CN108295867A - A kind of heavy hydrocarbon fischer-tropsch synthetic catalyst of low-temperature treatment and its preparation method and application - Google Patents

A kind of heavy hydrocarbon fischer-tropsch synthetic catalyst of low-temperature treatment and its preparation method and application Download PDF

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CN108295867A
CN108295867A CN201810102109.4A CN201810102109A CN108295867A CN 108295867 A CN108295867 A CN 108295867A CN 201810102109 A CN201810102109 A CN 201810102109A CN 108295867 A CN108295867 A CN 108295867A
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catalyst
cobalt
carrier
tropsch synthesis
fischer
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黄礼春
燕来
周建强
郜文斌
李国强
刘润花
杨勇
李永旺
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SYNFUELS CHINA INNER MONGOLIA Co Ltd
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SYNFUELS CHINA INNER MONGOLIA Co Ltd
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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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
    • 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
    • C10G2/333—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 platinum-group

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Abstract

The invention discloses heavy hydrocarbon fischer-tropsch synthetic catalysts of a kind of low-temperature treatment and its preparation method and application.The catalyst is made of cobalt, metal promoter, precious metal additive and carrier, and in the Co based Fischer-Tropsch synthesis catalyst of every 100 mass parts, the content of each component is as follows：Cobalt 5~50；Metal promoter 0.5~10；Precious metal additive 0.05~5；The carrier of surplus.The preparation method of catalyst provided by the invention is directly restored catalyst activity component cobalt and precious metal additive by reduction reaction on the surface of the carrier, so as to avoid the high temperature firing steps after conventional method carried noble metal and cobalt, catalyst sintering phenomenon of precious metal additive and cobalt in high-temperature calcination process repeatedly is avoided to occur, precious metal additive and catalytic active component cobalt can be effectively improved in the dispersibility of carrier surface, improve the catalytic performance of catalyst.Catalyst of the present invention has many advantages, such as that high activity, methane selectively be low, heavy hydrocarbon high selectivity, is consequently adapted to be used as the catalyst that fixed bed F- T synthesis and syrup state bed Fischer Tropsch synthesize.

Description

A kind of heavy hydrocarbon fischer-tropsch synthetic catalyst of low-temperature treatment and its preparation method and application
Technical field
The present invention relates to a kind of fischer-tropsch synthetic catalysts and its preparation method and application, and in particular to a kind of low-temperature treatment Heavy hydrocarbon Co based Fischer-Tropsch synthesis catalyst and its preparation method and application, belongs to catalyst preparation technical field.
Background technology
Consumption figure reaches 5.56 hundred million tons, and external dependence degree reaches 65%, i.e. China's oil notch will be increasing.Oil Shortage has become limitation China's economic development and threatens the significant problem of Chinese energy safety.
F-T synthesis is the important channel for converting synthesis gas to liquid fuel.The selectivity of C5+ hydrocarbon is improved, methane is inhibited The generation of equal by-products is the main goal in research of F-T synthesis.Realize that the committed step of the target is high activity, highly selective F- The development and exploitation of T synthetic catalysts.How reasonably to arrange in pairs or groups active component, metal promoter, precious metal additive and carrier, prepares The fischer-tropsch synthetic catalyst for going out function admirable is the hot spot of research.Currently, F-T synthetic catalysts are mainly with iron-based and cobalt-based It is main.Cobalt-base catalyst becomes because its higher hydrogenation activity and lower Water gas shift/WGS are active before F-T synthesizes and most have development One of the catalyst on way.
Since the interaction between cobalt and carrier is strong, Co3O4Particle needs can just be reduced into metallic state at high temperature Co, however roasting reduction temperature is high, is easy to cause the sintering of precious metal additive and active cobalt species, reduces the dispersion of cobalt species Degree, chain carrier number reduce.CN 104815701A disclose a kind of also original place of the cobalt-base catalyst for F- T synthesis Reason method, this method improve catalysis by handling Co base catalyst with the hydrogen low temperature pressure reduction containing 1%~30%CO This catalyst is applied in preparing heavy hydrocarbon from synthesis gas, CO can be made to convert by activity, stability and the selectivity to heavy hydrocarbon of agent Rate reaches 40~60%, has good industrial applications foreground.CN101224430A uses the cobalt-based catalyst in silica gel load The processing of grafted hydrophobic group in agent, prepares a kind of hydrophobic organic modification of Co group Fischer-Tropsch synthesized catalyst, will be in pure hydrogen Reduction temperature is reduced to 200~300 DEG C, one step high selectivity intermediate oil of synthesis gas may be implemented, but relative to normal The preparation catalyst process of rule increases hydrophobic grouping grafting and toluene and the operation of two step of acetone extraction.CN 104174399A discloses a kind of autoreduction and prepares Fischer-Tropsch synthesis cobalt-based catalyst, and composition includes cobalt oxide, oxide carrier with Surface passivation cobalt oxide is introduced organic carbon source in the preparation process of catalyst carrier, is divided under an inert atmosphere using organic carbon source Solution generates the characteristics of weak reduction components simple substance charcoal, is roasted after containing high-area carbon dipping cobalt, realizes cobalt-base catalyst roasting and from also Former synchronization has the advantages that for fixed bed reactors and can be restored at low temperature, but the catalyst is difficult regeneration. CN102319569A discloses a kind of low-temperature reduction type Co based Fischer-Tropsch synthesis catalyst and preparation method, the catalyst with ZnO is carrier, and using Co as active component, the catalyst is suitable for restoring at low temperature, can prevent cobalt in reduction process Clustering phenomena occur, advantageously form the metallic state Co of small grain size, ensure the utilization ratio of cobalt in the reaction, but the catalysis Agent is selectively poor.
Invention content
The object of the present invention is to provide a kind of low-temperature treatment Co based Fischer-Tropsch synthesis catalyst, cobalt-based provided by the present invention takes Tropsch synthesis catalyst has preferable synthesis gas conversion ratio, lower methane selectively, higher heavy hydrocarbon-selective, in country Energy security indemnifying party face has important strategic importance.
Low-temperature treatment Co based Fischer-Tropsch synthesis catalyst provided by the present invention, by cobalt, metal promoter, precious metal additive and load Body forms；
In the Co based Fischer-Tropsch synthesis catalyst of every 100 mass parts, the content of each component is as follows：
Cobalt 5~50；
Metal promoter 0.5~10；
Precious metal additive 0.05~5；
The carrier of surplus.
In the Co based Fischer-Tropsch synthesis catalyst, the composition of the Co based Fischer-Tropsch synthesis catalyst of every 100 mass parts is such as Under：
1) cobalt 10~30；Metal promoter 1~4；Precious metal additive 0.1~0.3；The carrier of surplus；
2) cobalt 10；Metal promoter 2；Precious metal additive 0.2；The carrier of surplus；
3) cobalt 10；Metal promoter 3；Precious metal additive 0.1；The carrier of surplus；
4) cobalt 20；Metal promoter 3；Precious metal additive 0.1；The carrier of surplus；
5) cobalt 20；Metal promoter 1；Precious metal additive 0.2；The carrier of surplus；
6) cobalt 20；Metal promoter 4；Precious metal additive 0.3；The carrier of surplus；
7) cobalt 25；Metal promoter 3；Precious metal additive 0.2；The carrier of surplus；
8) cobalt 25；Metal promoter 1；Precious metal additive 0.3；The carrier of surplus；
9) cobalt 30；Metal promoter 1；Precious metal additive 0.1；The carrier of surplus.
The carrier can be Al2O3、TiO2And SiO2At least one of.
The metal promoter can be at least one of alkali metal, alkaline-earth metal, transition metal and rare earth metal；
The alkali metal includes lithium, sodium and potassium；
The alkaline-earth metal includes magnesium, calcium, strontium and barium；
The transition metal includes manganese, titanium, vanadium, iron, nickel, copper, zinc, zirconium, niobium, rhenium, thorium and molybdenum；
The rare earth metal includes scandium, yttrium, lanthanum, cerium, samarium, praseodymium, neodymium；
The preferred potassium of the metal promoter, manganese, titanium, magnesium, copper, zinc, barium, zirconium, rhenium, thorium, lanthanum, calcium, niobium and cerium；
The precious metal additive can be at least one of ruthenium, rhodium, palladium, iridium, platinum, Jin Heyin.
Invention further provides the preparation methods of the Co based Fischer-Tropsch synthesis catalyst, include the following steps：
(1) soluble-salt of the metal promoter is carried on the carrier using infusion process, through drying and is roasted To modified support；
(2) aqueous solution for preparing the soluble-salt and soluble cobalt of the precious metal additive, by the modified load The suspending liquid A for obtaining having certain solid content is added into the aqueous solution in body, adjusts the pH value of the suspending liquid A to 4~12, Obtain suspension B；
(3) reducing agent is added into the suspension B, the Co based Fischer-Tropsch synthesis catalyst is obtained through reduction.
In above-mentioned preparation method, in step (1), the infusion process uses incipient impregnation, crosses volume impregnation, primary leaching Stain or the mode repeatedly impregnated；
The step of infusion process, is as follows：
The carrier is impregnated to get the modified support using the aqueous solution of the soluble-salt of the metal promoter；
The modified support is the carrier of the oxide containing the metal promoter；
The temperature of the drying can be 60~200 DEG C, and the time can be 2~36h, such as dry 12h under conditions of 120 DEG C；
The temperature of the roasting can be 200~800 DEG C, and the time can be 2~30h, such as roast 5h under conditions of 500 DEG C；
The soluble-salt of the metal promoter can be the form of nitrate.
In above-mentioned preparation method, in step (2), the solid content of the suspending liquid A can be 10~600g/L, concretely 80~250g/L, 80~150g/L, 150~250g/L, 80g/L, 150g/L or 250g/L；
Stir the pH value that the suspending liquid A is adjusted after the 0.1~6h of suspending liquid A；
By the way that the pH value of salpeter solution and/or ethylenediamine solution realization to the suspending liquid A is added into the suspending liquid A Adjusting；
The concentration of the salpeter solution or the ethylenediamine solution can be 0.01~5mol/L.
In above-mentioned preparation method, in step (2), the soluble-salt of the precious metal additive can be Ru (NO) (NO3)3、Rh (NO3)3·2H2O、Pd(NO3)2·2H2O、IrCl3·3H2O、Pt(NO3)2、HAuCl4And AgNO3At least one of；
The soluble cobalt can be cobalt nitrate, cobalt acetate or at least one of with cobaltous sulfate.
In above-mentioned preparation method, in step (3), the reducing agent can be potassium borohydride or sodium borohydride；
It is added in the form of the aqueous solution of the reducing agent into the suspension B；
The molar ratio of the reducing agent and cobalt described in the Co based Fischer-Tropsch synthesis catalyst and the precious metal additive can It is 2~5：1, such as 3：1；
In the aqueous solution, the mass concentration of the reducing agent can be 0.1~10wt%, such as 0.5wt%.
Further include the steps that being filtered, washed and dried after the reduction；
The temperature of the drying can be 60~200 DEG C, and the time can be 2~36h, such as dry 12h under conditions of 120 DEG C.
The preparation method of catalyst provided by the invention is by reduction reaction directly by catalyst activity component cobalt and your gold Belong to auxiliary agent to restore on the surface of the carrier, so as to avoid the high temperature firing steps after conventional method carried noble metal and cobalt, keep away Catalyst sintering phenomenon of precious metal additive and cobalt in high-temperature calcination process repeatedly is exempted to occur, noble metal can be effectively improved and helped Agent and catalytic active component cobalt improve the catalytic performance of catalyst in the dispersibility of carrier surface.
Co based Fischer-Tropsch synthesis catalyst provided by the invention can be used as the catalyst of fixed bed fischer-tropsch synthesis process, catalysis The process conditions of reaction are as follows：Reducing condition is：H2, 200~400 DEG C, preferably 200~300 DEG C, 0.1~5MPa of pressure, preferably 0.1~3MPa, 100~5000h of volume space velocity-1, preferably 200~3000h-1, 3~36h of constant temperature, preferably 4~for 24 hours；Reaction condition For：160~250 DEG C, preferably 180~240 DEG C, 0.5~5.0MPa of pressure, preferably 1.0~4.0MPa, volume space velocity 300~ 20000h-1, preferably 500~10000h-1, H2:Volume ratio=1~3 CO:1, preferably 1.5~2.5:1.
Co based Fischer-Tropsch synthesis catalyst provided by the invention can be used as the catalyst of syrup state bed Fischer Tropsch synthesis technology, catalysis The process conditions of reaction are as follows：Reducing condition is：H2, 200~400 DEG C, preferably 200~300 DEG C；0.1~5MPa of pressure, preferably 0.1~3MPa；500~20000h of volume space velocity-1, preferably 2000~10000h-1；3~36h of constant temperature, preferably 6~for 24 hours.Reaction Condition is：160~250 DEG C, preferably 180~240 DEG C；0.5~5.0MPa of pressure, preferably 1.0~4.0MPa；Volume space velocity 500 ~20000h-1, preferably 2000~10000h-1；H2:Volume ratio=1~3 CO:1, preferably 1.5~2.5:1.
The present invention's has the prominent advantages that：
1) catalyst prepared by the present invention can be such that noble metal-cobalt nano-particle is directly grown on carrier, enhance catalysis The combination of agent particle and carrier makes catalyst more stablize；
2) preparation method of catalyst of the present invention is directly helped catalyst activity component cobalt and noble metal by reduction reaction Agent restores on the surface of the carrier, so as to avoid the high temperature firing steps after conventional method carried noble metal and cobalt, avoids Catalyst in high-temperature calcination process repeatedly the sintering phenomenon of precious metal additive and cobalt occur, can be effectively improved precious metal additive and Dispersibility of the catalytic active component cobalt in carrier surface；
3) in the preparation method of catalyst of the present invention by reduction reaction directly by catalyst activity component cobalt and noble metal Auxiliary agent restores on the surface of the carrier, helps to slow down surface atom migration rate, is conducive to the mutually nanocrystalline formation of highly disperse active, The catalyst metals active component morphology of preparation is regular, uniform particle diameter, good dispersion；
4) preparation method of catalyst of the present invention is reacted in aqueous phase system always, need not add stabilizer or surface is lived Property agent, system is relatively simple, green non-pollution；
5) preparation method of catalyst of the present invention is simple, and operability is strong, and preparation condition is mild, favorable reproducibility, has larger Synthesis application foreground, be suitble to large-scale industrial production；
Catalyst prepared by the present invention has many advantages, such as that high activity, methane selectively be low, heavy hydrocarbon high selectivity, therefore suitable In the catalyst as fixed bed F- T synthesis and syrup state bed Fischer Tropsch synthesis.
Specific implementation mode
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Embodiment 1 prepares catalyst C-1
(1) commercial alumina 50g is weighed, based on final catalyst Zn content 3wt% (percentage composition in aluminium oxide), Zinc nitrate obtained aqueous solution is weighed, incipient impregnation is in above-mentioned alumina support, aging 3h, 120 DEG C of dry 12h, in 500 DEG C 5h is roasted, the modified support A of containing metal oxide is obtained after roasting.
(2) based on final catalyst Co contents 20wt% and ruthenium content 0.1wt%, cobalt nitrate and nitrosyl nitric acid ruthenium are weighed Obtained aqueous solution B；The modified support A that step (1) obtains is added in aqueous solution B and prepares the suspension C that solid content is 80g/L, After stirring 0.5h, under lasting stirring, pH to 7~8 is adjusted with the ethylenediamine of 1mol/L, forms suspension D.
(3) 0.5wt% sodium borohydride aqueous solutions are added under lasting stirring, into suspension D, wherein sodium borohydride with (cobalt+ Ruthenium) molar ratio be 3：1, continue to stir 1h, slurries filter, and sodium ion is washed with deionized into filtrate and is less than 50ppm, 120 DEG C of dry 12h, obtain final catalyst C-1.
In catalyst C-1, cobalt：Zinc：Ruthenium：Aluminium oxide=20：3：0.1：76.9 (quality).
Catalyst Evaluation Test carries out in fixed bed reactors, and reducing condition is：H2, 250 DEG C, 1MPa, volume space velocity 1000h-1, constant temperature 5h；Reaction condition is：210 DEG C, 3.0MPa, volume space velocity 4000h-1, H2:Volume ratio=2 CO:1.Catalyst Evaluation result it is as shown in table 1.
Catalyst Evaluation Test carries out in paste state bed reactor, and reducing condition is：H2, 230 DEG C, 3MPa, volume space velocity 3000h-1, constant temperature 5h；Reaction condition is：190 DEG C, 3.0MPa, volume space velocity 6000h-1, H2:Volume ratio=2 CO:1.Catalyst Evaluation result it is as shown in table 1.
Embodiment 2 prepares catalyst C-2
(1) commercial alumina 50g is weighed, based on final catalyst manganese content 3wt% (percentage composition in aluminium oxide), The molten obtained aqueous solution of manganese nitrate is weighed, incipient impregnation is in above-mentioned alumina support, aging 3h, 120 DEG C of dry 12h, at 500 DEG C Middle roasting 5h obtains the modified support A of containing metal oxide after roasting.
(2) based on final catalyst Co contents 25wt% and ruthenium content 0.2wt%, cobalt nitrate and nitrosyl nitric acid ruthenium are weighed Obtained aqueous solution B；The modified support A that step (1) obtains is added in aqueous solution B and prepares the suspension C that solid content is 150g/L, After stirring 1h, under lasting stirring, pH to 7~8 is adjusted with the ethylenediamine of 1mol/L, forms suspension D.
(3) under lasting stirring, be added 0.5wt% sodium borohydride aqueous solution solution into suspension D, sodium borohydride with (cobalt+ Ruthenium) molar ratio be 3：1, continue to stir 2h, slurries filter, and sodium ion is washed with deionized into filtrate and is less than 50ppm, 120 DEG C of dry 12h, obtain final catalyst C-2.
In catalyst C-2, cobalt：Manganese：Ruthenium：Aluminium oxide=25：3：0.2：71.8 (quality).
Evaluating catalyst condition is the same as embodiment 1.The evaluation result of catalyst is as shown in table 1.
Embodiment 3 prepares catalyst C-3
(1) commercial alumina 50g is weighed, based on final catalyst lanthanum content 1wt% (percentage composition in aluminium oxide), Lanthanum nitrate obtained aqueous solution is weighed, incipient impregnation is in above-mentioned alumina support, aging 3h, 120 DEG C of dry 12h, in 500 DEG C 5h is roasted, the modified support A of containing metal oxide is obtained after roasting.
(2) based on final catalyst Co contents 20wt% and ruthenium content 0.2wt%, cobalt nitrate and nitrosyl nitric acid ruthenium are weighed Obtained aqueous solution B；The modified support A that step (1) obtains is added in aqueous solution B and prepares the suspension C that solid content is 250g/L, After stirring 2h, under lasting stirring, pH to 7~8 is adjusted with the ethylenediamine of 1mol/L, forms suspension D.
(3) under lasting stirring, be added 0.5wt% sodium borohydride aqueous solution solution into suspension D, sodium borohydride with (cobalt+ Ruthenium) molar ratio be 3：1, continue to stir 4h, slurries filter, and sodium ion is washed with deionized into filtrate and is less than 50ppm, 120 DEG C of dry 12h, obtain final catalyst C-3.
In catalyst C-3, cobalt：Lanthanum：Ruthenium：Aluminium oxide=20：1：0.2：78.8 (quality).
Evaluating catalyst condition is the same as embodiment 1.The evaluation result of catalyst is as shown in table 1.
Embodiment 4 prepares catalyst C-4
(1) commercial silica gel 50g is weighed, based on final catalyst lanthanum content 1wt% (percentage composition in aluminium oxide), is claimed Take lanthanum nitrate obtained aqueous solution, incipient impregnation is in above-mentioned silica-gel carrier, aging 3h, and 120 DEG C of dry 12h are roasted in 500 DEG C 5h obtains the modified support A of containing metal oxide after roasting.
(2) it based on final catalyst Co contents 30wt% and silver content 0.1wt%, weighs cobalt nitrate and silver nitrate prepares water Solution B；The modified support A that step (1) obtains is added in aqueous solution B and prepares the suspension C that solid content is 80g/L, stirring After 0.5h, under lasting stirring, pH to 6~7 is adjusted with the ethylenediamine of 1mol/L, forms suspension D.
(3) 0.5wt% potassium borohydride aqueous solutions are added under lasting stirring, into suspension D, potassium borohydride with (cobalt+ Silver) molar ratio be 3：1, continue to stir 1h, slurries filter, and potassium ion is washed with deionized into filtrate and is less than 50ppm, 120 DEG C of dry 12h, obtain final catalyst C-4.
In catalyst C-4, cobalt：Lanthanum：Silver：Silica gel=30：1：0.1：68.9 (quality).
Evaluating catalyst condition is the same as embodiment 1.The evaluation result of catalyst is as shown in table 1.
Embodiment 5 prepares catalyst C-5
(1) commercial silica gel 50g is weighed, (percentage composition in aluminium oxide claims based on final catalyst lanthanum content 1wt% Take lanthanum nitrate obtained aqueous solution, incipient impregnation is in above-mentioned silica-gel carrier, aging 3h, and 120 DEG C of dry 12h are roasted in 500 DEG C 5h obtains the modified support A of containing metal oxide after roasting.
(2) it based on final catalyst Co contents 25wt% and silver content 0.3wt%, weighs cobalt nitrate and silver nitrate prepares water Solution B；The modified support A that step (1) obtains is added in aqueous solution B and prepares the suspension C that solid content is 150g/L, stirs 1h Afterwards, under lasting stirring, pH to 6~7 is adjusted with the ethylenediamine of 1mol/L, forms suspension D.
(3) 0.5wt% potassium borohydride aqueous solutions are added under lasting stirring, into suspension D, potassium borohydride with (cobalt+ Silver) molar ratio be 3：1, continue to stir 2h, slurries filter, and potassium ion is washed with deionized into filtrate and is less than 50ppm, 120 DEG C of dry 12h, obtain final catalyst C-5.
In catalyst C-5, cobalt：Lanthanum：Silver：Silica gel=25：1：0.3：73.7 (quality).
Evaluating catalyst condition is the same as embodiment 1.The evaluation result of catalyst is as shown in table 1.
Embodiment 6 prepares catalyst C-6
(1) commercial silica gel 50g is weighed, based on final catalyst zirconium content 4wt%, weighs zirconium nitrate obtained aqueous solution, etc. Volume impregnation roasts 5h in above-mentioned silica-gel carrier, aging 3h, 120 DEG C of dry 12h in 500 DEG C, is obtained after roasting and contains metal oxygen The modified support A of compound.
(2) it based on final catalyst Co contents 20wt% and rhodium content 0.3wt%, weighs cobalt nitrate and rhodium nitrate prepares water Solution B；The modified support A that step (1) obtains is added in aqueous solution B and prepares the suspension C that solid content is 250g/L, stirs 2h Afterwards, under lasting stirring, pH to 8~9 is adjusted with the ethylenediamine of 1mol/L, forms suspension D.
(3) under lasting stirring, be added 0.5wt% sodium borohydride aqueous solution solution into suspension D, sodium borohydride with (cobalt+ Rhodium) molar ratio be 3：1, continue to stir 4h, slurries filter, and sodium ion is washed with deionized into filtrate and is less than 50ppm, 120 DEG C of dry 12h, obtain final catalyst C-6.
In catalyst C-6, cobalt：Zirconium：Rhodium：Silica gel=20：4：0.3：75.7 (quality).
Evaluating catalyst condition is the same as embodiment 1.The evaluation result of catalyst is as shown in table 1.
Embodiment 7 prepares catalyst C-7
(1) commercial silica gel 50g is weighed, based on final catalyst zirconium content 3wt%, weighs zirconium nitrate obtained aqueous solution, etc. Volume impregnation roasts 5h in above-mentioned silica-gel carrier, aging 3h, 120 DEG C of dry 12h in 500 DEG C, is obtained after roasting and contains metal oxygen The modified support A of compound.
(2) it based on final catalyst Co contents 10wt% and rhodium content 0.1wt%, weighs cobalt nitrate and rhodium nitrate prepares water Solution B；The modified support A that step (1) obtains is added in aqueous solution B and prepares the suspension C that solid content is 80g/L, stirs 1h Afterwards, under lasting stirring, pH to 6~7 is adjusted with the ethylenediamine of 1mol/L, forms suspension D.
(3) under lasting stirring, be added 0.5wt% sodium borohydride aqueous solution solution into suspension D, sodium borohydride with (cobalt+ Rhodium) molar ratio be 3：1, continue to stir 1h, slurries filter, and sodium ion is washed with deionized into filtrate and is less than 50ppm, 120 DEG C of dry 12h, obtain final catalyst C-7.
In catalyst C-7, cobalt：Zirconium：Rhodium：Silica gel=10：3：0.1：86.9 (quality).
Evaluating catalyst condition is the same as embodiment 1.The evaluation result of catalyst is as shown in table 1.
Embodiment 8 prepares catalyst C-8
(1) commercial alumina 50g is weighed, based on final catalyst lanthanum content 2wt%, weighs lanthanum nitrate obtained aqueous solution, Incipient impregnation roasts 5h in above-mentioned alumina support, aging 3h, 120 DEG C of dry 12h in 500 DEG C, is obtained containing gold after roasting Belong to the modified support A of oxide.
(2) it based on final catalyst Co contents 10wt% and silver content 0.2wt%, weighs cobalt nitrate and silver nitrate prepares water Solution B；The modified support A that step (1) obtains is added in aqueous solution B and prepares the suspension C that solid content is 150g/L, stirring After 0.5h, under lasting stirring, pH to 6~7 is adjusted with the ethylenediamine of 1mol/L, forms suspension D.
(3) under lasting stirring, be added 0.5% potassium borohydride aqueous solution into suspension D, potassium borohydride with (cobalt+ Silver) molar ratio be 3：1, continue to stir 1h, slurries filter, and potassium ion is washed with deionized into filtrate and is less than 50ppm, 120 DEG C of dry 12h, obtain final catalyst C-8.
In catalyst C-8, cobalt：Lanthanum：Silver：Aluminium oxide=10：2：0.2：87.8 (quality).
Evaluating catalyst condition is the same as embodiment 1.The evaluation result of catalyst is as shown in table 1.
Comparative example 1, C-8 comparative examples C-db
(1) commercial alumina 50g is weighed, based on final catalyst lanthanum content 2wt%, weighs lanthanum nitrate obtained aqueous solution, Incipient impregnation roasts 5h in above-mentioned alumina support, aging 3h, 120 DEG C of dry 12h in 500 DEG C, is obtained containing gold after roasting Belong to the modified support A of oxide.
(2) it based on final catalyst Co contents 10wt% and silver content 0.2wt%, weighs cobalt nitrate and silver nitrate is isometric It is impregnated in above-mentioned modified support A, 120 DEG C of dry 12h roast 5h in 350 DEG C, obtain final catalyst.
Evaluating catalyst condition is the same as embodiment 1.The evaluation result of catalyst is as shown in table 1.
Can be seen that from the data in table 1 has good reaction using catalyst prepared by method provided by the invention Performance, catalyst activity prepared by the method for the present invention is high, methane selectively is low, heavy hydrocarbon (C5+) high selectivity.
The evaluation result of catalyst in 1 embodiment of table

Claims (10)

1. a kind of low-temperature treatment Co based Fischer-Tropsch synthesis catalyst, is made of cobalt, metal promoter, precious metal additive and carrier；
In the Co based Fischer-Tropsch synthesis catalyst of every 100 mass parts, the content of each component is as follows：
Cobalt 5~50；
Metal promoter 0.5~10；
Precious metal additive 0.05~5；
The carrier of surplus.
2. Co based Fischer-Tropsch synthesis catalyst according to claim 1, it is characterised in that：The carrier is Al2O3、TiO2With SiO2At least one of.
3. Co based Fischer-Tropsch synthesis catalyst according to claim 1 or 2, it is characterised in that：The metal promoter is alkali gold At least one of category, alkaline-earth metal, transition metal and rare earth metal；
The precious metal additive is at least one of ruthenium, rhodium, palladium, iridium, platinum, Jin Heyin.
4. the preparation method of any one of the claim 1-3 Co based Fischer-Tropsch synthesis catalysts, includes the following steps：
(1) soluble-salt of the metal promoter is carried on the carrier using infusion process, is changed through dry and roasting Property carrier；
(2) aqueous solution for preparing the soluble-salt and soluble cobalt of the precious metal additive, the modified support is added Enter and obtain suspending liquid A into the aqueous solution, adjusts the pH value of the suspending liquid A to 4~12, obtain suspension B；
(3) reducing agent is added into the suspension B, the Co based Fischer-Tropsch synthesis catalyst is obtained through reduction.
5. preparation method according to claim 4, it is characterised in that：In step (1), the infusion process is using isometric leaching Stain crosses volume impregnation, single-steeping or the mode repeatedly impregnated；
The step of infusion process, is as follows：
The carrier is impregnated using the aqueous solution of the soluble-salt of the metal promoter；
The temperature of the drying is 60~200 DEG C, and the time is 2~36h；
The temperature of the roasting is 200~800 DEG C, and the time is 2~30h；
The soluble-salt of the metal promoter is nitrate.
6. preparation method according to claim 4 or 5, it is characterised in that：In step (2), the solid content of the suspending liquid A For 10~600g/L；
Stir the pH value that the suspending liquid A is adjusted after the 0.1~6h of suspending liquid A；
By the way that the tune of salpeter solution and/or ethylenediamine solution realization to the pH value of the suspending liquid A is added into the suspending liquid A Section.
7. according to the preparation method described in any one of claim 4-6, it is characterised in that：In step (2), the noble metal helps The soluble-salt of agent is Ru (NO) (NO3)3、Rh(NO3)3·2H2O、Pd(NO3)2·2H2O、IrCl3·3H2O、Pt(NO3)2、 HAuCl4And AgNO3At least one of；
The soluble cobalt is cobalt nitrate, cobalt acetate or at least one of with cobaltous sulfate.
8. according to the preparation method described in any one of claim 4-7, it is characterised in that：In step (3), the reducing agent is Potassium borohydride or sodium borohydride；
It is added in the form of the aqueous solution of the reducing agent into the suspension B；
The molar ratio of cobalt and the precious metal additive described in the reducing agent and the Co based Fischer-Tropsch synthesis catalyst can be 2~ 5：1；
Further include the steps that being filtered, washed and dried after the reduction；
The temperature of the drying is 60~200 DEG C, and the time is 2~36h.
9. application of any one of the claim 1-3 Co based Fischer-Tropsch synthesis catalysts in being catalyzed Fischer-Tropsch synthesis.
10. application according to claim 9, it is characterised in that：The Co based Fischer-Tropsch synthesis catalyst catalytic fixed bed is taken Hold in the palm synthetic reaction or syrup state bed Fischer Tropsch synthetic reaction.
CN201810102109.4A 2018-02-01 2018-02-01 A kind of heavy hydrocarbon fischer-tropsch synthetic catalyst of low-temperature treatment and its preparation method and application Pending CN108295867A (en)

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