (5) of the dipping of step (3), step (4), obtain target product and produce the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas；Put it in exsiccator with standby.
Further, the mass fraction of the fischer-tropsch synthetic catalyst composition described in step (1) is:
Catalyst carrier 100pbw；
Active component 15～45pbw；
Support modification auxiliary agent 1.5～20pbw.
Optionally, described cobalt is inorganic salt cobalt nitrate.
Optionally, the sintering temperature of step (2) is 350～450 DEG C.
Fischer-tropsch synthetic catalyst prepared by the present invention is when producing liquid hydrocarbon for synthesis gas, it is characterised in that needing reduction activation before using, reduction process is: containing 5～10%H2Hydrogen nitrogen mixed gas atmosphere in, pressure 0.1MPa, air speed 500～4000h-1, reductase 12 4～48 hours under 260～500 DEG C of conditions of temperature；Or, carbon monoxide volume content be 5% containing in hydrogen atmosphere, pressure 0.1～2.0MPa, air speed 500～4000h-1, temperature 260～450 DEG C when reduction 12～72 hours.
The method have the advantages that
(1) provide a kind of be suitable for synthesis gas produce liquid hydrocarbon, adopt aluminium oxide, silicon oxide or the complex of the two as carrier, with cobalt for active component the fischer-tropsch synthetic catalyst adding appropriate modified additive titanium, zirconium, cerium, lanthanum, calcium.
(2) preparation method providing described fischer-tropsch synthetic catalyst, it, by adjusting roasting condition and reducing condition, improves selectivity of catalyst, stability, reduces production cost.
(3) it is a kind of have the high selectivity of important use meaning, high stability, have high value added product, life-span length, fischer-tropsch synthetic catalyst that cost is low.
Detailed description of the invention
The present invention introduced below is for the detailed description of the invention of the synthesis gas fischer-tropsch synthetic catalyst producing liquid hydrocarbon and preparation method thereof, it is provided that individual 12 embodiments and corresponding Application Example.It should be noted that the enforcement of the present invention is not limited to following embodiment.
Embodiment 1
The preparation method producing the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, comprises the steps of
(1) raw material prepares
The mass fraction of fischer-tropsch synthetic catalyst composition is:
Catalyst carrier 100pbw, the cartwheel pattern aluminium oxide adopting diameter 5.0mm is catalyst carrier；
Cobalt 25pbw, adopts cobalt nitrate；
Support modification auxiliary agent 20pbw, adopting zirconium (Zr) is support modification auxiliary agent.
(2) catalyst carrier pretreatment
The catalyst carrier of step (1) mass fraction is put in Muffle furnace, in Muffle furnace, is warmed up to 550 DEG C of roastings 6 hours with the speed of 2 DEG C/min, after Temperature fall, obtains catalyst carrier, put it in exsiccator with standby.
(3) modified catalyst supports
Weigh support modification auxiliary agent zirconium by the mass fraction of step (1) and step (2) processes the catalyst carrier obtained and is configured to certain density auxiliary agent nitrate solution；By equi-volume impregnating, catalyst carrier is carried out impregnation process, stand 12 hours under room temperature.
(4) dry
The impregnated catalyst carrier that step (3) processes is put in the baking oven that temperature is 110 DEG C and dry 12 hours.
(5) roasting
Step (4) dried catalyst carrier is carried out roasting by the method for step (2) again, obtains the catalyst carrier modifiied, put it in exsiccator with standby.
(6) catalyst preparing
The modified catalyst carrier cobalt nitrate of step (1) mass fraction and step (5) prepared prepares certain density cobalt nitrate solution, repeat the roasting of the dry and step (5) of the dipping of the present embodiment step (3), step (4), sintering temperature is 400 DEG C, obtain target product and produce the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, be numbered catalyst A；Put it in exsiccator with standby.
Embodiment 2
The preparation method producing the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, comprises the steps of
(1) raw material prepares
The mass fraction of fischer-tropsch synthetic catalyst composition is:
Catalyst carrier 100pbw, the cartwheel pattern aluminium oxide adopting diameter 4.0mm is catalyst carrier；
Cobalt 25pbw, adopts cobalt nitrate；
Support modification auxiliary agent 12pbw, adopting Zr is support modification auxiliary agent.
(2) catalyst carrier pretreatment (with embodiment 1).
(3) modified catalyst supports
Basic with embodiment 1, institute the difference is that: stand 24 hours under room temperature.
(4) dry
The impregnated catalyst carrier that step (3) processes is put in the baking oven that temperature is 90 DEG C and dry 24 hours.
(5) roasting (with embodiment 1).
(6) catalyst preparing (with embodiment 1).
Obtain target product and produce the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, be numbered catalyst B；Put it in exsiccator with standby.
Embodiment 3
The preparation method producing the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, comprises the steps of
(1) raw material prepares
The mass fraction of fischer-tropsch synthetic catalyst composition is:
Catalyst carrier 100pbw, the cartwheel pattern aluminium oxide adopting diameter 3.0mm is catalyst carrier；
Cobalt 25pbw, adopts cobalt nitrate；
Support modification auxiliary agent 5.3pbw, wherein, adopting zirconium 5pbw and lanthanum 0.3pbw is support modification auxiliary agent.
(2) catalyst carrier pretreatment (with embodiment 1).
(3) modified catalyst supports
Weigh support modification auxiliary agent zirconium and lanthanum by the mass fraction of step (1) and step (2) processes the catalyst carrier obtained and is configured to certain density auxiliary agent nitrate solution；By equi-volume impregnating, catalyst carrier is carried out impregnation process, stand 24 hours under room temperature.
(4) dry (with embodiment 1).
(5) roasting (with embodiment 1).
(6) catalyst preparing (with embodiment 1)
Obtain target product and produce the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, be numbered catalyst C；Put it in exsiccator with standby.
Embodiment 4
The preparation method producing the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, comprises the steps of
(1) raw material prepares
The mass fraction of fischer-tropsch synthetic catalyst composition is:
Catalyst carrier 100pbw, the cartwheel pattern aluminium oxide adopting diameter 3.0mm is catalyst carrier；
Cobalt 25pbw, adopts cobalt nitrate；
Support modification auxiliary agent 3.1pbw, wherein, adopting zirconium 3pbw and calcium (Ca) 0.1pbw is support modification auxiliary agent.
(2) catalyst carrier pretreatment
The catalyst carrier of step (1) mass fraction is put in Muffle furnace, in Muffle furnace, is warmed up to 400 DEG C of roastings 6 hours with the speed of 2 DEG C/min, after Temperature fall, obtains catalyst carrier, put it in exsiccator with standby.
(3) modified catalyst supports (with embodiment 1).
Weigh support modification auxiliary agent zirconium and calcium by the mass fraction of step (1) and step (2) processes the catalyst carrier obtained and is configured to certain density auxiliary agent nitrate solution；By equi-volume impregnating, catalyst carrier is carried out impregnation process, stand 12 hours under room temperature.
(4) dry
The impregnated catalyst carrier that step (3) processes is put in the baking oven that temperature is 120 DEG C and dry 12 hours.
(5) roasting (with embodiment 1).
(6) catalyst preparing
The modified catalyst carrier cobalt nitrate of step (1) mass fraction and step (5) prepared prepares certain density cobalt nitrate solution, repeat the roasting of the dry and step (5) of the dipping of the present embodiment step (3), step (4), sintering temperature is 450 DEG C, obtain target product and produce the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, be numbered catalyst D；Put it in exsiccator with standby.
Embodiment 5
The preparation method producing the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, comprises the steps of
(1) raw material prepares
The mass fraction of fischer-tropsch synthetic catalyst composition is:
Catalyst carrier 100pbw, the cartwheel pattern aluminium oxide adopting diameter 3.0mm is catalyst carrier；
Cobalt 25pbw, adopts cobalt nitrate；
Support modification auxiliary agent 3.2pbw, wherein, adopting zirconium 3pbw and lanthanum 0.2pbw is support modification auxiliary agent.
(2) catalyst carrier pretreatment (with embodiment 1).
(3) modified catalyst supports
Weigh support modification auxiliary agent zirconium and lanthanum by the mass fraction of step (1) and step (2) processes the catalyst carrier obtained and is configured to certain density auxiliary agent nitrate solution；By equi-volume impregnating, catalyst carrier is carried out impregnation process, stand 12 hours under room temperature.
(4) dry (with embodiment 1).
(5) roasting (with embodiment 1).
(6) catalyst preparing (with embodiment 1)
Obtain target product and produce the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, be numbered catalyst E；Put it in exsiccator with standby.
Embodiment 6
The preparation method producing the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, comprises the steps of
(1) raw material prepares
The mass fraction of fischer-tropsch synthetic catalyst composition is:
Catalyst carrier 100pbw, the cartwheel pattern aluminium oxide adopting diameter 3.0mm is catalyst carrier；
Cobalt 10pbw, adopts cobalt nitrate；
Support modification auxiliary agent 9.1pbw, wherein, adopting cerium (Ce) 9pbw and lanthanum (La) 0.1pbw is support modification auxiliary agent.
(2) catalyst carrier pretreatment (with embodiment 1).
(3) modified catalyst supports
Weigh support modification auxiliary agent cerium and lanthanum by the mass fraction of step (1) and step (2) processes the catalyst carrier obtained and is configured to certain density auxiliary agent nitrate solution；By equi-volume impregnating, catalyst carrier is carried out impregnation process, stand 12 hours under room temperature.
(4) dry (with embodiment 1).
(5) roasting (with embodiment 1).
(6) catalyst preparing (with embodiment 1)
The modified catalyst carrier cobalt nitrate of step (1) mass fraction and step (5) prepared prepares certain density cobalt nitrate solution, repeat the roasting of the dry and step (5) of the dipping of the present embodiment step (3), step (4), sintering temperature is 550 DEG C, obtain target product and produce the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, be numbered catalyst F；Put it in exsiccator with standby.
Embodiment 7
The preparation method producing the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, comprises the steps of
(1) raw material prepares
The mass fraction of fischer-tropsch synthetic catalyst composition is:
Catalyst carrier 100pbw, the cartwheel pattern aluminium oxide adopting diameter 3.0mm is catalyst carrier；
Cobalt 15pbw, adopts cobalt nitrate；
Support modification auxiliary agent 7pbw, wherein, adopting zirconium 5pbw and titanium (Ti) 2pbw is support modification auxiliary agent.
(2) catalyst carrier pretreatment
The catalyst carrier of step (1) mass fraction is put in Muffle furnace, in Muffle furnace, is warmed up to 800 DEG C of roastings 6 hours with the speed of 2 ° of C/min, after Temperature fall, obtains catalyst carrier, put it in exsiccator with standby.
(3) modified catalyst supports
Weigh support modification auxiliary agent zirconium and titanium by the mass fraction of step (1) and step (2) processes the catalyst carrier obtained and is configured to certain density auxiliary agent nitrate solution；By equi-volume impregnating, catalyst carrier is carried out impregnation process, stand 12 hours under room temperature.
(4) dry (with embodiment 1).
(5) roasting (with embodiment 1).
(6) catalyst preparing (with embodiment 1)
The modified catalyst carrier cobalt nitrate of step (1) mass fraction and step (5) prepared prepares certain density cobalt nitrate solution, repeat the roasting of the dry and step (5) of the dipping of the present embodiment step (3), step (4), sintering temperature is 600 DEG C, obtain target product and produce the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, be numbered catalyst G；Put it in exsiccator with standby.
Embodiment 8
The preparation method producing the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, comprises the steps of
(1) raw material prepares
The mass fraction of fischer-tropsch synthetic catalyst composition is:
Catalyst carrier 100pbw, the cartwheel pattern aluminium oxide adopting diameter 3.0mm is catalyst carrier；
Cobalt 30pbw, adopts cobalt nitrate；
Support modification auxiliary agent 5.2pbw, wherein, adopting titanium 5pbw and calcium 0.2pbw is support modification auxiliary agent.
(2) catalyst carrier pretreatment
The catalyst carrier of step (1) mass fraction is put in Muffle furnace, in Muffle furnace, is warmed up to 600 DEG C of roastings 6 hours with the speed of 2 ° of C/min, after Temperature fall, obtains catalyst carrier, put it in exsiccator with standby.
(3) modified catalyst supports
Weigh support modification auxiliary agent titanium and calcium by the mass fraction of step (1) and step (2) processes the catalyst carrier obtained and is configured to certain density auxiliary agent nitrate solution；By equi-volume impregnating, catalyst carrier is carried out impregnation process, stand 12 hours under room temperature.
(4) dry
The impregnated catalyst carrier that step (3) processes is put in the baking oven that temperature is 110 DEG C and dry 24 hours.
(5) roasting (with embodiment 1).
(6) catalyst preparing
The modified catalyst carrier cobalt nitrate of step (1) mass fraction and step (5) prepared prepares certain density cobalt nitrate solution, repeat the roasting of the dry and step (5) of the dipping of the present embodiment step (3), step (4), sintering temperature is 350 DEG C, obtain target product and produce the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, be numbered catalyst H；Put it in exsiccator with standby.
Embodiment 9
The preparation method producing the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, comprises the steps of
(1) raw material prepares
The mass fraction of fischer-tropsch synthetic catalyst composition is:
Catalyst carrier 100pbw, adopts diameter 2.36～3.35mm(6～8 orders) silica supports bead；
Cobalt 25pbw, adopts cobalt nitrate；
Support modification auxiliary agent 12.7pbw, wherein, adopting zirconium 12.5pbw and lanthanum (La) 0.4pbw is support modification auxiliary agent.
(2) catalyst carrier pretreatment
The catalyst carrier of step (1) mass fraction is put in Muffle furnace, in Muffle furnace, is warmed up to 800 DEG C of roastings 6 hours with the speed of 2 DEG C/min, after Temperature fall, obtains catalyst carrier, put it in exsiccator with standby.
(3) modified catalyst supports
Weigh support modification auxiliary agent zirconium and lanthanum by the mass fraction of step (1) and step (2) processes the catalyst carrier obtained and is configured to certain density auxiliary agent nitrate solution；By equi-volume impregnating, catalyst carrier is carried out impregnation process, stand 12 hours under room temperature.
(4) dry (with embodiment 1).
(5) roasting (with embodiment 1).
(6) catalyst preparing
The modified catalyst carrier cobalt nitrate of step (1) mass fraction and step (5) prepared prepares certain density cobalt nitrate solution, repeat the roasting of the dry and step (5) of the dipping of the present embodiment step (3), step (4), sintering temperature is 800 DEG C, obtain target product and produce the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, be numbered catalyst I；Put it in exsiccator with standby.
Embodiment 10
The preparation method producing the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, comprises the steps of
(1) raw material prepares
The mass fraction of fischer-tropsch synthetic catalyst composition is:
Catalyst carrier 100pbw, adopts diameter 1.4～1.7mm(10～12 orders) silica supports bead；
Co 60 pbw, adopts cobalt nitrate；
Support modification auxiliary agent 1.5pbw, wherein, adopting zirconium 1.0pbw and cerium (Ce) 0.5pbw is support modification auxiliary agent.
(2) catalyst carrier pretreatment
The catalyst carrier of step (1) mass fraction is put in Muffle furnace, in Muffle furnace, is warmed up to 800 DEG C of roastings 6 hours with the speed of 2 DEG C/min, after Temperature fall, obtains catalyst carrier, put it in exsiccator with standby.
(3) modified catalyst supports
Weigh support modification auxiliary agent zirconium and cerium by the mass fraction of step (1) and step (2) processes the catalyst carrier obtained and is configured to certain density auxiliary agent nitrate solution；By equi-volume impregnating, catalyst carrier is carried out impregnation process, stand 12 hours under room temperature.
(4) dry (with embodiment 1).
(5) roasting (with embodiment 1).
(6) catalyst preparing
The modified catalyst carrier cobalt nitrate of step (1) mass fraction and step (5) prepared prepares certain density cobalt nitrate solution, repeat the roasting of the dry and step (5) of the dipping of the present embodiment step (3), step (4), sintering temperature is 400 DEG C, obtain target product and produce the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, be numbered catalyst J；Put it in exsiccator with standby.
Embodiment 11
The preparation method producing the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, comprises the steps of
(1) raw material prepares
The mass fraction of fischer-tropsch synthetic catalyst composition is:
Catalyst carrier 100pbw, adopts particle diameter 0.20～0.43mm(40～60 orders) carrier particles of silica；
Cobalt 50pbw, adopts cobalt nitrate；
Support modification auxiliary agent 1.7pbw, wherein, adopting zirconium 1.5pbw and cerium (Ce) 0.2pbw is support modification auxiliary agent.
(2) catalyst carrier pretreatment (with embodiment 10).
(3) modified catalyst supports
Weigh support modification auxiliary agent zirconium and cerium by the mass fraction of step (1) and step (2) processes the catalyst carrier obtained and is configured to certain density auxiliary agent nitrate solution；By equi-volume impregnating, catalyst carrier is carried out impregnation process, stand 12 hours under room temperature.
(4) dry (with embodiment 1).
(5) roasting (with embodiment 1).
(6) catalyst preparing (with embodiment 1)
Obtain target product and produce the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, be numbered catalyst K；Put it in exsiccator with standby.
Embodiment 12
The preparation method producing the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, comprises the steps of
(1) raw material prepares
The mass fraction of fischer-tropsch synthetic catalyst composition is:
Catalyst carrier 100pbw, adopts particle diameter 0.5～1.4mm(12～35 orders) silica supports bead；
Cobalt 45pbw, adopts cobalt nitrate；
Support modification auxiliary agent 18.7pbw, wherein, adopting zirconium 18.5pbw and lanthanum (La) 0.4pbw is support modification auxiliary agent.
(2) catalyst carrier pretreatment (with embodiment 10).
(3) modified catalyst supports
Weigh support modification auxiliary agent zirconium and lanthanum by the mass fraction of step (1) and step (2) processes the catalyst carrier obtained and is configured to certain density auxiliary agent nitrate solution；By equi-volume impregnating, catalyst carrier is carried out impregnation process, stand 12 hours under room temperature.
(4) dry (with embodiment 1).
(5) roasting (with embodiment 1).
(6) catalyst preparing
The modified catalyst carrier cobalt nitrate of step (1) mass fraction and step (5) prepared prepares certain density cobalt nitrate solution, repeat the roasting of the dry and step (5) of the dipping of the present embodiment step (3), step (4), sintering temperature is 550 DEG C, obtain target product and produce the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, be numbered catalyst L；Put it in exsiccator with standby.
Application Example
Catalyst A～L prepared by embodiment 1～12 is applied to produce the preparation process of liquid hydrocarbon with synthesis gas.
Before using, by described catalyst A～L at content 5～10%H2Hydrogen nitrogen mixed gas atmosphere in, pressure 0.1MPa, air speed 500～4000h-1, reductase 12 4～48 hours under 260～500 DEG C of conditions of temperature；Or, carbon monoxide volume content be 5% containing in hydrogen atmosphere, pressure 0.1～2.0MPa, air speed 500～4000h-1, temperature 260～450 DEG C when reduction 12～72 hours.
In preparation process, adopting tubular fixed-bed reactor to react, reaction temperature is 190～260 DEG C, and reaction pressure is 1.8～4.2MPa, and synthesis gas air speed is 400～4000h-1；Consist of at synthesis gas: H2Being 64%, CO is 32%, and all the other are N2When carry out.The appreciation condition of described catalyst A～L is in Table 1；The Fischer-Tropsch synthesis evaluation result carried out under the described conditions is in Table 2.
Table 1.The appreciation condition of catalyst A～L
。
Table 2.The evaluation result of catalyst A～L
。
The evaluation result of Application Example shows:
Fischer-tropsch synthetic catalyst (catalyst label A～L) prepared by the present invention has the F-T synthesis performance of excellence, has high activity, high C5 +Hydrocarbon-selective, low CH4Selectivity.For fixed bed reactors, fischer-tropsch synthetic catalyst prepared by the present invention is conducive to material to transmit, and CO conversion ratio is high, and has the advantage that the axial pressure drop of reaction tube is relatively low.
Claims (10)
1. produce the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas, with silicon dioxide (SiO2) or aluminium oxide (Al2O3) as catalyst carrier, using cobalt nitrate (Co) as active component, using titanium (Ti), zirconium (Zr), cerium (Ce), lanthanum (La), calcium (Ca) oxide as support modification auxiliary agent, it is characterised in that the mass fraction (pbw) of described fischer-tropsch synthetic catalyst composition is:
Catalyst carrier 100pbw；
Active component 10～60pbw；
Support modification auxiliary agent 1.5～20pbw.
2. the fischer-tropsch synthetic catalyst producing liquid hydrocarbon for synthesis gas according to claim 1, it is characterised in that the mass fraction of described fischer-tropsch synthetic catalyst composition is:
Catalyst carrier 100pbw；
Active component 15～45pbw；
Support modification auxiliary agent 1.5～20pbw.
3. the fischer-tropsch synthetic catalyst producing liquid hydrocarbon for synthesis gas according to claim 1, it is characterised in that described silica supports is the silicon oxide bead of diameter 0.20mm～3.35mm, 6～60 orders.
4. the fischer-tropsch synthetic catalyst producing liquid hydrocarbon for synthesis gas according to claim 1, it is characterised in that described alumina support is the cartwheel pattern carrier of diameter 3～5mm.
5. the fischer-tropsch synthetic catalyst producing liquid hydrocarbon for synthesis gas according to claim 1, it is characterised in that described support modification auxiliary agent be titanium, zirconium, cerium, lanthanum, calcium nitrate one or more.
6. the preparation method of the fischer-tropsch synthetic catalyst producing liquid hydrocarbon for synthesis gas described in claim 1, it is characterised in that comprise the steps of
(1) raw material prepares
With silicon dioxide (SiO2) or aluminium oxide (Al2O3) as catalyst carrier, using cobalt (Co) as active component, using titanium (Ti), zirconium (Zr), cerium (Ce), lanthanum (La), calcium (Ca) oxide as support modification auxiliary agent, the mass fraction of fischer-tropsch synthetic catalyst composition is:
Catalyst carrier 100pbw,
Active component 10～60pbw,
Support modification auxiliary agent 1.5～20pbw；
(2) catalyst carrier pretreatment
The catalyst carrier of step (1) mass fraction is put in Muffle furnace, in Muffle furnace, is warmed up to 350～800 DEG C of roastings 6 hours with the speed of 2 DEG C/min, after Temperature fall, obtains catalyst carrier, put it in exsiccator with standby；
(3) modified catalyst supports
Weigh one or more support modification auxiliary agents by the mass fraction of step (1) and step (2) processes the catalyst carrier obtained, be configured to certain density auxiliary agent nitrate solution；By equi-volume impregnating, catalyst carrier is carried out impregnation process, stand 12～24 hours under room temperature；
(4) dry
The impregnated catalyst carrier that step (3) processes is put in the baking oven that temperature is 90～120 DEG C and dry 12～24 hours；
(5) roasting
Step (4) dried catalyst carrier is carried out roasting by the method for step (2) again, obtains the catalyst carrier modifiied, put it in exsiccator with standby；
(6) catalyst preparing
The modified catalyst carrier cobalt of step (1) mass fraction and step (5) prepared prepares certain density cobalt nitrate solution, repeat the roasting of the dry and step (5) of the dipping of step (3), step (4), obtain target product and produce the fischer-tropsch synthetic catalyst of liquid hydrocarbon for synthesis gas；Put it in exsiccator with standby.
7. the preparation method according to claim 6 or 7, it is characterised in that the mass fraction of the fischer-tropsch synthetic catalyst composition described in step (1) is:
Catalyst carrier 100pbw；
Active component 15～45pbw；
Support modification auxiliary agent 1.5～20pbw.
8. preparation method according to claim 6, it is characterised in that the cobalt described in step (1) is inorganic salt cobalt nitrate.
9. preparation method according to claim 6, it is characterised in that the sintering temperature of step (2) is 350～450 DEG C.
10. the fischer-tropsch synthetic catalyst described in claim 1 is when producing liquid hydrocarbon for synthesis gas, it is characterised in that needing reduction activation before using, reduction process is: containing 5～10%H2Hydrogen nitrogen mixed gas atmosphere in, pressure 0.1MPa, air speed 500～4000h-1, reductase 12 4～48 hours under 260～500 DEG C of conditions of temperature；Or, carbon monoxide volume content be 5% containing in hydrogen atmosphere, pressure 0.1～2.0MPa, air speed 500～4000h-1, temperature 260～450 DEG C when reduction 12～72 hours.
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