Classifications

• • 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
  • 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
  • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
  • B01J35/391—Physical properties of the active metal ingredient
  • B01J35/393—Metal or metal oxide crystallite 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
  • B01J35/40—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
  • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
  • B01J35/51—Spheres
• • 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
  • B01J35/64—Pore diameter
  • B01J35/647—2-50 nm
• • 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
  • B01J37/0201—Impregnation
• • 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
  • B01J37/08—Heat treatment
  • B01J37/10—Heat treatment in the presence of water, e.g. steam
• • 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
• • 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
  • B01J37/18—Reducing with gases containing free hydrogen
• • 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
  • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
  • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
  • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
  • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
  • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
  • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
  • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/70—Catalyst aspects

Definitions

• the present invention relates to a catalyst used for the Fischer-Tropsch synthesis reaction, a method for producing the catalyst, and a method for producing hydrocarbons by the Fischer-Tropsch synthesis reaction using the catalyst.
• Examples of the method for producing such clean fuels include a method in which hydrocarbons are synthesized by utilizing the so-called Fischer-Tropsch synthesis reaction (hereinafter, sometimes called as “FT synthesis reaction”) reducing a carbon monoxide with a molecular hydrogen (hereinafter, sometimes called as “FT synthesis method”), using a synthesis gas obtained by reforming a hydrocarbon such as a natural gas, that is, a mixed gas of carbon monoxide and molecular hydrogen (hydrogen gas), as a feedstock.
• FT synthesis reaction the so-called Fischer-Tropsch synthesis reaction
• FT synthesis method reducing a carbon monoxide with a molecular hydrogen
• FT synthesis catalyst As the catalyst used for the FT synthesis method (hereinafter, sometimes called as “FT synthesis catalyst”), a catalyst in which an active metal such as iron, cobalt, and ruthenium is supported on a porous inorganic carrier such as silica or alumina is generally used (for example, see Patent Literature 1).
• an active metal such as iron, cobalt, and ruthenium is supported on a porous inorganic carrier such as silica or alumina
• Patent Literature 1 As the catalyst used for the FT synthesis catalyst, a catalyst in which an active metal such as iron, cobalt, and ruthenium is supported on a porous inorganic carrier such as silica or alumina is generally used (for example, see Patent Literature 1).
• the FT synthesis catalyst it is reported that by using the above active metal in combination with a second component metal compound, the catalyst performance is enhanced (for example, see Patent Literature 2 and Patent Literature 3).
• the second component metal include sodium, magnesium,
• Patent Literature 1 Japanese Patent Application Laid-Open Publication No. Hei-4-227847
• Patent Literature 2 Japanese Patent Application Laid-Open Publication No. Sho-59-102440
• Patent Literature 3 Japanese Patent Application Laid-Open Publication No. 2008-238096
• an active metal is distributed selectively in the proximity of the outer surface of a catalyst particle having a size of 10 ⁇ m to 10 mm and the distribution of the active metal is not controlled between the pore inside/pore outside (outer surface) of a porous inorganic carrier with a pore having a size of several tens nm.
• an FT synthesis catalyst having further excellent performance is considered to be obtained.
• the active metal is distributed in a large amount in an inside of pore of a porous inorganic carrier and is not effectively utilized for the reaction.
• the inventors of the present invention have made a study for solving the problem of developing an FT synthesis catalyst in which the distribution of the active metal in the inside/outside of the pore of the porous inorganic carrier is controlled.
• the inventors of the present invention found a simple method for controlling the distribution of the active metal in a micro-scale and a novel FT synthesis catalyst having the distribution of the active metal which could not be obtained conventionally based on the above method, and completed the present invention.
• the present invention provides a Fischer-Tropsch synthesis catalyst containing 10 to 30% by mass, as a metal atom, of metallic cobalt and/or cobalt oxide, based on the mass of the catalyst, supported on a carrier containing silica, in which the carrier has an average pore diameter of 8 to 25 nm, and the metallic cobalt and/or cobalt oxide has an average crystallite diameter of not less than the average pore diameter of the carrier and less than 35 nm.
• the cobalt atom/silicon atom molar ratio measured by an X-ray photoelectron spectroscopy is preferably 0.05 to 2.00.
• the FT synthesis catalyst of the present invention preferably further contains 0.5 to 10% by mass of zirconium as zirconium oxide, based on the mass of the catalyst.
• the present invention provides a method for producing above-described Fischer-Tropsch synthesis catalyst comprising; a step of loading an active metal for loading a cobalt compound on a carrier containing silica having an average pore diameter of 8 to 25 nm so that the loading amount of the cobalt compound as a cobalt atom becomes 10 to 30% by mass, based on the mass of the catalyst; a step of calcining for calcining the carrier supporting the cobalt compound to obtain a catalyst precursor in which the cobalt compound is converted into cobalt oxide; a step of first reduction for reducing the catalyst precursor in an atmosphere containing at least molecular hydrogen to obtain a reduced catalyst precursor; and a step of steaming for treating the reduced catalyst precursor obtained through the step of first reduction with a mixed gas containing 1 to 30% by volume of steam and an inert gas at a temperature of 100 to 300° C. to obtain a Fischer-Tropsch synthesis catalyst.
• the method for producing the Fischer-Tropsch synthesis catalyst of the present invention preferably comprises a step of loading zirconium for loading 0.5 to 10% by mass of zirconium as zirconium oxide, based on the mass of the catalyst, on particles containing silica having an average pore diameter of 8 to 25 nm and a step of calcining a carrier for calcining the zirconium-loaded particles containing silica to obtain a carrier containing silica before the step of loading an active metal.
• the method for producing the FT synthesis catalyst of the present invention contains preferably a step of second reduction for further reducing the Fischer-Tropsch synthesis catalyst obtained through the step of steaming in an atmosphere containing molecular hydrogen or carbon monoxide.
• the present invention provides a method for producing a hydrocarbon by subjecting a feedstock containing carbon monoxide and molecular hydrogen to the Fischer-Tropsch synthesis reaction in the presence of the above-described FT synthesis catalyst to synthesize hydrocarbons.
• an FT synthesis catalyst having high activity in which the distribution of the active metal between inside and outside of the pore of the carrier is controlled, a method for producing the catalyst, and an efficient method for producing a hydrocarbon using the catalyst.
• the carrier constituting the FT synthesis catalyst of the present embodiments contains silica.
• the carrier containing silica include, beside silica, silica containing a small amount of an inorganic oxide such as alumina, boria, titania, and magnesia, and silica further containing a metal component such as sodium, magnesium, lithium, zirconium, and hafnium, in addition to silica or the above-described silica containing a small amount of another inorganic oxide.
• a carrier containing silica has an average pore diameter measured by utilizing a BJH method from an adsorption-desorption isotherm of nitrogen of 8 to 25 nm, preferably 10 to 20 nm.
• the average pore diameter of the carrier controls the size of a crystallite of the active metal supported on the carrier and existing in the pore, and it is therefore an important factor determining the performance of the catalyst.
• the average pore diameter is less than 8 nm, the active metal may migrate excessively to the surface of the catalyst in the step of steaming and the aggregation is excessively progressed, which is not preferred.
• the average pore diameter is more than 25 nm, a crystallite of the active metal grows in the pore during the step of steaming and becomes too large, so that the catalyst becomes of low activity.
• the specific surface area of the carrier containing silica is not particularly limited, the specific surface area measured by a nitrogen adsorption method is preferably 50 to 800 m 2 /g, more preferably 100 to 500 m 2 /g.
• the shape of the carrier containing silica is not particularly limited, in consideration of practicality, a spherical shape, a cylindrical shape, and a cylindrical shape having a modified cross-section such as a three-leaf shape and a four-leaf shape which are generally used in fields of petroleum refining and petrochemical industry, are preferred.
• the particle diameter thereof is also not particularly limited, in terms of practicality, it is preferably 10 ⁇ m to 10 mm.
• the shape of the catalyst is preferably a spherical shape, and the average particle diameter thereof is preferably 10 to 300 ⁇ m, more preferably 30 to 150 ⁇ m.
• the carrier constituting the FT synthesis catalyst of the present embodiments is preferably silica containing at least zirconium.
• the carrier contains zirconium, the activity of the catalyst is enhanced and in the FT synthesis, an activity decrease of the catalyst with time can be suppressed.
• Zirconium is supported on particles containing silica preferably in a state of zirconium oxide. In addition, this zirconium oxide is preferably supported selectively in the proximity of the outer surface of particles containing silica.
• particles containing silica refers to, besides silica particles, silica particles containing a small amount of an inorganic oxide such as alumina, boria, titania, and magnesia, and silica particles further containing a metal component such as sodium, magnesium, lithium, zirconium, and hafnium, in addition to silica or the above-described silica containing a small amount of another inorganic oxide.
• characteristics of said particles containing silica that is an average pore diameter, a specific surface area, a shape, and an average particle diameter are the same as that of the above-described carrier containing silica, and therefore, explanation is omitted in terms of avoiding redundancy.
• zirconium can be loaded selectively in the proximity of the outer surface of particles containing silica.
• particles containing silica are subjected to a pretreatment with an aqueous solution having a pH value of 7 or lower.
• examples of the aqueous solution (pretreating solution) having a pH value of 7 or lower include a nitric acid aqueous solution, an acetic acid aqueous solution, a sulfuric acid aqueous solution, a hydrochloric acid aqueous solution, ion-exchanged water, and distilled water.
• the pretreating solution has a pH value of, preferably 5 to 7, more preferably 6 to 7.
• the pH value is lower than 5, in order to load a zirconium compound in a necessary amount in the loading of a zirconium compound performed after the pretreatment, the concentration of the used zirconium compound solution is necessary to be increased, which is economically not preferred.
• the pretreatment can be performed, for example, by adding a pretreating solution into a container containing particles containing silica.
• the time for immersing particles containing silica in the pretreating solution is preferably around 10 to 72 hours in the case of leaving the pretreating solution at rest, around 1 to 12 hour(s) in the case of applying vibration to the pretreating solution, and around 1 to 30 minute(s) in the case of irradiating the pretreating solution with a supersonic wave.
• Irradiating the pretreating solution in which the particles containing silica is immerged with a supersonic wave is preferably performed in order to remove bubbles existing in the pore in the particles containing silica.
• the excessive amount means a volume amount which is two times or more the apparent volume constituted by the particles containing silica.
• zirconium compound examples include zirconyl sulfate, zirconyl acetate, zirconyl ammonium carbonate, and zirconium trichloride, and among them, zirconyl ammonium carbonate and zirconyl acetate are preferred.
• the amount of zirconium to be loaded is preferably 0.5 to 10% by mass, more preferably 2 to 6% by mass as zirconium oxide, based on the mass of the catalyst (FT synthesis catalyst).
• the loading amount is less than 0.5% by mass, the effect of enhancing the activity of the catalyst and the like by adding zirconium tends to become unsatisfactory, whereas when the loading amount is more than 10% by mass, the above effect is not further enhanced, which tends to become economically disadvantageous.
• the time for immerse the particles containing silica in a solution containing a zirconium compound to load zirconium on the particles containing silica depends on the objective loading amount and is not particularly limited, it is ordinarily 3 to 72 hours.
• the remaining solution containing the zirconium compound and the solid are separated by solid-liquid separation means such as filtration, the solid thus separated is washed with water, and the solid is dried.
• the drying method is not particularly limited and examples thereof include heating-drying in air and evacuating-drying under reduced pressure. Ordinarily, the drying is performed at a temperature of 100 to 200° C., preferably 110 to 130° C. for 2 t o 24 hours, preferably 5 to 12 hours.
• the particles containing silica on which a zirconium compound is loaded may be calcined (step of calcining the carrier).
• the calcining condition is not particularly limited, the calcining may ordinarily be performed at 340 to 600° C., preferably 400 to 450° C. in an air atmosphere for 1 to 5 hour(s).
• the calcining in this stage may not be performed and instead of the calcining in this stage, the calcining may be performed after loading the active metal.
• the carrier on which a zirconium compound is supported can be obtained.
• cobalt as the active metal is loaded supported (step of loading the active metal).
• the active metal in an FT synthesis catalyst ordinarily include cobalt, ruthenium, and iron, as the active metal in the FT synthesis catalyst of the present embodiments, cobalt or a combination of cobalt with ruthenium is preferred.
• the cobalt compound used for performing the loading of cobalt is not particularly limited and a salt of a mineral acid or an organic acid or complex can be used. Specific examples thereof include cobalt nitrate, cobalt chloride, cobalt formate, cobalt propionate, cobalt acetate, and cobalt acetylacetonate.
• the ruthenium compound used when ruthenium is supported together with cobalt include ruthenium chloride, ruthenium nitrate, and tetraoxoruthenate.
• the loading amount of cobalt is 10 to 30% by mass, preferably 15 to 25% by mass as a metal atom, based on the mass of the catalyst (FT synthesis catalyst).
• the loading amount is less than 10% by mass, the activity of the catalyst tends to become unsatisfactory, whereas when the loading amount is more than 30% by mass, an activity lowering of the catalyst due to an aggregation of cobalt is easily caused and simultaneously, the specific gravity of the catalyst becomes large, so that when such a catalyst is used in a slurry bed type reaction apparatus, it tends to become difficult to secure the fluidity of the catalyst.
• the loading method of a cobalt compound is not particularly limited and as the loading method, a publicly-known method is utilized and an impregnation method typified by the Incipient Wetness method can be preferably used.
• a carrier supporting a cobalt compound is dried, for example, at a temperature of 100 to 200° C., preferably 110 to 130° C. for 2 to 24 hours, preferably 5 to 10 hours and then, is calcined at 340 to 600° C., preferably 400 to 500° C. in an air atmosphere for 1 to 5 hour(s) to convert the cobalt compound into an oxide to obtain a catalyst precursor (step of calcining).
• the catalyst precursor is reduced to convert the cobalt oxide into metallic cobalt (step of first reduction).
• Reduction is performed in an atmosphere containing molecular hydrogen.
• the gas used for reduction is not particularly limited so long as the gas contains molecular hydrogen (hydrogen gas), the gas is a gas containing molecular hydrogen in a content of preferably 70% by volume or more, more preferably 95% by volume or more. When the content of molecular hydrogen is less than 70% by volume, the reducing efficiency tends to become unsatisfactory, which is not preferred.
• the gas used for reduction examples include a hydrogen gas and a mixed gas of a hydrogen gas with an inert gas such as a nitrogen gas, and among them, a hydrogen gas is particularly preferred.
• a hydrogen gas is particularly preferred.
• the gas used for reduction further contains carbon monoxide, during reduction, the FT synthesis reaction is effected and it is concerned that the problem of a heat generation or the like is caused, which is not preferred; however, the contamination of carbon monoxide in a trace amount can be allowed.
• the temperature for reduction is preferably 250 to 500° C., more preferably 350 to 450° C.
• the reduction degree of a cobalt atom ratio of the number of moles of a cobalt atom in a metal state relative to the number of moles of a cobalt atom in all states in the catalyst after the step of reduction
• the temperature for reduction is higher than 500° C.
• aggregation of metallic cobalt is excessively progressed so that the activity of the catalyst tends to be lowered.
• the pressure for the step of first reduction is not particularly limited, normal pressure to around 5 MPa is selected.
• the time for reduction largely depends on the temperature, the atmosphere, the apparatus to be used, and the like so that it is difficult to determine the time for reduction in a simple manner; however, it is generally around 0.5 to 60 hours.
• the step of first reduction may be performed in a catalyst producing equipment, or an equipment for performing the production of hydrocarbons by the FT synthesis method or equipments annexed thereto.
• the catalyst obtained through the step of first reduction is subjected to a treatment with a mixed gas containing steam and an inert gas while being heated (step of steaming).
• step of steaming is the most important step in the method for producing the FT synthesis catalyst of the present invention.
• the content of steam in the mixed gas used in the step of steaming is 1 to 30% by volume, preferably 5 to 20% by volume.
• the content of steam is less than 1% by volume, the migration of metallic cobalt to the outer surface of the carrier which is described below is considered not to satisfactorily progress and the enhancement of the catalyst activity tends to become unsatisfactory.
• the content of steam is more than 30% by volume, the migration from inside of the pore of the carrier to the outer surface of the carrier and aggregation of metallic cobalt and/or cobalt oxide are considered to be excessively progressed, so that the catalyst activity tends to be lowered.
• the temperature for the step of steaming is 100 to 300° C., preferably 150 to 250° C.
• the temperature is lower than 100° C.
• the migration of metallic cobalt and/or cobalt oxide from inside of the pore of the carrier to the outer surface is considered to be hardly progressed and the catalyst activity tends to be hardly enhanced.
• the temperature is higher than 300° C.
• the migration from inside of the pore of the carrier to the outer surface of the carrier and aggregation of metallic cobalt and/or cobalt oxide are considered to be excessively progressed, so that the catalyst activity tends to be lowered.
• pressure for the step of steaming is not particularly limited, normal pressure to around 5 MPa is selected.
• the time for the step of steaming is largely influenced by the temperature and the like and is not defined in a simple manner, around 0.1 to 10 hours is selected.
• the step of steaming may be performed in a catalyst producing equipment, or an equipment for performing the production of hydrocarbons by the FT synthesis method or equipments annexed thereto.
• a catalyst producing equipment or an equipment for performing the production of hydrocarbons by the FT synthesis method or equipments annexed thereto.
• the step of first reduction is performed in an equipment for performing the production of hydrocarbons the FT synthesis method or equipments annexed thereto, consequently, also the step of steaming is performed in the same equipment.
• the reduction degree of a cobalt atom contained in the thus obtained FT synthesis catalyst is rather lowered by a weak oxidation action of steaming in comparison with a cobalt atom in a catalyst that has been subjected to the step of first reduction and has not yet been subjected to the step of steaming, the catalyst as it is can also be subjected to the FT synthesis reaction. This is because by a reduction action of molecular hydrogen and carbon monoxide which are feedstocks for the FT synthesis reaction, the cobalt atom is reduced again during the reaction.
• the gas used as an atmosphere for the step of second reduction is preferably a gas containing molecular hydrogen or carbon monoxide.
• the gas containing molecular hydrogen may be the same gas as the gas used in the step of first reduction.
• the temperature and the pressure for reduction may be the same as those in the step of first reduction and although the time for reduction is not necessarily defined, it is around 0.5 to 30 hours.
• a gas containing carbon monoxide and no molecular hydrogen may also be used as the atmosphere for reduction.
• the gas containing carbon monoxide is not particularly limited, examples thereof include a carbon monoxide gas and a mixed gas of carbon monoxide with an inert gas such as nitrogen, and a carbon monoxide gas is preferred.
• the gas contains molecular hydrogen, it is concerned that water which may inhibit reduction of cobalt oxide is generated and that the FT synthesis reaction by carbon monoxide and molecular hydrogen is effected to cause the problem of heat generation and the like. Therefore, the gas contains preferably no molecular hydrogen, with proviso that the contamination of the gas with molecular hydrogen in a trace amount is allowed.
• the temperature for reduction is 200 to 400° C., preferably 250 to 350° C.
• a satisfactory reduction degree of the cobalt atom tends to be hardly obtained.
• a carbon typified by a carbon nanotube tends to be easily generated from carbon monoxide.
• the pressure for reduction is normal pressure to around 5 MPa and the time for reduction is generally around 0.5 to 30 hours, though it depends largely on the temperature for reduction or the like and it is difficult to define the time in a simple manner.
• the step of second reduction may be performed in a catalyst producing equipment, or an equipment for performing the production of hydrocarbons by the FT synthesis method or equipments annexed thereto.
• the step of first reduction or the step of steaming is performed in an equipment for performing the production of hydrocarbons by the FT synthesis method or equipments annexed thereto, consequently, also the step of second reduction is performed in the same equipment.
• the FT synthesis catalyst activated by reduction When the FT synthesis catalyst activated by reduction is contacted with air, it is concerned that the activity of the FT synthesis catalyst is lowered by oxidation of the active metal.
• the transport of the catalyst and the like is ordinarily performed after subjecting the catalyst to a stabilization treatment.
• a method of coating the surface of the activated FT synthesis catalyst with a wax or the like to seal the catalyst from the air and a method of slightly oxidizing the surface of the activated FT synthesis catalyst to form an oxide layer to prevent the further progression of oxidation by the contact with air, and the like are generally used.
• the catalyst producing equipment or the hydrocarbon producing equipment to perform the step of first reduction, the step of steaming, and the step of second reduction
• various combinations can be considered.
• the catalyst is preferably subjected to a stabilization treatment to be transported.
• the stabilization treatment by a method of coating the surface of the catalyst with a wax or the like
• the step of steaming and/or the step of second reduction are(is) performed in the hydrocarbon producing equipment or equipments attached thereto after the transportation of the catalyst, it is concerned that a disadvantage is caused.
• the stabilization treatment is preferably performed by a method of slightly oxidizing the surface of the activated catalyst.
• the FT synthesis catalyst of the present invention encompasses all the FT synthesis catalysts which have been subjected to the stabilization treatment after any one of the step of first reduction, the step of steaming, and the step of second reduction.
• the average crystallite diameter of metallic cobalt and/or cobalt oxide must be the average pore diameter of the carrier and more, and less than 35 nm.
• the average crystallite diameter of the active metal (containing a metal and oxide thereof) existing in the pore of the carrier is a value smaller than the average pore diameter due to the geometric constraint by the pore.
• the fact that the average crystallite diameter of metallic cobalt and/or cobalt oxide in the FT synthesis catalyst of the present embodiments is not less than the average pore diameter of the carrier indicates that at least a portion of metallic cobalt and/or cobalt oxide has migrated from the inside of the pore to the outside of the pore, that is, the outer surface of the catalyst by the step of steaming and has been aggregated to some extent at the outer surface.
• the inventors of the present invention assume that by this migration of the active metal, although the aggregation is caused to some extent, as the ratio of active sites existing on the outer surface of the catalyst relative to active sites existing in the pore is elevated, the FT synthesis reaction activity of the catalyst is enhanced.
• the FT synthesis catalyst of the present embodiments has a cobalt atom/silicon atom molar ratio calculated from an elemental component analysis by an X-ray photoelectron spectroscopy (XPS) of preferably 0.05 to 2.00.
• XPS is an analysis technique aiming as the analysis object only at a range in which the depth in the sample surface is extremely small (generally 3 to 5 nm). Therefore, the cobalt atom/silicon atom molar ratio obtained by the analysis method becomes an indicator of the concentration of cobalt atoms existing in the proximity of (in micro scale) the outer surface of the catalyst.
• the concentration of cobalt atoms existing in the proximity of the outer surface of the catalyst fails, so that the catalyst tends to have low activity.
• the concentration of cobalt atoms in the proximity of the outer surface of the catalyst is high and metallic cobalt and/or cobalt oxide are(is) excessively aggregated, so that the catalyst tends to have low activity.
• the method for producing hydrocarbons by the FT synthesis reaction using the FT synthesis catalyst of the present embodiments and using carbon monoxide and molecular hydrogen as feedstocks is not particularly limited except for using the FT synthesis catalyst of the present embodiments and can adopt a publicly-known method.
• the reaction apparatus therefor is preferably a fixed-bed reaction apparatus or a slurry-bed reaction apparatus.
• the reaction is effected under the condition that the conversion of carbon monoxide as a feedstock is preferably 50% or more, more preferably 55 to 90%.
• Examples of the usable reaction apparatus include a bubble column type fluidized-bed reaction apparatus.
• a bubble column type fluidized-bed reaction apparatus a slurry in which the FT synthesis catalyst of the present embodiments is suspended in hydrocarbons (ordinarily, FT synthetic hydrocarbons produced in the same reaction apparatus) which are in a liquid form at the reaction temperature, is housed, and into the shiny, a mixed gas (generally, a synthetic gas obtained by reforming of a hydrocarbon such as a natural gas) of a carbon monoxide gas and molecular hydrogen is introduced from the bottom of a reaction column, While the mixed gas ascends in the reaction column in a form of a bubble, the mixed gas is dissolved in the hydrocarbons and when the mixed gas is contacted with the catalyst, hydrocarbons are generated.
• a mixed gas generally, a synthetic gas obtained by reforming of a hydrocarbon such as a natural gas
• a cooling tube in which a coolant for removing a reaction heat is passed through is provided and a reaction heat is removed by heat exchange.
• the FT synthesis catalyst of the present embodiments to be used is supplied in a state in which the catalyst has been subjected to the step of first reduction, the step of steaming, and if necessary, the step of second reduction in the method for producing the FT synthesis catalyst of the present embodiments, and then, to the stabilizing treatment in the catalyst producing equipment, the FT synthesis catalyst as it is may be used in the FT synthesis reaction. Also in the case of a catalyst subjected to a stabilizing treatment by coating with a wax or the like, a wax or the like is dissolved in the hydrocarbons so that the activity of the catalyst is developed.
• the catalyst when a catalyst in a state in which the catalyst has been subjected to the step of first reduction and the stabilization treatment is supplied in the catalyst producing equipment, the catalyst should be subjected to the step of steaming and if necessary, the step of second reduction in an FT synthesis reaction apparatus or apparatuses attached thereto to be used for the FT synthesis reaction.
• the reaction temperature for the FT synthesis reaction can be determined depending on the objective carbon monoxide conversion, and is preferably 150 to 300° C., more preferably 170 to 250° C.
• the reaction pressure is preferably 0.5 to 5.0 MPa, more preferably 2.0 to 4.0 MPa.
• the reaction pressure is less than 0.5 MPa, the carbon monoxide conversion tends to hardly become 50% or more, whereas when the reaction pressure is more than 5.0 MPa, a localized heat generation tends to be easily caused, which is not preferred.
• the ratio (molar ratio) of molecular hydrogen/carbon monoxide in a feedstock gas is preferably 0.5 to 4.0, more preferably 1.0 to 2.5.
• the reaction temperature is necessary to be raised in order to keep the conversion of carbon monoxide at a predetermined value and the catalyst activity tends to decrease rapidly during the reaction, and on the other hand, when the molar ratio is more than 4.0, the amount of generated methane which is an undesirable by-product tends to increase.
• the gas space velocity of the feedstock gas is preferably 500 to 5,000 h ⁇ 1 , more preferably 1,000 to 2,500 h ⁇ 1 .
• the productivity relative to the same catalyst amount is low and on the other hand, when the gas space velocity is more than 5,000 h ⁇ 1 , the conversion of carbon monoxide is hard to become 50% or more, which is not preferred.
• the FT synthesis catalyst of the present embodiments has high reaction activity (carbon monoxide conversion) and has high chain growth probability ( ⁇ ), so that by using this catalyst, hydrocarbons containing as main components, normal paraffins corresponding to a wax fraction, a middle distillate (kerosene and gas oil fraction), and a naphtha fraction can be obtained with a high yield. Particularly hydrocarbons rich in a wax fraction and a middle distillate can be obtained with a high yield.
• the mixture was filtered using a filtration paper and thereafter the resultant solid was washed using 1,000 mL of distilled water (step of loading zirconium). After washing, the obtained solid content was dried at 120° C. overnight and then calcined at 500° C. for 1 hour to obtain a carrier composed of silica containing a zirconium oxide (step of calcining carrier). Next, the carrier was impregnated with an aqueous solution containing cobalt nitrate in an amount which becomes 24% by mass as a cobalt atom, based on the mass of the catalyst after loading, by the Incipient Wetness method (step of loading active metal). After impregnation, the carrier was dried at 120° C.
• the obtained catalyst precursor was subjected to a composition analysis.
• This catalyst precursor was charged in a fixed-bed circulation type reaction apparatus and was subjected to reduction in a hydrogen gas stream at 400° C. for 7 hours (step of first reduction).
• the FT synthesis catalyst obtained through the steaming step was subjected to reduction in a hydrogen gas stream at 400° C.
• the objective FT synthesis catalyst was obtained.
• the obtained FT synthesis catalyst is composed of metallic cobalt, cobalt oxide, silica, and zirconium oxide, and from the result of the composition analysis of the catalyst precursor, the loading amount of cobalt as a metal atom, and the loading amount of zirconium oxide in the FT synthesis catalyst were calculated. The result is shown in Table 1.
• a portion of the FT synthesis catalyst obtained by the above catalyst preparation as a sample for the analysis was immersed in decane in an inert atmosphere.
• a portion of thus prepared sample was transferred into an X-ray diffraction analysis (XRD) apparatus in an inert atmosphere to subject the sample to the analysis.
• a portion of the catalyst sample immersed in decane was subjected to the analysis using an X-ray photoelectron spectroscopic analysis (XPS) apparatus in an inert atmosphere.
• XPS X-ray photoelectron spectroscopic analysis
• PHI Quantera SXM was used; as an X-ray source, AlK ⁇ (using a monochromator) was used; and as the analysis range, a diameter of 250 ⁇ m was used. From the XPS analysis result, the molar ratio of Co/Si was calculated. The result is shown in Table 1.
• the gas composition at an outlet of the autoclave was analyzed with time by gas chromatography and from the analysis data the CO conversion was calculated.
• the generated hydrocarbons were analyzed by gas chromatography and the chain growth probability was measured according to a conventional method. The result is shown in Table 1.
• Sphere-shaped silica particles having an average pore diameter of 12 nm and an average particle diameter of 70 ⁇ m were impregnated with an aqueous solution containing cobalt nitrate in an amount which becomes 26% by mass as a cobalt atom, based on the mass of the catalyst after loading, by the Incipient Wetness method (step of loading active metal).
• the carrier was dried at 120° C. overnight and then calcined at 450° C. for 2 hours to obtain a catalyst precursor (step of calcining).
• the obtained catalyst precursor was subjected to a composition analysis. This catalyst precursor was charged in a fixed-bed circulation type reaction apparatus and was subjected to reduction in a hydrogen gas stream at 400° C.
• the FT synthesis catalyst obtained through the steaming step was subjected to reduction in a hydrogen gas stream at 400° C. for 3 hours in the same reaction apparatus (step of second reduction).
• the objective FT synthesis catalyst was obtained.
• the obtained FT synthesis catalyst is composed of metallic cobalt, cobalt oxide, and silica, and the loading amount of cobalt was calculated in substantially the same manner as in Example 1. The result is shown in Table 1.
• the FT synthesis catalyst was subjected to the analysis in substantially the same manner as in Example 1. The result is shown in Table 1.
• the FT synthesis catalyst was subjected to the reaction evaluation in substantially the same manner as in Example 1. The result is shown in Table 1.
• the catalyst preparation, the analysis, and the reaction evaluation were performed in substantially the same manner as in Example 1, except that the reduction after steaming (step of second reduction) was not performed.
• the obtained FT synthesis catalyst is composed of metallic cobalt, cobalt oxide, silica, and zirconium oxide, and the loading amounts of cobalt and zirconium oxide were calculated in substantially the same manner as in Example 1. The result is shown in Table 1.
• the catalyst preparation, the analysis, and the reaction evaluation were performed in substantially the same manner as in Example 1, except that the conditions for reduction after steaming (step of second reduction) were changed to in a stream of carbon monoxide, at 300° C., and for 3 hours respectively.
• the obtained FT synthesis catalyst is composed of metallic cobalt, cobalt oxide, silica, and zirconium oxide, and the loading amounts of cobalt and zirconium oxide were calculated in substantially the same manner as in Example 1. The result is shown in Table 1.
• the mixture was filtered using a filtration paper and thereafter the resultant solid was washed using 1,000 mL of distilled water. After washing, the obtained solid was dried at 120° C. overnight and then calcined at 500° C. for 1 hour to obtain a carrier composed of silica containing a zirconium oxide.
• the carrier was impregnated with an aqueous solution containing cobalt nitrate in an amount which becomes 12% by mass as a Co atom, based on the mass of the catalyst after loading, by the Incipient Wetness method. After impregnation, the carrier was dried at 120° C. overnight and then calcined at 450° C. for 2 hours to obtain a catalyst precursor.
• the obtained catalyst precursor was subjected to a composition analysis.
• This catalyst precursor was charged in a fixed-bed circulation type reaction apparatus and was subjected to reduction in a hydrogen gas stream at 400° C. for 7 hours.
• the FT synthesis catalyst obtained by the steaming was subjected to reduction in a stream of hydrogen at 400° C. for 3 hours in the same reaction apparatus.
• the FT synthesis catalyst for comparison was obtained.
• the obtained FT synthesis catalyst for comparison is composed of metallic cobalt, cobalt oxide, silica, and zirconium oxide, and the loading amounts of cobalt and zirconium oxide were calculated in substantially the same manner as in Example 1. The result is shown in Table 2.
• the FT synthesis catalyst for comparison was subjected to the analysis in substantially the same manner as in Example 1. The result is shown in Table 2.
• the FT synthesis catalyst for comparison was subjected to the reaction evaluation in substantially the same manner as in Example 1. The result is shown in Table 2.
• the mixture was filtered using a filtration paper and thereafter the resultant solid was washed using 1,000 mL of distilled water. After washing, the obtained solid was dried at 120° C. overnight and next, calcined at 500° C. for 1 hour to obtain a carrier composed of silica containing zirconium oxide.
• the carrier was impregnated with an aqueous solution containing cobalt nitrate in an amount which becomes 25% by mass as a cobalt atom, based on the mass of the catalyst after loading, by the Incipient Wetness method. After impregnation, the carrier was dried at 120° C. overnight and then calcined at 450° C. for 2 hours to obtain a catalyst precursor.
• the obtained catalyst precursor was subjected to a composition analysis.
• This catalyst precursor was charged in a fixed-bed circulation type reaction apparatus and was subjected to reduction in a hydrogen stream at 400° C. for 7 hours.
• the FT synthesis catalyst obtained by the steaming was subjected to reduction in a stream of hydrogen at 400° C. for 3 hours in the same reaction apparatus.
• the FT synthesis catalyst for comparison was obtained.
• the obtained FT synthesis catalyst for comparison is composed of metallic cobalt, cobalt oxide, silica, and zirconium oxide, and the loading amounts of cobalt and zirconium oxide were calculated in substantially the same manner as in Example 1. The result is shown in Table 2.
• the FT synthesis catalyst for comparison was subjected to the analysis in substantially the same manner as in Example 1. The result is shown in Table 2.
• the FT synthesis catalyst for comparison was subjected to the reaction evaluation in substantially the same manner as in Example 1. The result is shown in Table 2.
• the catalyst preparation, the analysis, and the reaction evaluation were performed in substantially the same manner as in Example 1, except that the step of steaming was not performed.
• the obtained FT synthesis catalyst is composed of metallic cobalt, cobalt oxide, silica, and zirconium oxide, and the loading amounts of cobalt and zirconium oxide were calculated in substantially the same manner as in Example 1. The result is shown in Table 2.
• the catalyst preparation, the analysis, and the reaction evaluation were performed in substantially the same manner as in Example 2, except that the step of steaming was not performed.
• the obtained FT synthesis catalyst is composed of metallic cobalt, cobalt oxide, and silica, and the loading amount of cobalt was calculated in substantially the same manner as in Example 1. The result is shown in Table 2.
• the obtained FT synthesis catalyst is composed of metallic cobalt, cobalt oxide, silica, and zirconium oxide, and the loading amounts of cobalt and zirconium oxide were calculated in substantially the same manner as in Example 1. The result is shown in Table 2.
• an FT synthesis catalyst having high activity in which the distribution of an active metal in the inside/outside of a pore of a carrier is controlled, a method for producing the catalyst, and an efficient method for producing a hydrocarbon using the catalyst are provided.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• Physics & Mathematics (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• General Chemical & Material Sciences (AREA)
• Optics & Photonics (AREA)
• Health & Medical Sciences (AREA)
• Plasma & Fusion (AREA)
• Toxicology (AREA)
• Thermal Sciences (AREA)
• Catalysts (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Nanotechnology (AREA)
• Crystallography & Structural Chemistry (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Applications Claiming Priority (3)

Related Parent Applications (1)

Related Child Applications (1)

Publications (1)

Family

ID=44542010

Family Applications (2)

Family Applications After (1)

Country Status (8)

Cited By (7)

Families Citing this family (9)

Family Cites Families (18)

• 2011
  • 2011-02-14 US US13/581,935 patent/US20120329890A1/en not_active Abandoned
  • 2011-02-14 MY MYPI2012700601A patent/MY160868A/en unknown
  • 2011-02-14 WO PCT/JP2011/053011 patent/WO2011108347A1/fr active Application Filing
  • 2011-02-14 JP JP2012503052A patent/JP5759447B2/ja not_active Expired - Fee Related
  • 2011-02-14 CA CA2791267A patent/CA2791267C/fr not_active Expired - Fee Related
  • 2011-02-14 RU RU2012142316/04A patent/RU2552517C2/ru not_active IP Right Cessation
  • 2011-02-14 CN CN201180012635.8A patent/CN102781574B/zh not_active Expired - Fee Related
  • 2011-02-14 AU AU2011222197A patent/AU2011222197B2/en not_active Ceased
• 2015
  • 2015-07-27 US US14/809,565 patent/US9868112B2/en not_active Expired - Fee Related

Non-Patent Citations (3)

Also Published As

Similar Documents

Legal Events