US20060223693A1 - Catalyst for producing hydrocarbon from synthsis gas and method for producing catalyst - Google Patents

Catalyst for producing hydrocarbon from synthsis gas and method for producing catalyst Download PDF

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US20060223693A1
US20060223693A1 US10/552,234 US55223405A US2006223693A1 US 20060223693 A1 US20060223693 A1 US 20060223693A1 US 55223405 A US55223405 A US 55223405A US 2006223693 A1 US2006223693 A1 US 2006223693A1
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catalyst
metallic compound
mass
catalyst support
silica
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Kenichiro Fujimoto
Kimihito Suzuki
Shouli Sun
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Nippon Steel Corp
Japan Oil Gas and Metals National Corp
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Assigned to JAPAN OIL, GAS AND METALS NATIONAL CORPORATION, NIPPON STEEL CORPORATION reassignment JAPAN OIL, GAS AND METALS NATIONAL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FUJIMOTO, KENICHIRO, SUN, SHOULI, SUZUKI, KIMIHITO
Publication of US20060223693A1 publication Critical patent/US20060223693A1/en
Priority to US12/750,451 priority Critical patent/US8178589B2/en
Priority to US13/445,484 priority patent/US8524788B2/en
Abandoned legal-status Critical Current

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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
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • 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
    • B01J37/06—Washing
    • 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
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g

Definitions

  • the present invention relates to a catalyst for producing hydrocarbon from a syngas, which is suitable for a hydrogenation of carbon monoxide and a hydrocarbon production from carbon monoxide, a method for producing the catalyst, and a method for producing a hydrocarbon using the catalyst.
  • This Fischer-Tropsch synthesis reaction converting the syngas into hydrocarbon with a catalyst is an exothermic reaction, where it is important to effectively remove reaction heat for a stable operation of the plant.
  • time-proven reaction processes there are gas-phase synthesis processes (in a fixed bed, entrained bed, or fluid bed) and a liquid-phase synthesis process (in a slurry bed) having respective features.
  • gas-phase synthesis processes in a fixed bed, entrained bed, or fluid bed
  • a liquid-phase synthesis process in a slurry bed
  • a higher catalytic activity is preferable, and especially, in the case of the slurry bed.
  • concentration of slurry may be needed to be a prescribed value or below so as to keep a favorable slurry state, so that the increase in the catalytic activity is an important factor to increase a process design flexibility.
  • the reported catalytic activities of various types of catalysts for the Fischer-Tropsch synthesis are approximately 1 (kg ⁇ hydrocarbon/kg ⁇ catalyst ⁇ hour) at most in view of the production rate of liquid hydrocarbon of a carbon number of five or above, which cannot be said always enough from the above-described viewpoints, as described in R. Oukaci et al., “Applied Catalysis A”, General, 186 (1999), p. 129-144, the entire disclosure of which is incorporated herein by reference.
  • the particle diameter of the catalyst for the Fischer-Tropsch synthesis reaction is preferably provided as small as practically as possible from the aspect of reducing a possibility in which the diffusions of heat and matters come to a rate-determining level.
  • the Fischer-Tropsch synthesis reaction in the slurry bed out of the generated hydrocarbon, the high-boiling point hydrocarbon is accumulated in the reactor, inevitably requiring a solid-liquid separating operation for separating a product from the catalyst, so that there may be another problem that the catalyst of a too small particle diameter reduces the efficiency of the separating operation.
  • the catalyst for the slurry bed there should be an optimum particle diameter range, and generally, the range from about 20 ⁇ m to about 250 ⁇ m, or about 40 ⁇ m to about 150 ⁇ m as an average particle diameter, is considered to be desirable. However, as discussed below, there may be a case where the catalyst is caused to be fractured and pulverized to have a smaller particle diameter in the course of the reaction, requiring a caution.
  • the operation can be frequently performed at an extremely high material-gas superficial velocity (>0.1 m/second), so that the catalyst particles clash furiously with each other during the reaction to possibly reduce their particle diameters during the reaction when the physical strength and abrasion resistance (resistance to be pulverized) are insufficient. This may at times cause an inconvenience in the separating operation.
  • volumes of water can be generated as a by-product.
  • the particle diameter of the catalyst is possibly reduced into a fine powder during the reaction, causing sometimes the inconvenience in the separating operation in the same manner as above.
  • the current catalytic activity may not yet be sufficient, and the catalyst with a higher catalytic activity has been requested as a pressing need, also from a viewpoint of extending the design flexibility in the plant.
  • the catalyst for the slurry bed can be frequently put into practical use there by being prepared through a size control procedure by way of a grinding to have an appropriate particle diameter as described above.
  • a catalyst of a ground type may frequently have a crack or sharp protrusion arisen originally, and can effectuate a lesser mechanical strength and abrasion resistance.
  • the catalyst is forced to fracture to generate fine powders, and it becomes difficult to separate the generated high-boiling point hydrocarbon from the catalyst when used in the Fischer-Tropsch synthesis reaction in the slurry bed.
  • a relatively highly-active catalyst can be obtained when a porous silica is used as the catalyst support for the Fischer-Tropsch synthesis reaction.
  • the size control based on the grinding may also lead to the strength deterioration due to the previously-described reason.
  • the silica has lesser water resistance, and is frequently fractured into powders when water exists, thus causing problems especially in the case of the slurry bed.
  • One of the objects of the present invention is to provide a catalyst for a Fischer-Tropsch synthesis, which brings a solution to the above-described problems and exhibits a high activity without deteriorating its catalytic strength and abrasion resistance; a producing method of the catalyst, and a producing method of hydrocarbon using the catalyst.
  • Exemplary embodiments of the present invention relates to a catalyst for a Fischer-Tropsch synthesis exhibiting a high strength and activity, a method for producing the catalyst, and a method for producing hydrocarbon using the catalyst. Additional details therefor are provided below.
  • a catalyst for producing hydrocarbon from a syngas including a catalyst support on which a metallic compound is loaded, in which an impurity content of the catalyst is in a range from 0.01 mass % to 0.15 mass %.
  • An alkali metal or an alkaline-earth metal content in the catalyst support can be in a range from 0.01 mass % to 0.1 mass %.
  • the catalyst support can satisfy a pore diameter in a range from 8 nm to 50 nm, a surface area in a range from 80 m 2 /g to 550 m 2 /g and a pore volume in a range from 0.5 mL/g to 2.0 mL/g, simultaneously.
  • the catalyst support in use allows the catalyst have a fractured or pulverized ratio of 10% or below when an ultrasonic wave is emitted for four hours at a room temperature to the catalyst dispersed in water.
  • the catalyst support may be silica of a spherical shape.
  • the metallic compound may contain iron, cobalt, nickel and/or ruthenium. This metallic compound can be made from a precursor of metallic compound of the alkali metal or alkaline-earth metal content of 5 mass % or lower.
  • a method for producing the catalyst described above in which the metallic compound is loaded on a catalyst support after a pretreatment to lower an impurity concentration of the catalyst support is performed to the catalyst support.
  • the pretreatment may include rinsing using at least one of acid and an ion-exchanged water.
  • the catalyst can be prepared using a catalyst support obtained using rinsing water of an alkali metal or alkaline-earth metal content of 0.06 mass % or lower in the production step of the catalyst support.
  • the catalyst support e.g., silica
  • the catalyst support may have a spherical shape shaped by a spraying method.
  • a method for producing hydrocarbon in which the hydrocarbon is produced from a syngas using the catalyst described herein above.
  • a catalyst for a Fischer-Tropsch synthesis with extremely high activity without deteriorating strength and abrasion resistance of the catalyst, and to perform a Fischer-Tropsch synthesis reaction exhibiting a high hydrocarbon production rate backed by the catalyst.
  • FIG. 1 is a graph showing a relation between metal contents in a catalyst support of silica and a CO conversion.
  • a catalyst according to an exemplary embodiment of the present invention is not specifically limited to some one as long as the catalyst contains metal having an activity for a Fischer-Tropsch synthesis reaction, and those catalysts containing iron, cobalt, nickel, ruthenium and the like are acceptable, and as for a catalyst support, preferably, a selection is made from porous oxides or the like made of silica, alumina, titania and the like appropriately to use the selection for the catalyst support.
  • a common impregnation method, an incipient wetness method, a precipitation method, an ion-exchange method and the like can be employed.
  • a loading amount in that the amount changes depending on respective metallic compounds in use, however, a range between a minimum amount exhibiting the activity or above and a loading amount, which causes a contribution efficiency reduction in a reaction due to a sharp drop in the dispersion of the metallic compound on a catalyst support, or below is acceptable.
  • the amount when the cobalt is in use, the amount is in the range from 5 mass % to 50 mass %, and, preferably, from 10 mass % to 40 mass %. In the case of the amount below the range, enough activity may not be obtained, and in the case of the amount above the range, the dispersion drops to a lower utilization efficiency of the cobalt loaded on the catalyst support uneconomically.
  • calcination and/or reduction can be performed as appropriate, so that a catalyst for the Fischer-Tropsch synthesis may be obtained.
  • the reduction of impurities, which is other than the metallic compound and an element composing the catalyst support, in the catalyst to control the impurities to be within a certain range has a great effect to improve the activity.
  • the silica in general, the silica frequently contains an alkali metal such as Na, an alkaline-earth metal such as Ca and Mg, and Fe, Al, and the like, as the impurities.
  • the effect of these impurities may be reviewed in detail using the cobalt as a metallic compound, and it has been determined that a large amount of the alkali metal and/or alkaline-earth metal causes a large activity reduction in the Fiseher-Tropsch synthesis reaction. Among those, it is found together that the strongest effect can be seen when sodium is contained.
  • the amount of impurities in the catalyst should be curbed to 0.15 mass % or below. If the impurity amount is above the range, the activity decreases largely, being extremely disadvantage. However, an excessive reduction of the impurities leads to diseconomy, so that a preferable impurity amount in the catalyst is 0.01 mass % or above. It is difficult to limit the impurity amount in the precursor of metallic compound, since it depends on the loading amount and the type of precursor. However, in order to reduce the impurity amount in the catalyst, it can be effective to curb the impurity amount in the precursor of metallic compound, especially, the alkali metal content or the alkaline-earth metal content to 5 mass % or lower.
  • the alkali metal content or the alkaline-earth metal content in the catalyst support are preferably 0.1 mass % or lower, and more preferably, they are 0.07 mass % or lower, and most preferably, they are 0.04 mass % or lower.
  • the impurity content in the catalyst support comes to 0.15 mass % or higher, the activity of the catalyst falls largely.
  • an excessive reduction of the alkali metal content and alkali-earth metal content in the catalyst support leads to diseconomy, the alkali metal and alkali-earth metal may exist in the catalyst to the extent of their contents not affecting adversely the catalytic activity.
  • the alkali metal content and alkaline-earth metal content in the catalyst support are reduced to 0.01 mass % or lower, enough effect can be obtained, so that the alkali metal content and alkaline-earth metal content are preferably 0.01 mass % or higher from a cost performance viewpoint.
  • a large quantity of rinsing water is used when producing a catalyst support of silica, however, when rinsing water containing impurities such as industrial water is used, a large amount of impurities remains in the catalyst support, causing the catalytic activity to fall largely, being unfavorable.
  • rinsing water of low impurity content or no impurity a favorable catalyst support of silica of a lesser impurity content can be obtained.
  • the alkali metal content or the alkaline-earth metal content in the rinsing water is favorably 0.06 mass % or lower, and the content above 0.06 mass % leads to the increase in the impurity content in the catalyst support of silica, which causes a substantial reduction in the catalytic activity after the preparation, being unfavorable.
  • the use of ion-exchanged water is favorable, in which the ion-exchanged water may be obtained by a production using an ion-exchange resin or the like, however, it may be obtained by a production through an ion exchange using a silica gel, for example, when employing a silica as the catalyst support, since the silica gel is generated in the silica production line as a substandard article.
  • the silica can capture the impurities in the rinsing water due to an ion exchange between hydrogen in a silanol on the surface of the silica and an impurity ion.
  • an exchanged ion amount may be in proportion to the amount of the rinsing water used, so that the reduction of the impurities in the silica can be realized by reducing the amount of the rinsing water, in other words, by increasing a usage efficiency of the water to the end of the water rinsing.
  • Such a pretreatment is effective for the improvement of the activity of the catalyst.
  • Such pretreatment may appropriately use a water rinsing technique, an acid rinsing technique, an alkalis rinsing technique and the like, and, for example, when rinsing the catalyst support of silica, rinsing with an acid solution such as a nitric acid solution, a hydrochloric acid solution, an acetic acid solution or the like, and rinsing with an ion-exchanged water are effective. After the rinsing with these acids, when a partial acid remaining in the catalyst support comes to be an obstacle, further rinsing with clean water such as ion-exchanged water is effective.
  • a pore diameter in the range from 8 nm to 50 nm a specific surface area in the range from 80 m 2 /g to 550 m 2 /g, and a pore volume in the range from 0.5 mL/g to 2.0 mL/g, as physical properties thereof, is preferable. It is also preferable to have together the pore diameter in the range from 8 nm to 30 nm, the specific surface area in the range from 150 m 2 /g to 450 m 2 /g, and the pore volume in the range from 0.6 mL/g to 1.5 mL/g.
  • pore diameter in the range from 8 nm to 20 nm
  • specific surface area in the range from 200 m 2 /g to 400 m 2 /g
  • pore volume in the range from 0.8 mL/g to 1.2 mL/g.
  • the specific surface area should be 80 m 2 /g or more under this specific surface area, the dispersion of the loaded metallic compound decreases to lower the contribution efficiency to the reaction of the metallic compound, which can be unfavorable. Above the specific surface area of 550 m 2 /g, it may be difficult to have the pore volume and the pore diameter satisfy the previously-described ranges together, which can be also unfavorable.
  • the pore volume is in the range from 0.5 mL/g to 2.0 mL/g. Under 0.5 mL/g, it can become difficult to satisfy the pore diameter and the specific surface area in the above-described ranges together; and above 2.0 mL/g, the strength deteriorates substantially, which is unfavorable.
  • the catalyst for the Fischer-Tropsch synthesis which is for the slurry bed, requires the abrasion resistance and strength. Further, in the Fischer-Tropsch synthesis reaction, a large amount of water is generated as a by-product, so that the use of a catalyst which is fractured into powders under the existence of water causes an inconvenience as described herein above, thus requiring caution. Accordingly, it is preferable to use a catalyst support having a spherical shape rather than a catalyst support of a shattered structure potentially having cracks at high probability in which a sharp angle thereof tends to suffer a damage and removal.
  • a granulation or spraying method is applicable, and particularly, when producing a spherical catalyst support of silica having a particle diameter of approximately 20 ⁇ m to 250 ⁇ m, the spraying method is appropriate, by which the spherical catalyst support of silica exhibiting excellent abrasion resistance and water resistance can be obtained.
  • a method for producing such a catalyst support of silica in accordance with another exemplary embodiment of the present invention is described below.
  • a silica sol is generated by mixing an alkali metal silicate solution and an acid solution under the condition from pH 2 to pH 10.5; the silica sol is sprayed into a gas medium or an organic solvent which the sol is insoluble, so that the sol becomes to a gel; and the silica gel goes through an acid treatment, a water rinsing treatment, and a dry treatment.
  • an alkali metal silicate solution a sodium silicate solution is desirable, in which, preferably, the mole ratio of Na 2 0:SiO 2 is 1:1 to 1:5, and the concentration of silica is 5 mass % to 30 mass %.
  • a nitric acid, a hydrochloric acid, a sulfuric acid, an organic acid, or the like is applicable, whereas, the sulfuric acid is preferable because the sulfuric acid is not corrosive to a container used in the production process and leaves no organic matter behind.
  • the concentration of the acid is, preferably, in the range from 1 mol/L to 10 mol/L. Under the range, the progress of the gelation slows significantly, and above the range, the gelation progresses too fast to be difficult to be controlled so that a desired physical property value is difficult to be obtained, being unfavorable. Further, when adopting the method of spraying into the organic solvent, as an organic solvent, kerosene, paraffin, xylene, toluene or the like can be employed.
  • the spherical catalyst support obtainable by the above-described producing method barely deteriorates by the crash between the catalysts, by the fracture due to water, and by the pulverization.
  • There are various quantification methods for the fracture and pulverization out of which the present inventors employed an abrasion resistance test to perform an evaluation, in which an ultrasonic wave is emitted at a temperature in the range from a room temperature to 400° C. while dispersing the catalyst into water.
  • an ultrasonic generator that of 47 kHz in frequency and 125 W in output power (manufacture: Branson Ultrasonics Corp., product name: BRANSONIC Model 2210J) is used, and 1 g of catalyst not containing particles below 20 ⁇ m is dispersed into 3 mL of pure water, the ultrasonic is emitted at a room temperature for, e.g., four hours, and mass % of the particles below 20 ⁇ m in the entire sample is defined as a fractured or pulverized ratio.
  • a catalyst for a Fischer-Tropsch synthesis which exhibits higher activity without deteriorating strength and abrasion resistance of the catalyst, can be obtained.
  • the catalyst for the Fischer-Tropsch synthesis according to the present invention, producing a product is enabled by the Fischer-Tropsch synthesis reaction with higher efficiency and lower costs.
  • the Fischer-Tropsch synthesis reaction can be carried out using the catalyst obtainable by the exemplary embodiments of the present invention, a selectivity of a liquid product having a carbon number of five or above as a main product is high, and the production rate of the liquid product per a catalyst unit mass (production rate of hydrocarbon) is extremely high.
  • the catalyst is barely pulverized and catalyst activity decrease is very small when it is in use, so that the catalyst has a longer catalytic life, as a feature. With these features, the Fischer-Tropsch synthesis reaction can be carried out with higher efficiency at lower costs.
  • Co/SiO 2 catalyst catalyst support of silica is manufactured by Fuji Silysia Chemical Ltd. and of a spherical shape having an average particle diameter of 100 ⁇ m, and Co loading amount is from 16 mass % to 30 mass %) and 50 mL of n-C 16 (n-hexadecane) were charged there into, and after that a Fischer-Tropsch synthesis reaction was carried out under conditions of 230° C.
  • a CO conversion, a CH 4 selectivity and a CO 2 selectivity can be calculated by the formulas shown below.
  • CO ⁇ conversion ⁇ ( % ) ( Supplied ⁇ CO amount ⁇ ( mol ) ) - ( CO ⁇ amount ⁇ in ⁇ gas at ⁇ reactor ⁇ outlet ⁇ ( mol ) ) Supplied ⁇ CO ⁇ amount ⁇ ( mol ) ⁇ 100
  • CH 4 ⁇ selectivity ⁇ ( % ) generated ⁇ CH 4 ⁇ amount ⁇ ( mol ) reacted ⁇ CO ⁇ amount ⁇ ( mol ) ⁇ 100
  • CO 2 ⁇ selectivity ⁇ ( % ) generated ⁇ CO 2 ⁇ amount ⁇ ( mol ) reacted ⁇ CO ⁇ amount ⁇ ( mol ) ⁇ 100
  • a catalyst support of silica having characteristics as shown in column G in Table 1 provided below was rinsed with a hydrochloric acid solution and an ion-exchanged water to obtain a catalyst support of silica as shown in column C in Table 1.
  • a 20 mass % of Co was loaded on the catalyst support of silica and a Fischer-Tropsch synthesis reaction was carried out and, as a result, the CO conversion was 74.1%, CH 4 selectivity was 4.8% and CO 2 selectivity was 1.0%.
  • an abrasion resistance test emitting a supersonic wave at the room temperature described before was carried out, and the fractured or pulverized rate was measured as a result, the mass ratio of particles of 20 ⁇ m or below was 0.00%.
  • the catalyst which had been subjected to the reaction for 1000 hours was collected, and a measurement was made for a particle size distribution. As a result, the mass ratio of particles of 20 ⁇ m or below was 0.00%.
  • Example 3 The same reaction as in the Example 3 was carried out only by letting a 30 mass % of Co to be loaded on the support and letting W/F to be 1.5 (g ⁇ h/mol). As a result, the CO conversion was 74.7%, CH 4 selectivity was 3.7% and CO 2 selectivity was 0.6%, and the production rate of the hydrocarbon having a carbon number of 5 or above was 2.1 (kg ⁇ hydrocarbon/kg ⁇ catalyst ⁇ hour).
  • a 30 mass % of Co was loaded on a catalyst support of silica having physical properties as shown in column E in Table 1 provided below and a Fischer-Tropsch synthesis reaction was carried out by setting the W/F to be 1.5.
  • the CO conversion was 71.7%
  • CH 4 selectivity was 4.4%
  • CO 2 selectivity was 0.7%
  • the production rate of the hydrocarbon having a carbon number of 5 or above was 1.9 (kg ⁇ hydrocarbon/kg ⁇ catalyst ⁇ hour).
  • a catalyst for a Fischer-Tropsch synthesis which exhibits an extremely high activity, can be produced without deteriorating strength and abrasion resistance of the catalyst, and a Fischer-Tropsch synthesis reaction exhibiting a higher hydrocarbon production rate can be carried out with the catalyst.

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US20100240777A1 (en) * 2006-08-25 2010-09-23 Kenichiro Fujimoto Catalyst for producing hydrocarbon from syngas, method for producing catalyst, method for regenerating catalyst, and method for producing hydrocarbon from sysngas
US20140039073A1 (en) * 2007-05-08 2014-02-06 Synfuels China Technology Co., Ltd. Transition metal nanocatalyst, method for preparing the same, and process for fischer-tropsch synthesis using the same
US8952076B2 (en) 2004-01-28 2015-02-10 Statoil Asa Fischer-Tropsch catalysts
US8969231B2 (en) 2009-09-01 2015-03-03 Gtl.Fi Ag Fischer-Tropsch catalysts
US20150209764A1 (en) * 2012-09-03 2015-07-30 Nippon Steel & Sumikin Engineering Co., Ltd, Catalyst for producing hydrocarbon from syngas, method for producing catalyst, method for regenerating catalyst, and method for producing hydrocarbon from syngas
US9242229B2 (en) 2010-08-09 2016-01-26 Gtl.F1 Ag Fischer-tropsch catalysts
US10040054B2 (en) 2009-11-18 2018-08-07 Gtl.Fi Ag Fischer-Tropsch synthesis

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JP4808688B2 (ja) * 2006-08-25 2011-11-02 新日本製鐵株式会社 合成ガスから炭化水素を製造する触媒、触媒の製造方法、触媒の再生方法、及び合成ガスから炭化水素を製造する方法
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JP7018754B2 (ja) * 2017-12-08 2022-02-14 日鉄エンジニアリング株式会社 合成ガスから炭化水素を製造する触媒、その触媒の製造方法、及び合成ガスから炭化水素を製造する方法、並びに触媒担体

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US8952076B2 (en) 2004-01-28 2015-02-10 Statoil Asa Fischer-Tropsch catalysts
US20080255256A1 (en) * 2004-09-23 2008-10-16 Erling Rytter Promoted Fischer-Tropsch Catalysts
US8143186B2 (en) * 2004-09-23 2012-03-27 Statoil Asa Promoted Fischer-Tropsch catalysts
US20100240777A1 (en) * 2006-08-25 2010-09-23 Kenichiro Fujimoto Catalyst for producing hydrocarbon from syngas, method for producing catalyst, method for regenerating catalyst, and method for producing hydrocarbon from sysngas
US9295976B2 (en) * 2006-08-25 2016-03-29 Nippon Steel Engineering Co., Ltd Catalyst for producing hydrocarbon from syngas, method for producing catalyst, method for regenerating catalyst, and method for producing hydrocarbon from sysngas
US20140039073A1 (en) * 2007-05-08 2014-02-06 Synfuels China Technology Co., Ltd. Transition metal nanocatalyst, method for preparing the same, and process for fischer-tropsch synthesis using the same
US8969231B2 (en) 2009-09-01 2015-03-03 Gtl.Fi Ag Fischer-Tropsch catalysts
US10040054B2 (en) 2009-11-18 2018-08-07 Gtl.Fi Ag Fischer-Tropsch synthesis
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US20150209764A1 (en) * 2012-09-03 2015-07-30 Nippon Steel & Sumikin Engineering Co., Ltd, Catalyst for producing hydrocarbon from syngas, method for producing catalyst, method for regenerating catalyst, and method for producing hydrocarbon from syngas
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EP1632289A1 (en) 2006-03-08
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US8178589B2 (en) 2012-05-15
AU2004228845A1 (en) 2004-10-21
EP1632289A4 (en) 2012-03-07
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CN1771086A (zh) 2006-05-10
RU2005134237A (ru) 2007-05-20
US20120289615A1 (en) 2012-11-15
RU2311230C2 (ru) 2007-11-27
US20100184876A1 (en) 2010-07-22
JP4429063B2 (ja) 2010-03-10
CN100479917C (zh) 2009-04-22

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