Classifications

• • 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
  • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
  • C10G31/10—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for with the aid of centrifugal force
• • 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
  • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
• • 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
  • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/889—Manganese, technetium or rhenium
  • B01J23/8892—Manganese
• • 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
  • B01J35/61—Surface area
  • B01J35/617—500-1000 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
  • B01J35/633—Pore volume less than 0.5 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
  • B01J35/635—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
• • 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
  • 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
  • B01J35/651—50-500 nm
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
  • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
  • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
  • C07C1/0425—Catalysts; their physical properties
  • C07C1/043—Catalysts; their physical properties characterised by the composition
  • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
  • C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
  • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
  • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
  • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds 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
  • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • C07C2523/32—Manganese, technetium or rhenium
  • C07C2523/34—Manganese
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

• the present invention relates to a method for producing unsaturated hydrocarbons and oxygen-containing compounds, a catalyst, and a method for producing the same.
• Fischer-Tropsch synthesis is known as a method for synthesizing hydrocarbons from synthesis gas (a mixture of carbon monoxide and hydrogen).
• unsaturated hydrocarbons that is, oxygenated compounds typified by olefins and alcohols are useful as chemical raw materials. Therefore, there is a method for producing unsaturated hydrocarbons and oxygenated compounds as target products from synthesis gas. It is being considered.
• Patent Documents 1 and 2 disclose an FT reaction for the purpose of producing an olefin in a high yield using an iron-based catalyst using a manganese-based compound as a carrier.
• Patent Document 3 discloses an FT reaction using a catalyst in which iron, copper, and potassium are supported on a silica porous support.
• Patent Documents 4 and 5 disclose a method for producing olefins from synthesis gas using a manganese compound as a carrier and a catalyst supporting ruthenium.
• Patent Documents 1 to 5 are not necessarily sufficient in terms of the conversion rate of carbon monoxide (CO conversion rate) in the synthesis gas, the selectivity of unsaturated hydrocarbons and oxygen-containing compounds, and the like. However, there is room for improvement in order to be put to practical use.
• CO conversion rate carbon monoxide
• the present invention has been made in view of such circumstances, and the object thereof is a method capable of achieving high CO conversion and high selectivity of unsaturated hydrocarbons and oxygen-containing compounds in the FT reaction. And a catalyst used in the method and a method for producing the catalyst.
• the present inventors have conducted a FT reaction under specific conditions using a catalyst containing manganese and supporting iron on a specific average pore diameter. It has been found that it provides a significantly higher CO conversion and has a significantly higher olefin and alcohol selectivity, resulting in a significantly higher total olefin and alcohol selectivity, thus completing the present invention.
• the present invention relates to a method for producing unsaturated hydrocarbons and oxygen-containing compounds described in (1) to (4) below, a catalyst described in (5) to (7) below, and a catalyst described in (8) below.
• a manufacturing method is provided.
• “syngas” refers to a mixed gas of carbon monoxide and hydrogen.
• a catalyst prepared by supporting iron on a support containing manganese and having an average pore diameter of 2 to 100 nm is dispersed in poly ⁇ -olefin and contains carbon monoxide or carbon monoxide and hydrogen.
• the first step of reducing the catalyst with the synthesis gas, the catalyst after the reduction in the first step and the synthesis gas are brought into contact under the conditions of a reaction temperature of 100 to 600 ° C.
• a second step of obtaining a reaction product containing a saturated hydrocarbon and an oxygen-containing compound A method for producing an unsaturated hydrocarbon and an oxygen-containing compound.
• the unsaturated hydrocarbon and oxygen-containing compound according to (1) or (2), wherein the catalyst is a catalyst prepared by further supporting copper and / or potassium on the carrier Manufacturing method.
• the method for producing unsaturated hydrocarbons and oxygenated compounds of the present invention and the catalyst of the present invention it is possible to achieve high CO conversion and high selectivity of unsaturated hydrocarbons and oxygenated compounds in the FT reaction. It becomes. Further, according to the method for producing a catalyst of the present invention, the catalyst of the present invention having excellent characteristics as described above can be obtained effectively.
• the catalyst of the present invention is prepared by supporting iron on a support containing manganese and having an average pore diameter of 2 to 100 nm.
• the carrier constituting the catalyst of the present invention contains manganese (Mn) as an essential element, but further contains an element selected from the elements of Group IA, IIA, IIIB, IVB, IIIA, and IVA in addition to Mn. Also good.
• the average pore diameter of the carrier is 2 to 100 nm, preferably 2 to 50 nm as described above. If the average pore diameter is less than 2 nm, pores are likely to be blocked during FT synthesis, and a suitable catalytic reaction cannot be maintained. On the other hand, if the average pore diameter exceeds 100 nm, the surface area per unit weight becomes remarkably small, and a sufficient amount of supported metal such as iron cannot be secured.
• the “average pore diameter” in the present invention refers to a value measured by a nitrogen adsorption method using a Quanta Chrome Autosorb-1 manufactured by Yuasa Ionics, which is an adsorption measuring device.
• the specific surface area of the carrier used in the present invention is not particularly limited, but the specific surface area by the BET method is preferably in the range of 100 to 1000 m 2 / g.
• the pore volume of the carrier is not particularly limited, but is preferably in the range of 0.2 to 2.0 ml / g.
• the shape of the carrier is not particularly limited, and for example, a shape suitable for the process to be used can be appropriately selected from shapes such as a spherical shape, a crushed product, and a cylindrical shape.
• a carrier not containing Mn such as silica, silica alumina, alumina and titania can be used in combination.
• any compound such as an inorganic salt of Fe or an organic complex can be used.
• sulfates, nitrates, organic acid salts, and chlorides are preferably used.
• the catalyst of the present invention may further contain a metal other than Fe as a supported metal.
• a metal other than Fe it is preferable in terms of catalytic activity that copper (Cu) and / or potassium (K) is supported on the carrier in addition to Fe.
• the compound used for supporting Cu and K is not particularly limited.
• any Cu compound such as an inorganic salt of Cu or an organic complex can be used.
• sulfates, nitrates, organic acid salts, and chlorides are preferably used. Specific examples include copper sulfate, copper nitrate, copper chloride, and copper acetate.
• the amount of the metal supported on the carrier is not particularly limited, but the amount of Fe supported is preferably 3 to 50% by weight, more preferably 5 to 40% by weight, still more preferably 10 to 10% by weight based on the carrier. It is preferably 30% by weight, particularly preferably 15 to 25% by weight.
• the amount of Cu supported is 0.5 to 6% by weight, more preferably 1 to 4% by weight, based on the carrier.
• a commonly used method such as an impregnation method or an ion exchange method can be appropriately selected.
• a particularly preferred method is an impregnation method, and an especially preferred method among the impregnation methods is an Incipient Wetness method.
• simultaneous impregnation or sequential impregnation can be selected, but simultaneous impregnation is preferred.
• the catalyst of this invention can be suitably obtained by the manufacturing method of the catalyst of this invention provided with the following 3 processes.
• A-1) a step of mixing a support containing Mn and having an average pore diameter of 2 to 100 nm and a solution containing Fe;
• A-2) A step of depressurizing and drying the mixture obtained in the step (A-1), and depositing iron in the pores of the support to obtain a catalyst precursor,
• A-3) A step of firing the catalyst precursor obtained in the step (A-2).
• a solvent can be used.
• the solvent is not particularly limited as long as it can disperse a carrier containing Mn and dissolve at least the Fe compound. Specific examples include water, ketone compounds such as acetone, and alcohol solvents such as methanol, ethanol, and isopropyl alcohol.
• the treatment temperature in step (A-1) is usually sufficient at normal temperature, but it is preferable to heat to about 60 ° C. and use ultrasonic vibration.
• these metals may be added to a solution containing Fe.
• the pressure during the pressure reduction / drying in the step (A-2) is 100 kPa or less and the temperature is 40 ° C. or more.
• the pressure during the pressure reduction / drying in the step (A-2) is 100 kPa or less and the temperature is 40 ° C. or more.
• metal components such as Fe, adhere uniformly in a pore, it is preferable to stir.
• the firing temperature in the step (A-3) is preferably 100 ° C. or higher, and the atmosphere is preferably an air atmosphere. More preferably, baking is performed at 120 ° C. for 12 hours or more in an air atmosphere.
• the manufacturing method of the unsaturated hydrocarbon and oxygen-containing compound of the present invention uses the catalyst of the present invention, and includes the following two steps.
• B-1 The catalyst of the present invention is dispersed in poly ⁇ -olefin (PAO), and the catalyst is synthesized with synthesis gas containing carbon monoxide or carbon monoxide and hydrogen (hereinafter simply referred to as “synthesis gas”).
• synthesis gas synthesis gas containing carbon monoxide or carbon monoxide and hydrogen
• Reducing step, (B-2) The catalyst after reduction in the step (B-1) and the synthesis gas are brought into contact under the conditions of a reaction temperature of 100 to 600 ° C. and a reaction pressure of 0.1 to 10 MPa, and unsaturated hydrocarbons and A step of obtaining a reaction product containing an oxygen-containing compound.
• the catalyst of the present invention in the step (B-1), it is preferable to introduce the catalyst of the present invention into a reactor and disperse it in PAO to adopt a slurry format.
• the catalyst of the present invention can be further enhanced by reducing the catalyst within the reactive group with synthesis gas (mixture of carbon monoxide and hydrogen, in any ratio) or with carbon monoxide. it can.
• the ratio of catalyst to PAO is basically arbitrary, but preferably 1 ml to 10 L of PAO is used per 1 g of catalyst.
• the reduction temperature is preferably in the range of 100 to 400 ° C.
• PAO to be used those having a boiling point of 300 ° C. or more are suitable.
• the production ratio of oxygen-containing compounds to unsaturated hydrocarbons in the step (B-2) is remarkably increased.
• unsaturated hydrocarbon / containing There is a tendency for the ratio of oxygen compounds to be significantly reduced.
• Step (B-1) is an in-situ reduction method in which the catalyst is activated in the system.
• FT synthesis is performed in step (B-2).
• the reaction temperature in the step (B-2) is selected from 100 to 600 ° C. If the reaction temperature is less than 100 ° C, the activity becomes insufficient and the conversion rate becomes extremely low. If the reaction temperature exceeds 600 ° C, decomposition of the reaction product and PAO tends to occur.
• a more preferred reaction temperature is in the range of 220 to 340 ° C., more preferably 280 ° C. plus or minus 20 ° C.
• the total value of the unsaturated hydrocarbon and the oxygen-containing compound is 25% or more, and the ratio of unsaturated hydrocarbon / oxygen-containing compound is within the range of 0.1 to 3.0.
• Olefin or alcohol useful as chemicals can be produced separately.
• the reaction pressure in the step (B-2) is selected from 0.1 to 10 MPa, preferably 0.5 to 5 MPa.
• the reaction pressure is less than 0.1 MPa, the contact probability between the catalyst dispersed in PAO and the synthesis gas becomes low, and the reactivity becomes insufficient.
• pressurization exceeding 10 MPa is not preferable because it is excessive pressurization and requires excessive equipment.
• the method for producing an unsaturated hydrocarbon and oxygen-containing compound of the present invention is most preferably applied to a slurry bed process advantageous for industrialization because wax precipitation hardly occurs on the catalyst surface and reaction heat is easily removed. It can also be used for conventionally known fixed bed processes and fluidized bed processes.
• the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.
• the unit “%” for CO conversion, yield and selectivity means mol%.
• Example 1 Manganese oxide carrier having a K content of 8% by weight (manufactured by Zude Chemie Catalysts, trade name N-190, BET specific surface area 398 m 2 / g, pore volume 0.70 ml / g, average pore diameter 10.1 nm) was divided into 20-40 meshes.
• This manganese oxide carrier 5g an aqueous solution containing an amount of Fe (NO 3) 3 ⁇ 9H 2 O , which corresponds to 20% by weight of manganese oxide as a metal iron was impregnated by Incipient Wettness method while using ultrasonic vibration. Vacuum drying was performed at 65 ° C. for 6 hours, drying at 120 ° C.
• the thus prepared catalyst 1g was introduced into the slurry-type reaction group vessel was added PAO (poly ⁇ - olefins) of 20 ml.
• PAO poly ⁇ - olefins
• the FT reaction was performed under the same conditions as the reduction, and a sample was taken 10 hours later, and the product was quantified by GC using transdecalin and 1-octanol as standard substances.
• the CO conversion was 80%, and the yields were CO 2 (47%), methane (3%), oxygenate (8%), olefin (24%), and paraffin (8%), respectively. Further, the total yield of unsaturated hydrocarbon and oxygen-containing compound was 32%, and the ratio of unsaturated hydrocarbon / oxygen-containing compound was 2.9.
• the olefin / paraffin ratio (hereinafter referred to as O / P) at C 2 -C 4 is 5, O / P at C 5 -C 11 is 3, and O at C 12 or higher. / P was 1.
• the selectivity of each component is methane (9%), C 2 -C 4 (38%), C 5 -C 11 (47%), C 12 or more (6% )Met.
• the main compound selectivity was methanol (12%), ethanol (49%), 1-propanol (13%), 1-butanol (7%).
• Example 2 Example 1 except that in addition to Fe (NO 3 ) 3 ⁇ 9H 2 O as a supported metal, Cu (NO 3 ) 2 ⁇ 3H 2 O in an amount corresponding to 3% by weight of manganese oxide was used as metallic copper. Thus, a catalyst was prepared, and an FT reaction was performed using the obtained catalyst. The CO conversion was 89%, and the yields were CO 2 (44%), methane (6%), oxygenate (15%), olefin (25%), and paraffin (10%), respectively. The total value of unsaturated hydrocarbon and oxygen-containing compound was 40%, and the ratio of unsaturated hydrocarbon / oxygen-containing compound was 1.7.
• the O / P at C 2 -C 4 was 5
• the O / P at C 5 -C 11 was 4, and the O / P at C 12 or higher was 1.
• the selectivity of each component is methane (9%), C 2 -C 4 (38%), C 5 -C 11 (39%), C 12 or more (15% )Met.
• the main compound selectivity was methanol (7%), ethanol (57%), 1-propanol (15%), 1-butanol (7%).
• Example 3 The FT reaction was carried out in the same manner as in Example 2 except that the reaction temperature was 300 ° C. The CO conversion was 93%, and the yield was CO 2 (44%), methane (1%), oxygenated compound (41%), olefin (6%), and paraffin (7%). The total yield of unsaturated hydrocarbon and oxygenated compound was 47%, and the ratio of unsaturated hydrocarbon / oxygenated compound was 0.1. Further, in the hydrocarbon not containing an oxygen-containing compound, the O / P at C 2 -C 4 was 5, the O / P at C 5 -C 11 was 4, and the O / P at C 12 or more was 3. . In hydrocarbons not containing oxygen-containing compounds, the selectivity of each component is methane (9%), C 2 -C 4 (37%), C 5 -C 11 (40%), C 12 or more (15% )Met.
• Example 4 The FT reaction was carried out in the same manner as in Example 2 except that the reaction temperature was 260 ° C.
• the CO conversion was 60%, and the yield was CO 2 (45%), methane (2%), oxygenated compound (7%), olefin (19%), and paraffin (6%).
• the total yield of unsaturated hydrocarbon and oxygenated compound was 25%, and the ratio of unsaturated hydrocarbon / oxygenated compound was 2.7.
• the O / P at C 2 -C 4 was 5, the O / P at C 5 -C 11 was 3, and the O / P at C 12 or more was 1.
• the selectivity of each component is methane (8%), C 2 -C 4 (34%), C 5 -C 11 (43%), C 12 or more (16% )Met.
• Manganese oxide carrier having a K content of 3% by weight (manufactured by Zude Chemie Catalysts, trade name MN-280, BET specific surface area 381 m 2 / g, pore volume 0.55 ml / g, average pore diameter 4.7 nm) was divided into 20-40 meshes.
• This manganese oxide carrier 5g the amount corresponding to 3 wt% of the amount of Fe (NO 3) 3 ⁇ 9H 2 O and metal copper as manganese oxide corresponding to 20% by weight of manganese oxide as a metal iron Cu (NO 3 ) an aqueous solution containing 2 ⁇ 3H 2 O, was impregnated simultaneously by I nc i p i ent Wettness method while using ultrasonic vibration. Vacuum drying was performed at 65 ° C. for 6 hours, drying at 120 ° C. for 12 hours, and the temperature was raised from room temperature to 400 ° C. at 2 ° C./min. Further, it was calcined at 400 ° C. for 2 hours.
• the total yield of unsaturated hydrocarbon and oxygenated compound was 37%, and the ratio of unsaturated hydrocarbon / oxygenated compound was 0.9.
• the olefin / paraffin ratio (hereinafter referred to as O / P) at C 2 -C 4 is 4, O / P at C 5 -C 11 is 2, and O at C 12 or higher.
• / P was 1.
• the selectivity of each component is methane (8%), C 2 -C 4 (37%), C 5 -C 11 (45%), C 12 or more (10% )Met.
• the main compound selectivity was methanol (8%), ethanol (57%), 1-propanol (16%), 1-butanol (7%). .
• Example 1 A catalyst was prepared in the same manner as in Example 2 except that a manganese oxide support having a K content of 8% by weight and an average pore diameter of 1 nm was used, and an FT reaction was performed using the obtained catalyst. . However, the activity disappeared 1 hour after the start of the reaction.
• the FT reaction was performed under the same conditions as the reduction, and a sample was taken 10 hours later, and the product was quantified by GC using transdecalin and 1-octanol as standard substances.
• the CO conversion was 41%, and the yields were CO 2 (39%), methane (1%), oxygenate (1%), olefin (16%), and paraffin (7%), respectively.
• the total yield of unsaturated hydrocarbons and oxygenated compounds was 17%, and the ratio of unsaturated hydrocarbons / oxygenated compounds was 12.1.
• O / P at C 2 -C 4 is 3
• O / P at C 5 -C 11 is 3
• O / P at C 12 or more is 0.5. there were.
• the selectivity of each component is methane (5%), C 2 -C 4 (21%), C 5 -C 11 (62%), C 12 or more (12% )Met.
• the main compound selectivity was methanol (17%), ethanol (43%), 1-propanol (17%), 1-butanol (9%).

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