WO2016060330A1 - Procédé de préparation de nanocatalyseur de type coquille d'œuf à base de cobalt/silice pour réaction de synthèse fischer-tropsch, et catalyseur et procédé de synthèse d'hydrocarbure liquide l'utilisant et hydrocarbure liquide - Google Patents

Procédé de préparation de nanocatalyseur de type coquille d'œuf à base de cobalt/silice pour réaction de synthèse fischer-tropsch, et catalyseur et procédé de synthèse d'hydrocarbure liquide l'utilisant et hydrocarbure liquide Download PDF

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WO2016060330A1
WO2016060330A1 PCT/KR2014/012316 KR2014012316W WO2016060330A1 WO 2016060330 A1 WO2016060330 A1 WO 2016060330A1 KR 2014012316 W KR2014012316 W KR 2014012316W WO 2016060330 A1 WO2016060330 A1 WO 2016060330A1
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silica
cobalt
shell
fischer
egg
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PCT/KR2014/012316
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Korean (ko)
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박지찬
양정일
정헌
이호태
천동현
홍성준
권재인
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한국에너지기술연구원
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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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing

Definitions

  • the present invention relates to a method for preparing a cobalt-silica egg-shell nanocatalyst for a Fischer-Tropsch synthesis reaction, a catalyst thereof, a method for synthesizing a liquid hydrocarbon using the same, and a liquid hydrocarbon thereof in detail.
  • Fischer-Tropsch (FT) synthesis was developed by German chemists Franz Fischer and Hans Tropsch in the 1920s, a mixture of carbon monoxide and hydrogen obtained by converting coal, natural gas and biomass resources. It is a technique for producing a synthetic fuel (hydrocarbon) as shown in the following formula through a catalytic reaction under high temperature, high pressure using.
  • a catalyst including cobalt and iron is mainly used, and reaction conditions such as reaction temperature, pressure, and gas composition are determined according to the type of catalyst applied.
  • the Fischer-Tropsch synthesis reaction is a low temperature Fischer-Tropsch (LTFT) that mainly forms diesel and wax between 180 and 260 ° C, depending on the desired product to be obtained through the reaction and the reaction temperature conditions for obtaining it effectively.
  • LTFT low temperature Fischer-Tropsch
  • HTFT high temperature Fischer-Tropsch
  • gasoline and light olefin gases ethylene, propylene
  • CTL coal-to-liquid
  • iron-based catalysts are used as Fischer-Tropsch reaction catalysts. It is also active in the water gas shift reaction, and the ratio of hydrogen to carbon monoxide synthesis gas can be used in various compositions within 1 to 2, and it can be used even in the presence of carbon dioxide, which is an impure gas.
  • the Fischer-Tropsch reaction using the iron-based catalyst also has the disadvantage of generating a large amount of carbon dioxide after the reaction, whereas the cobalt-based catalyst has a very low activity in the water gas transition reaction, and thus a long carbon chain chain with little generation of carbon dioxide.
  • cobalt-based catalysts have a disadvantage of being expensive compared to iron-based catalysts, they have advantages of high activity and long life. Therefore, in the case of the Fischer-Tropsch synthesis reaction using such a cobalt catalyst, high dispersion, high support and high temperature stability of the supported cobalt catalyst particles are required in order to compactly design the reactor and secure economical efficiency.
  • the egg-shell structure composed of cobalt and silica components, which are known to exhibit high activity in the Fischer-Tropsch reaction, has advantages in controlling heat of reaction or diffusion of reactants during the reaction, compared to general pellet type catalysts. (Gardezi, SA et. Al. Ind. Eng. Chem. Res. 2012, 51, 1703-1712).
  • the surface of the cobalt particles actually supported has a high dispersibility and rapid diffusion and contact with the reactants. There are some disadvantages.
  • the egg-shell catalyst manufactured in the conventional mm size region is mainly controlled by the metal salt impregnation time control or selective absorption technique using viscosity or affinity.
  • the selective uptake of metal salts is not easy, which makes it nearly impossible to make egg-shell catalysts on nanosized silica supports (Iglesia, E. et. Al. J. Catal. 1995, 153, 108-122).
  • An object of the present invention for solving the above problems is that the thermally stable, cobalt nano-scaled active cobalt particles are selectively dispersed in the pores of the nano-sized porous silica support shell and reacted during the Fischer-Tropsch reaction
  • the present invention provides a method for preparing a cobalt-silica egg-shell nanocatalyst having high activity in terms of fast diffusion and contact, and a catalyst thereof.
  • Another object of the present invention to provide a liquid hydrocarbon and a method for producing a liquid hydrocarbon effectively by having a high CO conversion and selectivity during the Fischer-Tropsch synthesis reaction using the cobalt-silica egg-shell nanocatalyst have.
  • the present invention to achieve the object as described above and to solve the conventional drawbacks is to (i) the precursor of silica Synthesizing silica structure particle powder using the method;
  • the step i) is to synthesize a silica structure having a spherical shape of 100 ⁇ 1000 nm size using the precursor TEOS (Tetraethyl orthosilicate) or TMOS (Tetramethyl orthosilicate) of silica in alcohol and water-based conditions It may be a step.
  • TEOS Tetraethyl orthosilicate
  • TMOS Tetramethyl orthosilicate
  • the step (iv) is a CTAB (Cetrimonium bromide, IUPAC Name: hexadecyl-trimethyl) having a long carbon chain of 16 carbons of step (ii) mixed with the silica precursor of step (i) -ammonium bromide) may be a step of forming pores by heat treatment to remove it.
  • CTAB Cosmetical bromide, IUPAC Name: hexadecyl-trimethyl
  • reaction time to melt-impregnated in step (iii) may be 4 to 48 hours.
  • the (iv) step is 400 ⁇ 700 °C to form a nanometer size cobalt particles by firing in a hydrogen atmosphere in the porous shell of the silica powder particles to be used as a support is optionally supported with a cobalt hydrate salt It can reduce in between.
  • the present invention is prepared according to the method described above, and the active nano-cobalt particles are uniformly formed only in the porous silica shell in the nano-silica structure in which the porous shell is formed of a tightly packed silica and many pores are formed near the shell. It is achieved by providing a cobalt-silica egg-shell nanocatalyst for a Fischer-Tropsch synthesis reaction characterized in that it is selectively positioned.
  • the size of the cobalt nanoparticles supported on the porous silica shell is 2 ⁇ 20 nm, the size of the entire particle including the silica structure is 100 ⁇ 1000 nm, the thickness of the porous silica shell is 10 ⁇ 100 nm.
  • the present invention comprises the steps of injecting the cobalt-silica egg-shell nanocatalyst for the Fischer-Tropsch synthesis reaction;
  • Fischer-Tropsch synthesis reaction comprising the It is achieved by providing a process for the preparation of liquid hydrocarbons using cobalt-silica egg-shell nanocatalysts.
  • the synthesis gas may be a mixture of one or two of a volume ratio of carbon monoxide and hydrogen, or a gas in which any one of an inert gas, methane, and carbon dioxide is mixed as impurities in carbon monoxide and hydrogen.
  • the syngas may be injected into the reactor within a gas hourly space velocity (GHSV) of 2.0 to 24.0 NL / g cat / hr.
  • GHSV gas hourly space velocity
  • reaction temperature may be carried out between 180 ⁇ 260 °C.
  • the present invention is also achieved in another embodiment by providing a liquid hydrocarbon prepared according to the method for preparing a liquid hydrocarbon using the cobalt-silica egg-shell nanocatalyst for the Fischer-Tropsch synthesis reaction.
  • the cobalt / silica egg-shell nanocatalyst of the present invention having the above characteristics is made of a porous silica structure formed of solid dense silica in the inside and many pores in the vicinity of the shell. While the active cobalt particles are uniformly supported, they can also be selectively positioned only inside large silica shells.
  • cobalt / silica egg-shell nano-catalyst is a structure that is advantageous for the diffusion and heat dissipation of the reactant when used to obtain a stable and excellent reaction results in the Fischer-Tropsch synthesis reaction proceeds at a high temperature of more than 180 degrees It is a useful invention having the advantage of being able to effectively obtain a hydrocarbon compound from a mixed gas of carbon monoxide and hydrogen is an invention that is expected to be greatly utilized in industry.
  • FIG. 1 is a schematic diagram of the production of egg-shell type high dispersion cobalt / silica nanocatalyst according to an embodiment of the present invention
  • FIG. 2 is a flow chart showing an egg-shell type highly dispersed cobalt / silica nanocatalyst manufacturing process according to one embodiment of the present invention
  • FIG. 3 is a SEM image of silica particles according to Example 1 of the present invention, (b) TEM image of a silica structure coated with a porous silica shell, and (c) egg-shell cobalt / cobalt-containing cobalt particles 10wt% / TEM image of silica nanoparticles, (d) HADDF-STEM image of egg-shell cobalt / silica nanoparticles, high-magnification TEM image of egg-shell cobalt / silica nanoparticle shell portion,
  • Example 4 is a TEM image of silica particles according to Example 2 of the present invention, (b) TEM image of a silica structure coated with a porous silica shell, and (c) an egg-shell cobalt containing 10 wt% of cobalt particles. XRD spectrum of the silica nanoparticles,
  • 5 is (a) a graph of nitrogen adsorption and desorption of a silica structure coated with a porous silica shell and (b) nitrogen of an egg-shell cobalt / silica nanoparticle in which 10 wt% of cobalt particles are loaded. Adsorption and desorption experiment graph,
  • FIG. 6 is a TEM image of (a) an egg-shell cobalt / silica nanoparticle having 20 wt% of cobalt particles according to Example 3 of the present invention, (b) a high magnification TEM image, (c) an XRD spectrum,
  • FIG. 7 is a time-phase FT activity of hydrocarbon production of an egg-shell cobalt / silica nano catalyst having 10 wt% of cobalt particles according to Example 4 of the present invention.
  • FIG. 8 is a time-phase FT activity of hydrocarbon production of an egg-shell cobalt / silica nano catalyst having 20 wt% of cobalt particles according to Example 5 of the present invention.
  • Example 9 is a liquid hydrocarbon compound photograph, a) oil, b) wax, actually produced for 90 hours using an egg-shell cobalt / silica nano catalyst having 20 wt% of cobalt particles according to Example 5 of the present invention.
  • FIG. 1 is a schematic view of the production of egg-shell high dispersion cobalt / silica nanocatalyst according to an embodiment of the present invention
  • Figure 2 is an egg-shell high dispersion cobalt / silica nanocatalyst according to an embodiment of the present invention It is a flowchart showing a manufacturing process.
  • the present invention relates to the production of a cobalt / silica nanostructure catalyst selectively dispersed in the shell of the porous silica structure particles in which the cobalt particles are used as a support at a small size of 2 to 20 nm while thermally stable.
  • the supporting method of the cobalt salt the procedure is easy, and a melt impregnation method which is advantageous for high dispersion of particles is used.
  • the silica structure particles used as a support is a conventionally known method
  • Silica spherical particles prepared by the method have a porous shell obtained through heat treatment after the silica coating again with a compound having a long carbon chain.
  • the porous silica structure is made of solid dense silica inside and many pores are formed near the shell, so that the active cobalt particles are uniformly supported when the particles are supported by the melt impregnation method. Will be located.
  • the cobalt / silica egg-shell catalyst of the present invention is formed at the nano level by selectively impregnating the cobalt salt only in the nanometer-level porous silica shell portion with pores.
  • the size of the cobalt nanoparticles supported on the porous silica shell is preferably between 2 and 20 nm in consideration of its dispersibility and optimal activity.
  • the total particle size including, may include from 100 nm to 1000 nm. The reason is that if the size of the spherical particles is too small, the loading of the cobalt particles becomes difficult, and if they are too large, they may be disadvantageous in reactant diffusion and heat dissipation.
  • the thickness of the stacked porous silica shell may be between 10 nm and 100 nm that can support the active cobalt particles well.
  • the present invention is well known Highly dispersed nano cobalt / silica egg-shell hybrid nanocatalysts are obtained through melt impregnation and thermal reduction of hydrated cobalt salt using nano-sized silica particles synthesized through the process.
  • the method for preparing the cobalt / silica egg-shell catalyst is (i) Synthesizing silica structure particles using the method, (ii) further coating silica using a CTAB (Cetyl trimethylammonium bromide) reagent to form a porous silica shell through heat treatment, and (iii) heat treating the porous silica powder.
  • CTAB Cosmetic Acid Trimethylammonium bromide
  • the silica structure synthesized in step (i) has a spherical shape and uses TEOS (Tetraethyl orthosilicate) as a precursor of silica under alcohol and water-based conditions. It can be synthesized through the method, and the particle size of the silica can be about 100 ⁇ 1000 nm.
  • TEOS Tetraethyl orthosilicate
  • Alcohol used in the method may be methanol, ethanol, propanol (2-propanol) and the like, and the use of ethanol is more preferable to obtain a silica of uniform shape.
  • the silica precursor can be used not only in TEOS (Tetraethyl orthosilicate) but also in TMOS (Tetramethyl orthosilicate). It is disadvantageous.
  • Cetrimonium bromide ((C 16 H 33 ) N (CH 3 ) 3 Br, cetyltrimethylammonium bromide, IUPAC Name: hexadecyl-trimethyl-ammonium bromide, CTAB) compound used in step (ii) is a long carbon chain consisting of 16 carbons Since it remains together when mixed with the silica precursor, it is removed during subsequent heat treatment to form pores.
  • the reaction time is preferably about 4 to 48 hours so that the cobalt salts are sufficiently dissolved to enter the pores of the silica shell.
  • the reduction temperature is preferably between 400 ⁇ 700 °C to achieve a sufficient reduction. This is because reduction may not be performed completely at a temperature below 400 ° C., and aggregation of particles may occur at a temperature of 700 ° C. or more.
  • Cobalt particles located in the cobalt / silica structure obtained through high temperature heat treatment in a hydrogen atmosphere may easily be oxidized when exposed to air, so a passivation process is required immediately after the heat treatment.
  • the passivation process for the stabilization of the activated catalyst under reducing conditions at a high temperature of 300 ° C. or higher in step (v) is a very important step in the subsequent catalytic reaction application of the nanoparticle powder. It will block the reaction of the.
  • the organic solvent can be used a variety of solvents such as ethanol, mineral oil, but can not use water or other oxidizing agents that can oxidize and change the catalyst.
  • Passivation is carried out by dipping the catalyst directly in an organic solvent so as not to be exposed to oxygen in nitrogen or other inert gas atmosphere. It is preferable to use volatile ethanol as a solvent for further analysis or reaction. Especially in the case of transition metal / silica nanostructures, the catalyst itself is magnetic, so it can be easily separated from the solvent using a magnet. desirable.
  • the highly dispersed cobalt / silica supported catalyst prepared as described above is a structure in which small cobalt particles are uniformly embedded in the silica shell, as well as the Fischer-Tropsch reaction, as well as the Pauson-Kand reaction or Carbo. It can be usefully applied to various liquid catalyst reactions such as phenoxycarbonyl reactions.
  • the cobalt / silica egg-shell nanocatalyst prepared by the method for preparing the catalyst may be used in the preparation of liquid hydrocarbons using Fischer-Tropsch synthesis reaction, which includes the step of putting the synthesis gas into a tubular fixed bed reactor. have.
  • the method for producing liquid hydrocarbon using Fischer-Tropsch synthesis reaction according to the present invention is as follows.
  • Syngas may be carbon monoxide, hydrogen, inert gas or methane, or a material composed of carbon dioxide. More preferably, the volume ratio of carbon monoxide and hydrogen is used in a ratio of 1: 2 in terms of yield of the product.
  • the synthesis gas is preferably injected into the fixed bed reactor in the range of the space velocity is 2.0 ⁇ 24.0 NL / gcat / hr.
  • reaction temperature can be used at 180 ⁇ 260 °C but if the high temperature stability of the catalyst is secured, the reaction may be suitable between 220 ⁇ 240 °C to increase the conversion of carbon monoxide and increase the yield of liquid hydrocarbon.
  • Silica nanoparticles that can be used as silica supports are well known It was prepared using the method.
  • silica spherical particles To obtain silica spherical particles, add 8 mL of ammonium hydroxide solution (28 wt%) and 20 mL of tetraethyl orthosilicate (TEOS) in a 1 L beaker containing 200 mL of ethanol and 32 mL of distilled water. Put and stirred for 2 hours.
  • ammonium hydroxide solution 28 wt%
  • TEOS tetraethyl orthosilicate
  • the silica particles obtained after 2 hours were used after being precipitated through centrifugation and dispersed in ethanol. In order to minimize ammonia that may remain even after washing, the dispersion-precipitation process was repeated two or more times using ethanol.
  • Ahead of Porous silica shells were further coated with a silica solution dispersed in ethanol obtained by the method.
  • Cetrimonium bromide ((C 16 H 33 ) N (CH 3 ) 3 Br, cetyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, CTAB) reagent was dissolved in a solution containing 20 mL of distilled water and 10 mL of ethanol.
  • the precipitate was precipitated by centrifugation, followed by water, ethanol, acetone, and washed again by repeating the dispersion-precipitation process. Finally, the powder obtained was sufficiently dried in an oven set at 100 ° C., and then heat-treated at 500 ° C. for 8 hours using an calcination apparatus.
  • the powder was cooled at room temperature, and then calcined at 400 ° C. for 4 hours in a hydrogen atmosphere using a baking oven to obtain an egg-shell cobalt / silica hybrid nanocatalyst having 10 wt% of cobalt.
  • the cobalt / silica hybrid catalyst since oxidation proceeds rapidly when exposed to air, the cobalt / silica hybrid catalyst was stored in ethanol which is effective for passivation under a nitrogen atmosphere after firing. At this time, it is important to blow nitrogen strongly at 500cc / min so as not to introduce external air that may cause oxidation, and to put it instantaneously into a container containing ethanol under a prepared nitrogen atmosphere.
  • Silica particles The method can be adjusted to various sizes depending on various conditions, such as the amount of water, ethanol or ammonia used in the synthesis. Accordingly, the overall size of the egg-shell particles can also be controlled. As an example, 4 mL of ammonium hydroxide solution (28 wt%) and 10 mL of tetraethyl orthosilicate (TEOS) were further added to an Erlenmeyer flask containing 50 mL of ethanol and 8 mL of distilled water, followed by stirring for 2 hours. .
  • TEOS tetraethyl orthosilicate
  • the silica particles obtained after 2 hours were used after being precipitated through centrifugation and dispersed in ethanol. In order to minimize ammonia that may remain even after washing, the dispersion-precipitation process was repeated two or more times using ethanol.
  • Ahead of Porous silica shells were further coated with a colloidal silica solution dispersed in ethanol obtained by the method.
  • a colloidal silica solution dispersed in ethanol obtained by the method.
  • 1.2 g of CTAB reagent was dissolved in a solution of 20 mL of distilled water and 10 mL of ethanol.
  • 100 mL of the 0.181 M silica solution obtained above with 200 mL of distilled water was added and stirred well for 30 minutes.
  • the silica particles were precipitated by centrifugation, followed by water, ethanol and acetone, followed by washing again by dispersing-precipitation. Finally, the powder obtained was sufficiently dried in an oven set at 100 ° C., and then heat-treated at 500 ° C. for 8 hours using a firing apparatus.
  • the powder After 24 hours, the powder is cooled at room temperature, and then fired at 500 ° C. for 4 hours in a hydrogen atmosphere flowing at 200 ml per minute using a tube-type baking oven to obtain an egg-shell cobalt / silica hybrid catalyst containing 10 wt% of cobalt. there was.
  • cobalt / silica mixed powder was stored in ethanol, which is effective for passivation under nitrogen atmosphere, in order to prevent rapid oxidation upon exposure to air.
  • X-ray diffraction (XRD) analysis for qualitative analysis showed that the crystal phase of the particles was metallic cobalt species, as shown in FIG.
  • An egg-shell nanocatalyst carrying 20 wt% of cobalt particles was prepared using silica particles coated with a porous silica shell prepared in the same manner as in Example 2.
  • mixed powder was placed in a 30 mL polypropylene container, the container was capped tightly, and put in a drying oven having a temperature set at 60 ° C., and aged for 24 hours.
  • the powder was cooled to room temperature, and then calcined at 500 ° C. for 4 hours using a baking oven to obtain an egg-shell cobalt / silica hybrid catalyst having 20 wt% of cobalt.
  • cobalt / silica hybrid powder was stored in ethanol under nitrogen atmosphere to prevent rapid oxidation upon exposure to air.
  • the Fischer-Tropsch synthesis reaction was carried out based on the cobalt / silica egg-shell catalyst containing 10 wt% of cobalt metal obtained in Example 2.
  • the reactor used a fixed-bed reactor, and the reaction process used an automated system that can be operated by a personal computer (PC).
  • PC personal computer
  • the Fischer-Tropsch synthesis reaction was carried out on the basis of the cobalt / silica egg-shell catalyst containing 20 wt% of the cobalt metal obtained in Example 3.
  • 0.5 g of a cobalt / silica egg-shell catalyst was dried and immediately loaded into a reactor having an inner diameter of 5 mm.
  • a synthesis gas maintained at a ratio of hydrogen to carbon monoxide at a ratio of 2: 1 was introduced into the reactor under a reaction pressure of 20 atm and a space velocity of 7.2 NL / G (cat) -h to carry out Fischer-Tropsch synthesis reaction at 230 ° C. was performed.

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Abstract

La présente invention concerne un procédé de préparation d'un nanocatalyseur de type coquille d'œuf à base de cobalt/silice pour une réaction de synthèse Fischer-Tropsch, ainsi que ledit catalyseur, et un procédé de synthèse d'hydrocarbure liquide l'utilisant, et ledit hydrocarbure liquide Plus précisément, l'invention concerne un procédé de préparation d'un nanocatalyseur de type coquille d'œuf à base de cobalt/silice, et ledit catalyseur qui présente des particules de cobalt actif qui sont thermiquement stables et sélectivement ajustées par taille nanométrique et hautement dispersées sur une coquille de support à base de silice poreuse de taille nanométrique présentant des pores développés sur celle-ci, ledit catalyseur présentant ainsi une activité élevée en termes de diffusion rapide et de contact d'un réactif au moment de la réaction de Fischer-Tropsch. L'invention concerne en outre un procédé de préparation d'un hydrocarbure liquide et ledit hydrocarbure liquide, le procédé présentant, du fait de l'utilisation du nanocatalyseur de type coquille d'œuf à base de cobalt/silice, les avantages d'un haut taux de conversion de Co et d'une haute sélectivité au moment de la réaction de synthèse Fischer-Tropsch.
PCT/KR2014/012316 2014-10-17 2014-12-15 Procédé de préparation de nanocatalyseur de type coquille d'œuf à base de cobalt/silice pour réaction de synthèse fischer-tropsch, et catalyseur et procédé de synthèse d'hydrocarbure liquide l'utilisant et hydrocarbure liquide WO2016060330A1 (fr)

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CN108996477B (zh) * 2018-07-26 2022-02-22 四川理工学院 一种基于Stober法合成金属氧化物微球的方法
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