WO2020027321A1 - Structure de catalyseur de synthèse d'hydrocarbures légers, appareil de production d'hydrocarbures légers, et procédé de production d'hydrocarbures légers - Google Patents

Structure de catalyseur de synthèse d'hydrocarbures légers, appareil de production d'hydrocarbures légers, et procédé de production d'hydrocarbures légers Download PDF

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WO2020027321A1
WO2020027321A1 PCT/JP2019/030482 JP2019030482W WO2020027321A1 WO 2020027321 A1 WO2020027321 A1 WO 2020027321A1 JP 2019030482 W JP2019030482 W JP 2019030482W WO 2020027321 A1 WO2020027321 A1 WO 2020027321A1
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light hydrocarbon
catalyst structure
metal
passage
carrier
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PCT/JP2019/030482
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English (en)
Japanese (ja)
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可織 関根
麻衣 西井
祐一郎 馬場
將行 福嶋
禎宏 加藤
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古河電気工業株式会社
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Priority to JP2020534772A priority Critical patent/JP7407713B2/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/08—Alkenes with four carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/08—Alkenes with four carbon atoms
    • C07C11/09—Isobutene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • 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 light hydrocarbon synthesis catalyst structure, a light hydrocarbon production apparatus, and a method for producing a light liquid hydrocarbon, and in particular, a light hydrocarbon capable of selectively producing light hydrocarbons from carbon monoxide and hydrogen.
  • the present invention relates to a synthetic catalyst structure, a light hydrocarbon production device, and a method for producing a light liquid hydrocarbon.
  • Patent Document 1 discloses a catalyst in which an active metal such as cobalt or iron is supported on a carrier such as silica or alumina. , Zirconium or titanium, and silica containing catalysts are disclosed.
  • the catalyst used in the FT synthesis reaction is, for example, a catalyst in which a cobalt oxide and / or ruthenium oxide is supported by impregnating a carrier such as silica or alumina with a cobalt salt, a ruthenium salt or the like, and calcining the impregnated carrier. Unreduced catalyst).
  • the catalyst is brought into contact with a reducing gas such as hydrogen gas as described in Patent Document 3 to perform a reduction treatment.
  • a reducing gas such as hydrogen gas as described in Patent Document 3 to perform a reduction treatment.
  • Patent Document 4 discloses that a core-shell type catalyst composed of a core part constituting an FT synthesis catalyst and a shell part which decomposes and reduces hydrocarbons is used to grow hydrocarbons with the FT synthesis catalyst in the core part.
  • a technique is disclosed in which a product obtained by an FT synthesis reaction is decomposed with a catalyst for decomposing hydrocarbons in a shell portion to lighten the generated hydrocarbons.
  • Patent Literature 4 discloses only a carbon number distribution mainly for hydrocarbons having 5 or more carbon atoms.
  • the carbon number of the hydrocarbon synthesized by the cobalt catalyst in the core is adjusted by the reaction of the surface of the zeolite in the shell, even after the softening of the product is prepared in the shell, the core or the adjacent shell is not affected. May react again with parts. For this reason, it is difficult to control the selectivity of hydrocarbons having a specific number of carbon atoms, and particularly to control the carbon number distribution for light hydrocarbons having a smaller number of carbon atoms.
  • light hydrocarbons such as propylene and butene produced as gas components in the FT synthesis reaction are known to be used as basic raw materials for various chemical products.
  • the FT synthesis reaction such light hydrocarbons can also be produced, but their selectivity is still low. That is, a technique for increasing the selectivity of light hydrocarbons over heavy hydrocarbons in products obtained by the FT synthesis reaction has not yet been established.
  • the additional operations such as the purification process required in the conventional synthesis process can be omitted, and the production efficiency can be improved. Is also desired.
  • An object of the present invention is to provide a light hydrocarbon synthesis catalyst structure capable of enhancing the selectivity of light hydrocarbons in hydrocarbon synthesis, a method for producing light hydrocarbons using the catalyst structure, and the catalyst structure It is to provide a light hydrocarbon production device having the following.
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, provided with a carrier having a porous structure composed of a zeolite type compound, and at least one metal fine particle contained in the carrier,
  • the carrier has a passage communicating with the outside of the carrier, an average inner diameter of a part of the passage is 0.95 nm or less, and the fine metal particles are present in a passage having the average inner diameter of 0.95 nm or less. It has been found that the use of such a catalyst structure can enhance the selectivity of light hydrocarbons in hydrocarbon synthesis, especially in FT synthesis reactions.
  • the gist configuration of the present invention is as follows.
  • the carrier has a passage communicating with the outside of the carrier, An average inner diameter of a part of the passage is 0.95 nm or less;
  • the passage may be one of a one-dimensional hole, a two-dimensional hole, and a three-dimensional hole defined by a skeletal structure of the zeolite-type compound, and may be one of the one-dimensional hole, the two-dimensional hole, and the three-dimensional hole.
  • Hydrogen synthesis catalyst structure [8] The light hydrocarbon synthesis catalyst according to the above [6] or [7], wherein the average particle diameter of the metal fine particles is larger than the entire average inner diameter of the passage and equal to or smaller than the inner diameter of the enlarged diameter portion. Structure. [9] The method according to any one of [1] to [8], wherein the metal element (M) of the metal fine particles is contained in an amount of 0.5% by mass or more based on the light hydrocarbon synthesis catalyst structure. The light hydrocarbon synthesis catalyst structure according to the above. [10] The amount of the metal-containing aqueous solution, which is the raw material of the metal fine particles, is adjusted with respect to the metal element (M) contained in the metal-containing aqueous solution.
  • the light hydrocarbon synthesis catalyst structure according to any one of the above [1] to [9], wherein the structure is 10 or more and 1000 or less in terms of the ratio of Si) (atomic ratio Si / M).
  • a light hydrocarbon production device having the light hydrocarbon synthesis catalyst structure according to any one of [1] to [11].
  • the light hydrocarbon production apparatus according to the above [12], further comprising a light hydrocarbon synthesis catalyst structure in which the range of the average inner diameter in a part of the passage differs according to the number of carbon atoms of the light hydrocarbon to be synthesized.
  • a method for producing a light hydrocarbon wherein the light hydrocarbon is synthesized from carbon monoxide and hydrogen using the light hydrocarbon synthesis catalyst structure according to any one of the above [1] to [11].
  • [15] The method for producing a light hydrocarbon according to the above [14], wherein a light hydrocarbon synthesis catalyst structure having a different average inner diameter range in a part of the passage according to the carbon number of the light hydrocarbon to be synthesized is used. .
  • FIG. 1 schematically shows the internal structure of a light hydrocarbon synthesis catalyst structure according to an embodiment of the present invention so that it can be seen.
  • FIG. 1 (a) is a perspective view (partly in cross section).
  • FIG. 1B is a partially enlarged cross-sectional view.
  • 2 is a partially enlarged cross-sectional view for explaining an example of a function of the light hydrocarbon synthesis catalyst structure of FIG. 1, in which FIG. 2 (a) illustrates a sieving function and FIG. 2 (b) illustrates a catalytic ability.
  • FIG. FIG. 3 is a flowchart showing an example of a method for producing the light hydrocarbon synthesis catalyst structure of FIG.
  • FIG. 1 is a diagram schematically showing a configuration of a light hydrocarbon synthesis catalyst structure (hereinafter, also simply referred to as a “catalyst structure”) according to an embodiment of the present invention, and FIG. (A part is shown by a cross section.), (B) is a partial enlarged sectional view.
  • the catalyst structure shown in FIG. 1 is an example, and the shapes, dimensions, and the like of the components according to the present invention are not limited to those shown in FIG.
  • the catalyst structure 1 includes a carrier 10 having a porous structure made of a zeolite type compound, and at least one metal fine particle 20 which is contained in the carrier 10.
  • the plurality of metal fine particles 20 are enclosed in the porous structure of the carrier 10.
  • the metal fine particles 20 are a catalytic substance having catalytic ability (catalytic activity).
  • the metal fine particles will be described later in detail.
  • the metal fine particles 20 may be particles containing a metal oxide, a metal alloy, or a composite material thereof.
  • the carrier 10 has a porous structure, and preferably has a plurality of holes 11a, 11a,... As shown in FIG. 1 (b) to form a passage 11 communicating with the outside of the carrier 10.
  • the average inner diameter of a part of the passage 11 of the carrier 10 is 0.95 nm or less
  • the metal fine particles 20 are present in the passage 11 having an average inner diameter of 0.95 nm or less, and preferably have an average inner diameter of 0.15 nm. It is held in a passage 11 of 95 nm or less.
  • the selectivity of light hydrocarbons can be increased in the synthesis of hydrocarbons, particularly in the FT synthesis reaction.
  • the movement of the metal fine particles 20 in the carrier 10 is regulated, and the aggregation of the metal fine particles 20, 20 is effectively prevented.
  • a decrease in the effective surface area of the metal fine particles 20 can be effectively suppressed, and the catalytic activity of the metal fine particles 20 can be maintained for a long time.
  • the catalyst structure 1 can suppress a decrease in the catalytic activity due to the aggregation of the metal fine particles 20, and can prolong the life of the catalyst structure 1.
  • the replacement frequency of the catalyst structure 1 can be reduced, the amount of used catalyst structure 1 disposed can be significantly reduced, and resource saving can be achieved. .
  • the catalyst structure 1 when the catalyst structure 1 is used in a fluid (for example, a synthesis gas), there is a possibility that an external force is received from the fluid.
  • a fluid for example, a synthesis gas
  • the metal microparticles 20 are merely held in an attached state on the outer surface of the carrier 10, there is a problem that the metal particles 20 are easily detached from the outer surface of the carrier 10 due to an external force from a fluid.
  • the metal fine particles 20 exist in at least the passage 11 of the carrier 10, even if the metal fine particles 20 are affected by an external force due to the fluid, the metal fine particles 20 are hard to be separated from the carrier 10.
  • the catalyst structure 1 when the catalyst structure 1 is in the fluid, the fluid flows into the passage 11 from the hole 11a of the carrier 10, and the speed of the fluid flowing in the passage 11 is determined by the flow passage resistance (frictional force). It is considered that the velocity is lower than the velocity of the fluid flowing on the outer surface of the carrier 10. Due to such an influence of the flow path resistance, the pressure that the metal fine particles 20 held in the passage 11 receives from the fluid becomes lower than the pressure that the metal fine particles receive from the fluid outside the carrier 10. Therefore, the detachment of the metal fine particles 20 existing in the carrier 10 can be effectively suppressed, and the catalytic activity of the metal fine particles 20 can be stably maintained for a long time.
  • the flow path resistance as described above is considered to increase as the passage 11 of the carrier 10 has a plurality of bends and branches and the inside of the carrier 10 has a more complicated and three-dimensional structure. .
  • the passage 11 is formed of one of a one-dimensional hole, a two-dimensional hole, and a three-dimensional hole defined by the skeleton structure of the zeolite-type compound, and one of the one-dimensional hole, the two-dimensional hole, and the three-dimensional hole.
  • the metal fine particles 20 are present at least in the enlarged diameter portion 12, and at least are included in the enlarged diameter portion 12. Is more preferable.
  • the enlarged diameter portion 12 communicates a plurality of holes 11a, 11a constituting any one of the one-dimensional hole, the two-dimensional hole, and the three-dimensional hole.
  • the one-dimensional hole means a tunnel-type or cage-type hole forming a one-dimensional channel, or a plurality of tunnel-type or cage-type holes forming a plurality of one-dimensional channels (a plurality of holes).
  • a two-dimensional hole refers to a two-dimensional channel in which a plurality of one-dimensional channels are two-dimensionally connected
  • a three-dimensional hole refers to a three-dimensional channel in which a plurality of one-dimensional channels are three-dimensionally connected. Point.
  • the inclusion includes a state in which the metal fine particles 20 are included in the carrier 10. At this time, the metal fine particles 20 and the carrier 10 do not necessarily need to be in direct contact with each other, and a state in which another substance (for example, a surfactant or the like) is interposed between the metal fine particles 20 and the carrier 10.
  • the metal fine particles 20 may be indirectly held by the carrier 10.
  • FIG. 1B shows a case where the metal fine particles 20 are included in the enlarged diameter portion 12.
  • the present invention is not limited to this configuration. It may be held in the passage 11 in a state of protruding outside. Further, the metal fine particles 20 may be partially buried in a portion of the passage 11 other than the enlarged diameter portion 12 (for example, an inner wall portion of the passage 11), or may be held by fixing.
  • the passage 11 is three-dimensionally formed inside the carrier 10 including a branch portion or a merging portion, and the enlarged diameter portion 12 is preferably provided at the branch portion or the merging portion of the passage 11. .
  • the average inner diameter DT of the entire passage 11 formed in the carrier 10 is calculated from the average value of the minor axis and the major axis of the hole 11a constituting one of the one-dimensional hole, the two-dimensional hole, and the three-dimensional hole.
  • the thickness is 0.10 nm or more and 1.50 nm or less, preferably 0.38 nm or more and 0.95 nm or less.
  • carbon monoxide and hydrogen are the raw materials in the FT synthesis reaction, and the molecular size of carbon monoxide is about 0.38 nm and the molecular size of hydrogen is about 0.29 nm. It is.
  • the entire average inner diameter DT of the passage 11 is preferably 0.40 nm or more and 1.50 nm or less, more preferably 0.49 nm or more and 0.95 nm or less, and 0.49 nm or more and 0.70 nm or less. Is more preferable.
  • the inner diameter DE of the enlarged diameter portion 12 is, for example, 0.5 nm or more and 50 nm or less, preferably 1.1 nm or more and 40 nm or less, and more preferably 1.1 nm or more and 3.3 nm or less.
  • the inner diameter D E of the enlarged diameter section 12 depends on for example the pore size of which will be described later precursor material (A), and the average particle diameter D C of the fine metal particles 20 to be inclusion.
  • the inner diameter DE of the enlarged diameter portion 12 is large enough to include the metal fine particles 20.
  • the carrier 10 is composed of a zeolite type compound.
  • the zeolite-type compound include silicate compounds such as zeolite (aluminosilicate), cation-exchanged zeolite, and silicalite; zeolite-related compounds such as aluminoborate, aluminoarsenate, and germanate; molybdenum phosphate; Phosphate-based zeolite-like substances.
  • the zeolite type compound is preferably a silicate compound.
  • the skeletal structure of the zeolite type compound is FAU type (Y type or X type), MTW type, MFI type, FER type (ferrierite), LTA type (A type), MWW type (MCM-22), MOR type (mordenite) ), LTL type (L type), BEA type (beta type), CHA type and the like.
  • FAU type Y type or X type
  • MTW type MFI type
  • MFI type FER type
  • a type MWW type
  • MCM-22 MOR type
  • MOR type mordenite
  • LTL type L type
  • BEA type beta type
  • CHA type CHA type and the like.
  • MFI type, MOR type, BEA type, and CHA type are preferable, and MFI type, MOR type, and BEA type are more preferable from the viewpoint of the pore size that allows sufficient molecular diffusion of the product whose selectivity is to be improved. preferable.
  • the zeolite-type compound is formed with a plurality of pores having a pore diameter corresponding to each skeletal structure.
  • the average pore diameter Is about 0.55 nm (5.50 °).
  • the short pore diameter is 0.38 nm (3.8 °)
  • the long pore diameter is 0.38 (no short side and long side) nm (3.8 °).
  • the average pore diameter is about 0.38 nm (3.8 °).
  • the inside diameter of the passage 11 existing inside the carrier 10 depending on the skeletal structure of the zeolite type compound is smaller than the size of the obtained product, for example, the molecular size (chain length size), the passage 11 The movement of such products is limited.
  • the carrier 10 composed of a zeolite-type compound having an average inner diameter DF of 0.95 nm or less in a part of the passage 11, that is, the passage in which the metal fine particles 20 as the catalyst substance are contained is used.
  • the growth of carbon chains is suppressed, and the production of heavy hydrocarbons having a relatively large molecular size is suppressed.
  • the average inner diameter DF of the passage 11 in which the metal microparticles 20 are present 0.95 nm or less, heavy hydrocarbons having 7 or more carbon atoms in hydrocarbon synthesis, for example, in a Fischer-Tropsch synthesis reaction.
  • the selectivity of light hydrocarbons having 6 or less carbon atoms can be enhanced while suppressing the production of hydrocarbons.
  • the lower limit of the average inner diameter DF is from the viewpoint that products having 2 or more carbon atoms are useful as raw materials for various synthetic substances. is preferably not less than 0.38 nm, from the viewpoint 3 or more products carbon atoms are useful as petrochemical raw material, the lower limit of the average inner diameter D F is more preferably greater than 0.39 nm.
  • the pores present in the zeolite type compound are not necessarily circular but may be polygonal. Therefore, the average inner diameter DF may be calculated from, for example, a value obtained by equally adding the long pore diameter (long axis) and the short pore diameter (short axis) in each pore.
  • the selectivity of the generated light hydrocarbon can be further increased, and in particular, the chain length size (length of the molecule in the major axis direction) equivalent to the average inner diameter DF
  • the chain length size (length of the long axis direction of the molecule) of the trait hydrocarbon having 2 carbon atoms is 0.36 nm or more and less than 0.43 nm
  • the length in the axial direction) is 0.49 nm or more and less than 0.59 nm.
  • the chain length of light hydrocarbons having 4 carbon atoms (the length in the major axis direction) is 0.50 nm or more and less than 0.70 nm.
  • the chain length size (length of the long axis direction of the molecule) of the light hydrocarbon having a carbon number of 5 is 0.50 nm or more and less than 0.79 nm, and the chain length size (the length of the long axis direction of the molecule) of the light hydrocarbon having 6 carbon atoms Is between 0.59 nm and less than 0.95 nm.
  • the chain length of n-hexene having 6 carbon atoms is about 0.91 nm
  • the chain length size of n-pentene having 5 carbon atoms is about 0.91 nm.
  • the chain length of n-butene having 4 carbon atoms is about 0.65 nm
  • the propylene chain having 3 carbon atoms is The long size (length in the major axis direction of the molecule) is about 0.52 nm
  • the chain length size (length in the major axis direction) of ethylene having 2 carbon atoms is about 0.39 nm.
  • the average inner diameter DF in a part of the passage 11 is preferably 0.75 nm or less.
  • the average inner diameter DF in a part of the passage 11 is more preferably less than 0.75 nm, and is more than 0.55 nm and less than 0.75 nm. Is more preferable.
  • the average in a part of the passage 11 can be improved. It is particularly preferable that the inner diameter DF is 0.63 nm or more and less than 0.75 nm.
  • the average inner diameter DF in a part of the passage 11 is preferably less than 0.68 nm, and more than 0.39 nm and less than 0.68 nm. Is more preferable.
  • the average inner diameter DF in a part of the passage 11 is preferably 0.38 nm or more and less than 0.55 nm.
  • the selectivity of the light hydrocarbon may be affected not only by the pore size formed in the zeolite type compound, but also by the skeleton structure of the zeolite type compound, the molecular motion of the generated light hydrocarbon, and the like.
  • the skeleton structure of the zeolite type compound is the MFI type
  • the selectivity of olefins such as propylene and butene (n-butene and isobutene) tends to increase.
  • selectivity can be increased by these effects.
  • the average particle diameter D C of the fine metal particles 20 are preferably the overall average of the passage 11 It is larger than the inner diameter D T and equal to or less than the inner diameter D E of the enlarged diameter portion 12 (D T ⁇ D C ⁇ D E ).
  • Such metal fine particles 20 are preferably present in the enlarged diameter portion 12 in the passage 11, and the movement of the metal fine particles 20 in the carrier 10 is restricted. Therefore, even when the metal microparticles 20 receive an external force from a fluid, the movement of the metal microparticles 20 in the carrier 10 is suppressed, and the enlarged diameter portions 12, 12,. . Can be effectively prevented from contacting with each other.
  • the ratio (D C / D T) of the average particle diameter D C of the fine metal particles 20 to the total of the average inner diameter D T of the passage 11 is preferably 0.05 to 300, more preferably 0.1 or more 30 or less, more preferably 1.1 or more and 30 or less, particularly preferably 1.4 or more and 3.6 or less.
  • the metal element (M) of the metal fine particles 20 is preferably contained in an amount of 0.5% by mass or more based on the catalyst structure 1, and 0.5% by mass or more based on the catalyst structure 1. It is more preferably contained at 5% by mass or less, and further preferably at 1.5% by mass or less.
  • the metal element (M) is Co
  • the content (% by mass) of the Co element is represented by ⁇ (mass of Co element) / (mass of all elements in catalyst structure 1) ⁇ ⁇ 100. .
  • the metal fine particles need only be composed of a metal that has not been oxidized.
  • the metal fine particles may be composed of a single metal, or may be composed of a mixture of two or more metals.
  • the “metal” (as a material) constituting the metal fine particles includes a simple metal containing one kind of metal element (M) and a metal alloy containing two or more kinds of metal elements (M). It means a general term for metals including the above metal elements.
  • the metal fine particles preferably contain Co, Fe, Ni, Ru or an alloy containing at least one of them, and from the viewpoint of improving selectivity. , Co, Fe, Ru, or an alloy containing at least one of them, and more preferably Co, Fe, or an alloy containing at least one of them from the viewpoint of manufacturing cost.
  • the ratio of the silicon (Si) constituting the carrier 10 to the metal element (M) constituting the metal fine particles 20 is preferably 10 or more and 1000 or less, and 50 or more and 200 or less. Is more preferable, and it is more preferable that it is 100 or more and 200 or less. If the above ratio is more than 1000, the activity of the metal fine particles as a catalyst substance may not be sufficiently obtained, such as a low activity. On the other hand, if the above ratio is less than 10, the ratio of the metal fine particles 20 becomes too large, and the strength of the carrier 10 tends to decrease.
  • the metal fine particles 20 referred to here are fine particles held or carried inside the carrier 10 and do not include metal fine particles attached to the outer surface of the carrier 10.
  • the content of the metal fine particles 20 in the catalyst structure 1 may be calculated from the metal-containing aqueous solution and the precursor material (A) used in the method for manufacturing the catalyst structure 1 described below.
  • the amount of the metal-containing aqueous solution that is the raw material of the fine metal particles 20 is such that silicon (Si) that constitutes the precursor material (A) that is the raw material of the carrier 10 with respect to the metal element (M) that is included in the metal-containing aqueous solution. ), (Atomic ratio Si / M), preferably from 10 to 1,000, more preferably from 50 to 200, even more preferably from 100 to 200.
  • the catalyst structure 1 includes the carrier 10 having a porous structure and at least one metal fine particle 20 existing in the carrier.
  • the catalyst structure 1 exhibits the catalytic ability of the metal fine particles 20 when the metal fine particles 20 existing in the carrier come into contact with the fluid. Specifically, the fluid in contact with the outer surface 10a of the catalyst structure 1 flows into the inside of the carrier 10 through the holes 11a formed in the outer surface 10a, is guided into the passage 11, and moves through the passage 11. Then, it goes out of the catalyst structure 1 through another hole 11a.
  • the catalyst structure 1 has a molecular sieving ability because the carrier has a porous structure.
  • molecules 15 a having a size equal to or less than the diameter of the hole 11 a in other words, having a size equal to or less than the inner diameter of the passage 11 can enter the carrier 10.
  • the molecules 15b having a size exceeding the diameter of the holes 11a cannot penetrate into the carrier 10.
  • a compound composed of molecules having a size equal to or smaller than the pore diameter of the hole 11a can exit the carrier 10 through the hole 11a, and is obtained as a reaction product.
  • a compound that cannot exit the carrier 10 through the hole 11a can exit the carrier 10 if it is converted into a compound composed of molecules having a size capable of exiting the carrier 10.
  • a molecule larger than the pore diameter of the hole 11a can also go out of the carrier 10 while expanding and contracting the molecule.
  • a specific reaction product can be selectively obtained by using the catalyst structure 1 in which the pore size of the pores 11a, particularly the pore size in which metal fine particles are present, is controlled.
  • the metal fine particles 20 are included in the enlarged diameter portion 12 of the passage 11.
  • the average particle diameter D C of the fine metal particles is greater than the average internal diameter D F at the part of the passage 11, and if smaller than the inner diameter D E of the enlarged diameter portion 12 (D F ⁇ D C ⁇ D E), a metal A small passage 13 is formed between the fine particles and the enlarged diameter portion 12. Then, as shown by the arrow in FIG. 2B, the fluid that has entered the small passage 13 comes into contact with the metal fine particles. Since each of the metal fine particles is included in the enlarged diameter portion 12, the movement in the carrier 10 is restricted. Thereby, aggregation of the metal fine particles in the carrier 10 is prevented. As a result, a large contact area between the metal fine particles and the fluid can be stably maintained.
  • a light gas (CH) can be obtained by using a mixed gas containing hydrogen and carbon monoxide as main components as a raw material. 4 ), preferably light hydrocarbons having C6 or less, particularly light hydrocarbons which are gaseous at normal temperature (C3-C4 hydrocarbons) can be selectively produced.
  • the FT synthesis reaction containing hydrogen and carbon monoxide as main components is performed at a high temperature of, for example, 180 ° C.
  • the metal fine particles 20 are contained in the carrier 10, the influence of the heating is affected. Hard to receive.
  • the metal fine particles 20 are present in the enlarged diameter portion 12, the movement of the metal fine particles 20 in the carrier 10 is further restricted, and aggregation (sintering) between the metal fine particles 20 is further suppressed.
  • a decrease in the catalyst activity is further suppressed, and the life of the catalyst structure 1 can be further extended.
  • the activation treatment (reduction treatment) of the metal fine particles 20 is easily performed because the metal fine particles 20 are not bonded to the carrier 10. be able to.
  • FIG. 3 is a flowchart showing a method for manufacturing the catalyst structure 1 of FIG.
  • Step S1 preparation step
  • a precursor material (A) for obtaining a carrier having a porous structure composed of a zeolite type compound is prepared.
  • the precursor material (A) is preferably a regular mesoporous substance, and can be appropriately selected according to the type (composition) of the zeolite-type compound constituting the carrier of the catalyst structure.
  • the regular mesoporous substance is composed of one-dimensional, two-dimensional, or three-dimensional pores having a pore diameter of 1 nm or more and 50 nm or less. It is preferable that the compound is a compound composed of a Si—O skeleton that has a uniform size in dimension and is regularly developed.
  • Such ordered mesoporous substances can be obtained as various synthetic substances depending on the synthesis conditions. Specific examples of the synthetic substances include, for example, SBA-1, SBA-15, SBA-16, KIT-6, FSM- 16, MCM-41 and the like, among which MCM-41 is preferable.
  • the pore size of SBA-1 is 10 nm or more and 30 nm or less
  • the pore size of SBA-15 is 6 nm or more and 10 nm or less
  • the pore size of SBA-16 is 6 nm
  • the pore size of KIT-6 is 9 nm
  • the pore size of FSM-16 is 10 nm or more and 5 nm or less
  • the pore diameter of MCM-41 is 1 nm or more and 10 nm or less.
  • ordered mesoporous materials include mesoporous silica, mesoporous aluminosilicate, and mesoporous metallosilicate.
  • the precursor material (A) may be a commercial product or a synthetic product.
  • synthesizing the precursor material (A) it can be performed by a known method for synthesizing a regular mesoporous substance. For example, a mixed solution containing a raw material containing the constituent elements of the precursor material (A) and a template for defining the structure of the precursor material (A) is prepared, and the pH is adjusted as necessary. And hydrothermal treatment (hydrothermal synthesis). Thereafter, the precipitate (product) obtained by the hydrothermal treatment is recovered (for example, by filtration), washed and dried if necessary, and further calcined to obtain a powdery regular mesoporous substance. The precursor material (A) is obtained.
  • a solvent of the mixed solution for example, water, an organic solvent such as alcohol, or a mixed solvent thereof can be used.
  • the raw material is selected according to the type of the carrier, and examples thereof include a silica agent such as tetraethoxysilane (TEOS), fumed silica, and quartz sand.
  • TEOS tetraethoxysilane
  • various surfactants, block copolymers, and the like can be used as the template agent, and it is preferable to select according to the type of the synthetic product of the ordered mesoporous material.
  • MCM-41 is produced Is preferably a surfactant such as hexadecyltrimethylammonium bromide.
  • the hydrothermal treatment can be performed, for example, in a closed container at 80 to 800 ° C. for 5 hours to 240 hours under the processing conditions of 0 to 2000 kPa.
  • the firing treatment can be performed, for example, in air at 350 to 850 ° C. for 2 to 30 hours.
  • Step S2 impregnation step
  • the prepared precursor material (A) is impregnated with a metal-containing solution to obtain a precursor material (B).
  • the metal-containing solution may be a solution containing a metal component (for example, a metal ion) corresponding to the metal element (M) constituting the metal fine particles of the catalyst structure.
  • a metal component for example, a metal ion
  • the metal element (M) may be added to a solvent. It can be prepared by dissolving the contained metal salt. Examples of such a metal salt include metal salts such as chlorides, hydroxides, oxides, sulfates, and nitrates, among which nitrates are preferred.
  • the solvent for example, water, an organic solvent such as an alcohol, or a mixed solvent thereof can be used.
  • the method for impregnating the precursor material (A) with the metal-containing solution is not particularly limited.
  • the precursor material (A) is stirred while the powdered precursor material (A) is stirred before the firing step described below. It is preferable that the metal-containing solution is added in small portions in a plurality of times.
  • a surfactant is added as an additive to the precursor material (A) before adding the metal-containing solution. It is preferable to add it.
  • Such an additive has a function of coating the outer surface of the precursor material (A), and suppresses a metal-containing solution to be subsequently added from adhering to the outer surface of the precursor material (A). It is considered that the contained solution is more likely to enter the inside of the pores of the precursor material (A).
  • nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, and polyoxyethylene alkyl phenyl ether. Since these surfactants have a large molecular size and cannot penetrate into the inside of the pores of the precursor material (A), they do not adhere to the inside of the pores, and the metal-containing solution does not penetrate into the pores. It does not seem to hinder.
  • a nonionic surfactant is added in an amount of 50% by mass or more and 500% by mass or less based on the precursor material (A) before the firing step described below. Is preferred.
  • the amount of the nonionic surfactant added to the precursor material (A) is less than 50% by mass, the above-described inhibitory effect is difficult to be exerted, and the nonionic surfactant is added to the precursor material (A) in an amount of 500%. It is not preferable to add more than mass% because the viscosity is too high. Therefore, the amount of the nonionic surfactant added to the precursor material (A) is set to a value within the above range.
  • the amount of the metal-containing solution added to the precursor material (A) depends on the amount of the metal element (M) contained in the metal-containing solution impregnated into the precursor material (A) (that is, the precursor material (B ) Is preferably adjusted in consideration of the amount of the metal element (M) to be included in the above.
  • the amount of the metal-containing solution added to the precursor material (A) is determined based on the amount of the metal element (M) contained in the metal-containing solution added to the precursor material (A).
  • the ratio is preferably adjusted to 10 or more and 1000 or less in terms of the ratio of silicon (Si) constituting the precursor material (A) (atomic ratio Si / M), and is preferably adjusted to 50 or more and 200 or less.
  • the adjustment is more preferable, and the adjustment is more preferably 100 or more and 200 or less.
  • the addition of the metal-containing solution to be added to the precursor material (A) By setting the amount to 50 or more and 200 or less in terms of the atomic ratio Si / M, the metal element (M) of the metal fine particles can be contained at 0.5% by mass or more based on the catalyst structure. , For example, in a range of 0.5% by mass or more and 2.5% by mass or less.
  • the amount of the metal element (M) existing inside the pores depends on the metal concentration of the metal-containing solution, the presence or absence of the additive, and other conditions such as temperature and pressure. If present, it is approximately proportional to the amount of the metal-containing solution added to the precursor material (A).
  • the amount of the metal element (M) contained in the precursor material (B) is in a proportional relationship with the amount of the metal element constituting the metal fine particles contained in the carrier of the catalyst structure.
  • the addition amount of the metal-containing solution to be added to the precursor material (A) to the above range, the inside of the pores of the precursor material (A) can be sufficiently impregnated with the metal-containing solution, and as a result, The amount of the fine metal particles contained in the carrier of the catalyst structure can be adjusted.
  • a cleaning treatment may be performed as necessary.
  • the cleaning solution water, an organic solvent such as alcohol, or a mixed solution thereof can be used.
  • the drying treatment include natural drying for about one night and high-temperature drying at 150 ° C. or lower.
  • the baking treatment described below is performed in a state where a large amount of water contained in the metal-containing solution and water of the cleaning solution remain in the precursor material (A), the regular mesopores of the precursor material (A) are obtained. It is preferable to dry sufficiently because the skeleton structure as a substance may be broken.
  • Step S3 firing step
  • the precursor material (B) in which the metal-containing solution is impregnated into the precursor material (A) for obtaining a carrier having a porous structure composed of a zeolite type compound is calcined to obtain the precursor material (C).
  • the baking treatment is preferably performed, for example, in air at 350 to 850 ° C. for 2 to 30 hours.
  • the metal component impregnated in the pores of the regular mesoporous substance grows as crystals, and metal fine particles are formed in the pores.
  • Step S4 hydrothermal treatment step
  • a mixed solution in which the precursor material (C) and the structure directing agent are mixed is prepared, and the precursor material (C) obtained by calcining the precursor material (B) is subjected to hydrothermal treatment to obtain a catalyst structure. Get the body.
  • the structure-directing agent is a template agent for defining the skeleton structure of the carrier of the catalyst structure, and for example, a surfactant can be used.
  • the structure-directing agent is preferably selected according to the skeleton structure of the carrier of the catalyst structure. For example, tetramethylammonium bromide (TMABr), tetraethylammonium bromide (TEABr), tetrapropylammonium bromide (TPABr), tetraethylammonium hydroxide Surfactants such as (TEAOH) are preferred.
  • the mixing of the precursor material (C) and the structure-directing agent may be performed during the main hydrothermal treatment step or may be performed before the hydrothermal treatment step.
  • the method for preparing the mixed solution is not particularly limited, and the precursor material (C), the structure-directing agent, and the solvent may be simultaneously mixed, or the precursor material (C) and the structure-defining solvent may be mixed in the solvent. After each of the agents is dispersed in each solution, the respective dispersion solutions may be mixed.
  • the solvent for example, water, an organic solvent such as an alcohol, or a mixed solvent thereof can be used. Further, it is preferable that the pH of the mixed solution is adjusted using an acid or a base before performing the hydrothermal treatment.
  • the hydrothermal treatment can be performed by a known method. For example, it is preferable to perform the hydrothermal treatment in a closed container at 80 to 800 ° C., for 5 hours to 240 hours, and at 0 to 2000 kPa.
  • the hydrothermal treatment is preferably performed in a basic atmosphere.
  • the reaction mechanism here is not necessarily clear, the skeleton structure of the precursor material (C) as a regular mesoporous substance is gradually destroyed by performing hydrothermal treatment using the precursor material (C) as a raw material.
  • the structure directing agent By the action of the structure directing agent, a new skeletal structure (porous structure) as a carrier of the catalyst structure is formed while the position of the metal fine particles inside the pores of the precursor material (C) is substantially maintained. .
  • the catalyst structure obtained in this way includes a carrier having a porous structure and metal fine particles contained in the carrier, and the carrier further has a passage in which a plurality of holes communicate with each other due to the porous structure. Is at least partially present in the passage of the carrier.
  • a mixed solution in which the precursor material (C) and the structure directing agent are mixed is prepared, and the precursor material (C) is subjected to hydrothermal treatment.
  • the precursor material (C) may be subjected to hydrothermal treatment without mixing the precursor material (C) and the structure directing agent.
  • the precipitate (catalyst structure) obtained after the hydrothermal treatment is preferably collected (for example, filtered), and then, if necessary, washed, dried and calcined.
  • the cleaning solution water, an organic solvent such as alcohol, or a mixed solution thereof can be used.
  • the drying treatment include natural drying for about one night and high-temperature drying at 150 ° C. or lower. If the baking treatment is performed in a state where a large amount of water remains in the precipitate, the skeleton structure as a carrier of the catalyst structure may be broken. Therefore, it is preferable to sufficiently dry the catalyst structure.
  • the firing treatment can be performed, for example, in air at 350 to 850 ° C. for 2 to 30 hours.
  • the structure directing agent attached to the catalyst structure is burned off.
  • the catalyst structure can be used as it is without subjecting the collected precipitate to a baking treatment, depending on the purpose of use. For example, when the environment in which the catalyst structure is used is a high-temperature environment of an oxidizing atmosphere, by exposing it to the usage environment for a certain period of time, the structure-directing agent is burned out, and the same catalyst structure as in the case of the firing treatment is obtained. Since it is obtained, it can be used as it is.
  • the manufacturing method described above is an example in which the metal element (M) contained in the metal-containing solution to be impregnated into the precursor material (A) is a metal species (for example, a noble metal) that is hardly oxidized.
  • a metal species for example, a noble metal
  • the metal element (M) contained in the metal-containing solution to be impregnated into the precursor material (A) is a metal species (for example, Fe, Co, Cu, or the like) that is easily oxidized
  • the metal element (M) contained in the metal-containing solution is a metal species that is easily oxidized
  • the metal component is oxidized by the heat treatment in the steps (Steps S3 to S4) after the impregnation processing (Step S2). . Therefore, the metal oxide fine particles are inherent in the carrier formed in the hydrothermal treatment step (Step S4).
  • the recovered precipitate is calcined, and further reduced under a reducing gas atmosphere such as hydrogen gas.
  • a reducing gas atmosphere such as hydrogen gas.
  • the metal oxide fine particles existing in the carrier are reduced, and metal fine particles corresponding to the metal element (M) constituting the metal oxide fine particles are formed.
  • M metal element
  • a catalyst structure in which metal fine particles are present in the carrier is obtained.
  • such a reduction treatment may be performed as needed.For example, when the environment in which the catalyst structure is used is a reducing atmosphere, the metal oxide fine particles are exposed to the use environment for a certain period of time. Since the catalyst is reduced, the same catalyst structure as in the case of the reduction treatment is obtained, so that the carrier can be used as it is in the state where the oxide fine particles are inherent.
  • a method for producing a light hydrocarbon wherein a light hydrocarbon is synthesized from carbon monoxide and hydrogen using a catalyst.
  • a catalyst includes a carrier 10 having a porous structure composed of a zeolite-type compound, and at least one metal fine particle 20 existing in the carrier 10.
  • the carrier 10 has a passage 11 communicating with the outside of the carrier. Then, the average internal diameter in a part of the passage 11 is 0.95 nm or less, and the metal fine particles 20 include the catalyst structure 1 existing in the passage 11 having the average internal diameter of 0.95 nm or less. That is, the present invention provides a method for producing a light hydrocarbon that synthesizes a light hydrocarbon from carbon monoxide and hydrogen using the above light hydrocarbon synthesis catalyst structure.
  • the raw material for producing light hydrocarbons using the FT synthesis reaction is not particularly limited as long as it is a synthesis gas containing molecular hydrogen and carbon monoxide as main components.
  • a synthesis gas having a molar ratio of 1.5 to 2.5 is preferable, and a synthesis gas having a molar ratio of 1.8 to 2.2 is more preferable.
  • the reaction conditions of the FT synthesis reaction are not particularly limited, and the reaction can be performed under known conditions.
  • the reaction temperature is preferably 200 to 500 ° C. and 200 to 350 ° C.
  • the pressure (absolute pressure) is preferably 0.1 to 3.0 MPa.
  • the FT synthesis reaction can be carried out in a process known as a Fischer-Tropsch synthesis reaction process, for example, a fixed bed, a supercritical fixed bed, a slurry bed, a fluidized bed and the like.
  • a Fischer-Tropsch synthesis reaction process for example, a fixed bed, a supercritical fixed bed, a slurry bed, a fluidized bed and the like.
  • Preferred processes include fixed beds, supercritical fixed beds, and slurry beds.
  • a light hydrocarbon production device having the above catalyst structure may be provided.
  • a light hydrocarbon production apparatus is not particularly limited as long as it can synthesize a light hydrocarbon using the above-mentioned catalyst structure.
  • a normally used production apparatus such as a reaction apparatus and a reaction column can be used.
  • the device can be used.
  • the catalyst structure according to the present invention in such a light hydrocarbon producing apparatus, the producing apparatus can also exhibit the same effects as described above.
  • the catalyst structure in which the range of the average inner diameter DF in a part of the passage 11 varies depending on the number of carbon atoms. Thereby, the selectivity of the generated light hydrocarbon can be further increased, and in particular, the selectivity of the light hydrocarbon having the same size as the average inner diameter DF can be increased. Further, when there are a plurality of desired light hydrocarbons, a plurality of reaction columns are prepared in advance, and a catalyst structure having a different range of the average inner diameter DF is set in each reaction column according to the intended light hydrocarbons.
  • the catalyst structure already used in the reaction column may be replaced with another catalyst structure having a different range of the average inner diameter DF , or the reaction column provided with the catalyst structure may be replaced with an average inner diameter DF May be replaced with a reaction column provided with another catalyst structure having a different range.
  • the catalyst structure according to the embodiment of the present invention As described above, the catalyst structure according to the embodiment of the present invention, a method for producing the same, a method for producing a hydrocarbon using the catalyst structure, and a hydrocarbon production apparatus having the catalyst structure have been described.
  • the present invention is not limited to the embodiments, and various modifications and changes can be made based on the technical idea of the present invention.
  • a mixed aqueous solution is prepared by mixing a silica agent (tetraethoxysilane (TEOS), manufactured by Wako Pure Chemical Industries, Ltd.) and a surfactant as a template, and the pH is adjusted as appropriate. For 100 hours. Thereafter, the generated precipitate was separated by filtration, washed with water and ethanol, and further calcined at 600 ° C. for 24 hours in the air to obtain a precursor material (A) having a type and a pore diameter shown in Table 1. .
  • TEOS tetraethoxysilane
  • CTAB hexadecyltrimethylammonium bromide
  • metal fine particles metal salt
  • Co Cobalt (II) nitrate hexahydrate (Wako Pure Chemical Industries, Ltd.) ⁇ Ni: Nickel (II) nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) ⁇ Fe: Iron (III) nitrate nonahydrate (Wako Pure Chemical Industries, Ltd.) ⁇ Ru: Ruthenium (III) chloride anhydrous (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • the metal-containing aqueous solution is added to the powdered precursor material (A) in small portions in a plurality of portions, and dried at room temperature (20 ° C. ⁇ 10 ° C.) for 12 hours or more to obtain the precursor material (B). I got
  • the condition for the presence or absence of the additive shown in Table 1 was set to “Yes”, and the precursor material (A) before the addition of the metal-containing aqueous solution was added to polyoxyethylene (15) oleyl ether (NIKKOL) as an additive.
  • NIKKOL polyoxyethylene (15) oleyl ether
  • the amount of the metal-containing aqueous solution to be added to the precursor material (A) (the amount charged) is determined based on the amount of silicon (Si) constituting the precursor material (A) with respect to the metal element (M) contained in the metal-containing aqueous solution. ) (Atomic ratio Si / M) was adjusted so as to be the value shown in Table 1.
  • precursor material (B) impregnated with the metal-containing aqueous solution obtained as described above was calcined at 600 ° C. for 24 hours in air to obtain a precursor material (C).
  • the precursor material (C) obtained as described above and the structure-directing agent shown in Table 1 were mixed to prepare a mixed aqueous solution. Hydrothermal treatment was performed under the condition of time. Thereafter, the formed precipitate was separated by filtration, washed with water, dried at 100 ° C. for 12 hours or more, and further calcined at 600 ° C. for 24 hours in the air. Thereafter, the calcined product was recovered and subjected to a reduction treatment at 500 ° C. for 60 minutes under flowing hydrogen gas to obtain a catalyst structure having a carrier and metal fine particles as a catalyst substance shown in Table 1 (Examples). 1 to 24).
  • Comparative Example 1 MFI-type silicalite was mixed with cobalt oxide powder (II, III) having an average particle size of 50 nm or less (manufactured by Sigma-Aldrich Japan GK), and subjected to a hydrogen reduction treatment in the same manner as in the Example to obtain a carrier.
  • cobalt oxide powder II, III
  • a catalyst structure was obtained in which cobalt particles having high activity as a catalyst substance were attached to the outer surface of silicalite.
  • the MFI-type silicalite was synthesized in the same manner as in Example 1 except for the step of adding a metal.
  • the catalyst structure in which the metal is iron fine particles (Fe) was cut out by FIB (focused ion beam) processing, and then subjected to SEM (SU8020, manufactured by Hitachi High-Technologies Corporation) and EDX (X-Max). , Manufactured by Horiba, Ltd.). As a result, Fe element was detected from inside the support. From the results of the cross-sectional observation using the TEM and SEM / EDX, it was confirmed that iron fine particles were present inside the carrier.
  • the average inner diameter DF is based on literature values described in a database of zeolite structures (http://www.iza-structure.org/databases/), and for each pore of each zeolite structure, It was calculated from the value obtained by equally adding the major axis and the minor axis.
  • iron fine particles of various sizes randomly exist in the range of about 50 nm to 400 nm in diameter, whereas iron particles having an average particle diameter of 1.2 nm to 2.0 nm obtained from the TEM image were obtained.
  • a scattering peak having a particle diameter of 10 nm or less was detected also in the measurement result of SAXS. From the measurement results of SAXS and the cross-sectional measurement by SEM / EDX, it was found that the catalyst substance having a particle size of 10 nm or less was present in the support in a uniform state and in a very high dispersion state.
  • Quantification of the amount of metal was performed using ICP (high frequency inductively coupled plasma) alone or a combination of ICP and XRF (X-ray fluorescence analysis).
  • XRF energy dispersive X-ray fluorescence spectrometer "SEA1200VX", manufactured by SSI NanoTechnology Inc.
  • SE1200VX energy dispersive X-ray fluorescence spectrometer
  • SEA1200VX acceleration voltage of 50 kV
  • the amount of metal included in the catalyst structure increased with an increase in the amount of the metal-containing solution at least in the range of the atomic ratio Si / M of 50 to 1,000. Was done.
  • a C3 compound group containing a hydrocarbon having 3 carbon atoms (hereinafter, also simply referred to as “C3”) or a C4 compound group containing a hydrocarbon having 4 carbon atoms (hereinafter, simply referred to as “C3”)
  • C3 a C3 compound group containing a hydrocarbon having 3 carbon atoms
  • C4 a C4 compound group containing a hydrocarbon having 4 carbon atoms
  • the compounds included in the C3 compound group include propane, propylene, and propanol
  • the compounds included in the C4 compound group include n-butane, n-butene, isobutane, isobutene, n-butanol, isobutanol, and the like. No.
  • the selectivity of light hydrocarbons is judged to be acceptable (acceptable), and " ⁇ ", the selectivity of propylene or butene (n-butene and isobutene) is 3%. When it was less than 1, it was determined that the selectivity of the light hydrocarbon was poor (impossible), and was evaluated as “x”.
  • the selectivity of light hydrocarbons is mainly related to the pore diameter (average inner diameter DF ) depending on the framework structure of the zeolite type compound. Therefore, in Examples 1 to 24, the selectivity of light hydrocarbons could be improved by selecting a zeolite having an appropriate skeleton structure according to the desired molecular size of light hydrocarbons.
  • a support having a skeletal structure composed of MFI-type zeolite is used. Therefore, the selectivity of propylene and butene (n-butene and isobutene) as olefins tends to be improved.
  • MFI-type zeolite the average inner diameter D F of [010] axis is 0.55 nm, the average inner diameter D F of [100] axis is 0.53 nm, the average inner diameter D F of each axis of n- butenes Despite being smaller than the molecular size, it showed good or excellent selectivity for butenes (n-butene and isobutene).
  • the catalyst structures show excellent light hydrocarbon selectivity in the synthesis of hydrocarbons, particularly in the FT synthesis reaction for synthesizing light hydrocarbons from carbon monoxide and hydrogen. I understood that.
  • additional operations such as a purification process required in a conventional synthesis process can be omitted, and as a result, production efficiency can be improved. .

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Abstract

Une structure de catalyseur de synthèse d'hydrocarbures légers (1) selon la présente invention comprend : un support (10) qui est configuré à partir d'un composé à zéolite, tout en ayant une structure poreuse; et au moins une particule fine métallique (20) qui est présente à l'intérieur du support (10). Le support (10) a un passage (11) qui est en communication avec l'extérieur du support (10); le diamètre interne moyen d'une partie du passage (11) est de 0,95 nm ou moins; et la particule fine métallique (20) est présente dans le passage (11) qui a un diamètre interne moyen de 0,95 nm ou moins.
PCT/JP2019/030482 2018-08-03 2019-08-02 Structure de catalyseur de synthèse d'hydrocarbures légers, appareil de production d'hydrocarbures légers, et procédé de production d'hydrocarbures légers WO2020027321A1 (fr)

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