WO2020183932A1 - 触媒部材及び反応器 - Google Patents
触媒部材及び反応器 Download PDFInfo
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- WO2020183932A1 WO2020183932A1 PCT/JP2020/002415 JP2020002415W WO2020183932A1 WO 2020183932 A1 WO2020183932 A1 WO 2020183932A1 JP 2020002415 W JP2020002415 W JP 2020002415W WO 2020183932 A1 WO2020183932 A1 WO 2020183932A1
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- Prior art keywords
- catalyst
- layer
- support
- catalyst member
- reactor
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 159
- 230000010287 polarization Effects 0.000 claims abstract description 56
- 238000005192 partition Methods 0.000 claims description 19
- 239000000919 ceramic Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 230000002093 peripheral effect Effects 0.000 claims description 8
- 239000011982 enantioselective catalyst Substances 0.000 claims description 6
- 150000004696 coordination complex Chemical group 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 239000003989 dielectric material Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 28
- 238000000034 method Methods 0.000 description 25
- 239000002994 raw material Substances 0.000 description 15
- 239000007795 chemical reaction product Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 239000012530 fluid Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012466 permeate Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000009881 electrostatic interaction Effects 0.000 description 3
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 2
- WSMQKESQZFQMFW-UHFFFAOYSA-N 5-methyl-pyrazole-3-carboxylic acid Chemical compound CC1=CC(C(O)=O)=NN1 WSMQKESQZFQMFW-UHFFFAOYSA-N 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical group C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
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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
- 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
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
-
- 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
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
-
- 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
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
-
- 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
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/02—Apparatus characterised by their chemically-resistant properties
- B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
- B01J2219/0254—Glass
-
- 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
- Y02P20/584—Recycling of catalysts
Definitions
- the present invention relates to a catalyst member and a reactor.
- the present invention relates to catalyst members and reactors used in the synthesis of compounds used in pharmaceuticals, fragrances and the like.
- Compounds are generally synthesized by using a batch method in which raw materials, catalysts, etc. are put into a reactor and reacted, and when the reaction is completed, the reaction product is taken out.
- the batch method can synthesize compounds having a complicated structure used in pharmaceuticals, fragrances, etc., but has problems such as low productivity because it is necessary to separate and recover the catalyst from the reaction product.
- Non-Patent Document 1 proposes a method in which a mixture containing a raw material and a liquid catalyst is circulated in a tubular reactor to carry out the reaction. Further, Patent Document 1 proposes a method of carrying out a reaction by circulating a raw material through a reactor (microchannel) in which a catalyst is supported on a support forming a flow path of the raw material.
- Non-Patent Document 1 uses a liquid catalyst, it is necessary to separate and recover the liquid catalyst from the reaction product after the reaction. Further, in the method of Patent Document 1, the catalyst is rarely detached from the support in the gas reaction, but the catalyst is easily detached from the support in the liquid reaction, and the catalyst may be mixed in the reaction product. .. Therefore, even with this method, it may be necessary to separate and recover the catalyst from the reaction product. In addition, as the catalyst is desorbed from the support, the reaction efficiency decreases, so that it becomes necessary to replace the reactor.
- the present invention has been made to solve the above problems, and provides a catalyst member and a reactor in which the catalyst is difficult to be detached from the support and the catalyst does not need to be separated and recovered from the reaction product. With the goal.
- the catalyst layer can be firmly fixed to the support by providing a polarization layer between the support and the catalyst layer.
- the present invention has been completed.
- the catalyst member according to one aspect of the present invention has a support, a polarization layer provided on the support, and a catalyst layer provided on the polarization layer.
- the polarization layer is formed of a dielectric material.
- the catalyst member according to one aspect of the present invention includes a catalyst in which the catalyst layer has a metal.
- the catalyst is a metal complex catalyst.
- the metal complex catalyst is an asymmetric catalyst.
- the support is formed of ceramics. In another embodiment of the catalyst member according to one aspect of the present invention, the support has a translucent property, and a polarization layer and a catalyst layer are not provided in a part of the support. In another embodiment of the catalyst member according to one aspect of the present invention, at least a part of a support, a polarization layer, and a catalyst layer is translucent. In another embodiment of the catalyst member according to one aspect of the present invention, the support is a partition wall of a honeycomb structure.
- the reactor according to another aspect of the present invention includes the above-mentioned catalyst member.
- the reactor according to another aspect of the present invention further comprises a container for accommodating the catalyst member.
- at least a part of the container is translucent.
- the reactor according to another aspect of the present invention is a tubular container in which the support of the catalyst member is a partition wall of the honeycomb structure and the container covers the outer peripheral wall of the honeycomb structure. ..
- the reactor according to another aspect of the invention is used in flow synthesis in another embodiment.
- the present invention it is possible to provide a catalyst member and a reactor in which the catalyst is difficult to be detached from the support and the catalyst does not need to be separated and recovered from the reaction product.
- FIG. 1 is a cross-sectional view of the catalyst member according to the first embodiment of the present invention.
- the catalyst member 10 according to the first embodiment of the present invention includes a support 11, a polarization layer 12 provided on the support 11, and a catalyst layer 13 provided on the polarization layer 12. And.
- the material and shape of the support 11 are not particularly limited as long as it does not inhibit the reaction.
- the material of the support 11 include ceramics, metal, silica, polyethylene, polystyrene and the like.
- the material of the support 11 is preferably ceramic from the viewpoint of adhesion to the polarization layer 12 (particularly, the polarization layer 12 formed of the dielectric).
- the ceramics are not particularly limited, and examples thereof include zirconia, cordierite, zeolite, and alumina.
- the support 11 preferably has a thermal conductivity of 2 W / m ⁇ K or more.
- the shape of the support 11 examples include a honeycomb shape, a foam shape, a monolith shape, a corrugated shape, and the like.
- the shape of the support 11 is preferably a honeycomb shape. Since the honeycomb-shaped support 11 has a large specific surface area, the reaction efficiency can be improved and the catalyst member 10 can be miniaturized. In addition, these shapes can be obtained by an extrusion molding method or a mold cast molding method.
- the polarization layer 12 is not particularly limited as long as it is formed of a material capable of electric polarization.
- a material capable of electric polarization for example, a dielectric can be used.
- the ferroelectric for example, lithium niobate (LiNbO 3), lithium tantalate (LiTaO 3), barium titanate (BaTiO 3), lead zirconate titanate (PbZrTiO 3; PZT), a portion of the lead PZT PLZT in which is replaced with lantern La and the like can be mentioned.
- the polarization layer 12 is polarized to a positive charge on the support 11 side and a negative charge on the catalyst layer 13 side. Since the polarized layer 12 polarized in this way can be bonded to the catalyst layer 13 having a positive charge by electrostatic interaction, the catalyst layer 13 is less likely to be detached from the polarized layer 12.
- the polarization layer 12 is preferably an oriented polarization layer in which the crystal orientations (crystal axes) are aligned in one direction. Since the oriented polarization layer is a layer having a dense structure, the catalyst layer 13 can be satisfactorily formed on the oriented polarization layer. Further, the oriented polarization layer can be supported while maintaining the chirality of the asymmetric catalyst when an asymmetric catalyst is used as the catalyst used for the catalyst layer 13.
- the catalyst layer 13 is not particularly limited and may be a layer formed from a known catalyst.
- the type of catalyst may be appropriately selected according to the type of reaction in which the catalyst member 10 is used, and is not particularly limited.
- the catalyst preferably has a metal from the viewpoint of the binding force with the polarization layer 12. Since the catalyst having a metal has a positive charge and can be bonded to the surface of the polarization layer 12 polarized to a negative charge by electrostatic interaction, the catalyst layer 13 is difficult to be detached from the polarization layer 12.
- the catalyst having a metal examples include precious metals such as platinum and palladium, iron oxide and the like. Further, a noble metal may be used as a catalyst by supporting it on a carrier such as activated carbon or silica gel. Further, a metal complex catalyst in which a ligand is bonded to a metal ion, particularly an asymmetric catalyst having an asymmetric ligand may be used as the catalyst. By using such a catalyst, it becomes possible to synthesize a compound having a complicated structure (for example, a compound having at least one asymmetric atom). Examples of the asymmetric catalyst include those in which an asymmetric ligand such as BINAP is bonded to a metal ion such as ruthenium, rhodium, and palladium.
- the catalyst member 10 having the above-mentioned structure can be manufactured by sequentially forming the polarization layer 12 and the catalyst layer 13 on the support 11.
- the method for forming the polarization layer 12 is not particularly limited, and can be performed according to a known method.
- the polarization layer 12 can be formed by using a hydrothermal synthesis method or the like. If necessary, the polarization layer 12 may be subjected to a polarization process in which a high voltage is applied in order to align the directions of polarization.
- the method for forming the catalyst layer 13 is not particularly limited, and the catalyst layer 13 can be formed according to a known method.
- the catalyst layer 13 can be formed by applying a liquid in which the catalyst is dissolved or dispersed on the polarization layer 12 and drying the solution.
- the catalyst layer 13 is firmly fixed to the polarization layer 12. Therefore, in the catalyst member 10, the catalyst layer 13 is hard to be separated from the polarization layer 12, the catalyst can be prevented from being mixed into the reaction product, and the catalyst function is hard to be deteriorated.
- FIG. 2 is a cross-sectional view of the catalyst member according to the second embodiment of the present invention.
- the same components as those of the catalyst member 10 according to the first embodiment of the present invention are designated by the same reference numerals, and the overlapping portions will be omitted.
- the catalyst member 20 according to the second embodiment of the present invention is not provided with the polarization layer 12 and the catalyst layer 13 in a part of the support 11.
- the support 11 has translucency. With the above configuration, it is possible to confirm the reaction status on the catalyst layer 13 side via the support 11.
- the term "translucency" as used herein means that in a sample having a thickness of 0.5 mm, the linear transmittance is 20 when the linear transmittance of visible light, particularly light having a wavelength of 400 to 700 nm is measured. It means that it is% or more.
- the linear transmittance is preferably 30% or more, more preferably 40% or more, still more preferably 50% or more.
- the linear transmittance of light can be measured using a spectrophotometer (LAMBDA 900 ultraviolet visible near infrared spectrophotometer manufactured by PerkinElmer).
- the material of the support 11 having translucency is not particularly limited, and examples thereof include translucent ceramics containing zirconia or alumina as a main component, quartz glass, and the like.
- translucent ceramics containing zirconia as a main component for example, translucent zirconia made of cubic yttria-stabilized zirconia (YSZ) can be used. This translucent zirconia has a linear transmittance of about 25% and a thermal conductivity of 3 W / m ⁇ K.
- translucent ceramic containing alumina as a main component for example, translucent alumina made of high-purity alumina can be used. This translucent alumina has a linear transmittance of about 50% and a thermal conductivity of 38 W / m ⁇ K.
- the light-transmitting polarization layer 12 is not particularly limited, and examples thereof include a layer formed of a transparent dielectric such as PLZT, gallium nitride, and aluminum nitride.
- the polarization layer 12 may be a single crystal or a polycrystal, but it is preferable to orient the crystal on an axis having a large polarization.
- the light-transmitting catalyst layer 13 is not particularly limited, and may be a layer that can be formed from a light-transmitting catalyst, and the amount of adhesion of the catalyst is reduced (that is, the thickness of the catalyst layer 13 is reduced). By doing so, translucency may be ensured.
- FIG. 3 is a perspective view of the catalyst member according to the third embodiment of the present invention.
- FIG. 4 is a cross-sectional view (cross-sectional view perpendicular to the direction in which the cell extends) of the catalyst member according to the third embodiment of the present invention.
- the same components as those of the catalyst members 10 and 20 according to the first and second embodiments of the present invention are designated by the same reference numerals, and the overlapping portions will be omitted.
- the internal structure observed through the outer surface is represented by a dotted line.
- the support 11 has a honeycomb shape, that is, a partition wall 33 of a honeycomb structure.
- the catalyst member 30 is provided on a partition wall 33 for partitioning a plurality of cells 32 extending from the fluid inflow end surface 31a to the fluid outflow end surface 31b, a polarization layer 12 provided on the partition wall 33, and a polarization layer 12. It has a provided catalyst layer 13. Since the outer peripheral surface of the catalyst member 30 is surrounded by the outer peripheral wall 34, the catalyst member 30 itself can be used as a reactor.
- the shape of the cross section perpendicular to the direction in which the cell 32 of the honeycomb structure extends is not particularly limited, but may be various shapes such as a circle, an ellipse, a triangle, a quadrangle, a hexagon, and an octagon. Among them, the shape of the honeycomb structure is preferably circular.
- the size of the honeycomb structure is not particularly limited, and may be appropriately adjusted according to the type and scale of the reaction.
- the shape of the cell 32 (the shape of the cell 32 in the cross section perpendicular to the direction in which the cell 32 extends) is not particularly limited, but may be various shapes such as a circle, an ellipse, a triangle, a quadrangle, a hexagon, and an octagon. it can. Among them, the shape of the cell 32 is preferably a quadrangle (square or rectangle).
- the size of the cell 32 is not particularly limited, but the diameter of the cell 32 in the cross section perpendicular to the extending direction of the cell 32 is preferably 1 to 3 mm, more preferably 1.5 to 2.5 mm.
- the diameter of the cell 32 By setting the diameter of the cell 32 to 1 mm or more, the amount of raw materials that can be supplied into the cell 32 can be increased. Further, by setting the diameter of the cell 32 to 3 mm or less, the contact area with the catalyst is increased, so that the reaction efficiency can be improved.
- the diameter of the cell 32 means the length of the portion having the maximum diameter.
- the thickness of the partition wall 33 is not particularly limited, but is preferably 0.05 to 0.3 mm, more preferably 0.08 to 0.15 mm. Strength can be ensured by setting the thickness of the partition wall 33 to 0.05 mm or more. Further, by setting the thickness of the partition wall 33 to 0.3 mm or less, the amount of raw materials that can be supplied into the cell 32 can be increased.
- the catalyst member 30 having the above-mentioned structure can carry out the reaction in the cell 32 by putting the raw material into the cell 32.
- the catalyst member 30 can be used by either the batch method or the flow method, but is particularly suitable for use in the flow method.
- the raw material is housed in the cell 32 and the reaction is carried out by sealing the cell 32 of the fluid outflow end face 31b.
- the catalyst member 30 is used by the flow method, the raw material is continuously charged from the fluid inflow end face 31a to carry out the reaction in the cell 32, and the reaction product is continuously discharged from the fluid outflow end face 31b.
- the catalyst layer 13 is difficult to be separated from the polarization layer 12, it is possible to suppress the catalyst from being mixed into the reaction product in either the batch method or the flow method, and the catalyst function is also deteriorated. hard.
- the partition wall 33 which is the support 11 has translucency, and the polarization layer 12 and the catalyst layer 13 are not provided in a part of the partition wall 33.
- the partition wall 33 and the outer peripheral wall 34 of the honeycomb structure are preferably formed of a material that does not allow the gas to permeate. Examples of such materials include metals, silica, polyethylene, polystyrene and the like.
- the partition wall 33 and the outer peripheral wall 34 of the honeycomb structure are preferably formed of a material that does not permeate the liquid and permeates the gas. With such a configuration, it becomes possible to separate the gas generated during the reaction through the outer peripheral wall 34.
- the material that does not permeate the liquid and permeates the gas include a porous material such as ceramics.
- Such a porous material can be obtained by controlling the pore size.
- the pore diameter of the porous material may be larger than the molecular diameter of the gas generated during the reaction and smaller than the molecular diameter of the raw material or reaction product used in the reaction.
- the pore size of the porous material can be controlled by adjusting the type and blending ratio of the components (for example, pore-forming agent) used for preparing the porous material.
- the reactor according to the fourth embodiment of the present invention further includes a container for accommodating the catalyst members 10, 20, and 30 according to the first to third embodiments of the present invention.
- a container for accommodating the catalyst members 10, 20, and 30 according to the first to third embodiments of the present invention.
- the container is not particularly limited as long as it can accommodate the catalyst members 10, 20, and 30 and does not inhibit the reaction.
- the container can be made of, for example, metal, glass, ceramics, plastic or the like.
- the reactor 40 includes a catalyst member 30 and a tubular container 41 that covers the outer peripheral wall 34 of the catalyst member 30.
- the reactor 40 When the reactor 40 is used in the flow method, the raw materials are continuously charged from the fluid inflow end face 31a of the catalyst member 30 to carry out the reaction in the cell 32, and the reaction product is continuously supplied from the fluid outflow end face 31b of the catalyst member 30. To discharge.
- the arrow indicates the flow direction of the raw material. Since the reactor 40 uses the catalyst member 30, it is possible to prevent the catalyst from being mixed into the reaction product, and the catalyst function is unlikely to deteriorate.
- the partition wall 33 of the catalyst member 30 is translucent and the polarization layer 12 and the catalyst layer 13 are not provided on a part of the partition wall 33, it is preferable that at least a part of the tubular container 41 is translucent. .. With such a configuration, it is possible to check the inside of the reactor 40. Similarly, when at least a part of the partition wall 33, the polarization layer 12 and the catalyst layer 13 of the catalyst member 30 is translucent, it is preferable that at least a part of the tubular container 41 is translucent. With such a configuration, it is possible to check the inside of the reactor 40.
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Abstract
Description
また、特許文献1の方法は、気体反応では触媒が支持体から脱離することは少ないが、液体反応では触媒が支持体から脱離し易く、反応生成物に触媒が混入してしまうことがある。そのため、この方法でも、反応生成物から触媒を分離回収しなければならないことがある。また、支持体から触媒が脱離するにつれて反応効率も低下するため、反応器を交換する必要も生じてしまう。
本発明は、上記のような問題を解決するためになされたものであり、支持体から触媒が脱離し難く、反応生成物から触媒を分離回収する必要がない触媒部材及び反応器を提供することを目的とする。
本発明の一側面に係る触媒部材は、一実施形態において、分極層が誘電体から形成されている。
本発明の一側面に係る触媒部材は、別の一実施形態において、触媒層が、金属を有する触媒を含む。
本発明の一側面に係る触媒部材は、別の一実施形態において、触媒が金属錯体触媒である。
本発明の一側面に係る触媒部材は、別の一実施形態において、金属錯体触媒が不斉触媒である。
本発明の一側面に係る触媒部材は、別の一実施形態において、支持体が透光性を有し、且つ支持体の一部に分極層及び触媒層が設けられていない。
本発明の一側面に係る触媒部材は、別の一実施形態において、支持体、分極層及び触媒層の少なくとも一部が透光性を有する。
本発明の一側面に係る触媒部材は、別の一実施形態において、支持体がハニカム構造体の隔壁である。
本発明の別の一側面に係る反応器は、一実施形態において、触媒部材を収容する容器をさらに備える。
本発明の別の一側面に係る反応器は、別の一実施形態において、容器の少なくとも一部が透光性を有する。
本発明の別の一側面に係る反応器は、別の一実施形態において、触媒部材の支持体がハニカム構造体の隔壁であり、容器が、ハニカム構造体の外周壁を被覆する管状容器である。
本発明の別の一側面に係る反応器は、別の一実施形態において、フロー合成に用いられる。
図1は、本発明の実施形態1に係る触媒部材の断面図である。図1に示されるように、本発明の実施形態1に係る触媒部材10は、支持体11と、支持体11上に設けられた分極層12と、分極層12上に設けられた触媒層13とを備える。
支持体11の材質としては、例えば、セラミックス、金属、シリカ、ポリエチレン、ポリスチレンなどが挙げられる。これらの中でも、支持体11の材質は、分極層12(特に、誘電体から形成された分極層12)との接着性の観点から、セラミックスであることが好ましい。セラミックスとしては、特に限定されないが、ジルコニア、コージェライト、ゼオライト、アルミナなどが挙げられる。
強誘電体としては、例えば、ニオブ酸リチウム(LiNbO3)、タンタル酸リチウム(LiTaO3)、チタン酸バリウム(BaTiO3)、ジルコン酸チタン酸鉛(PbZrTiO3;PZT)、PZTの鉛の一部をランタンLaで置換したPLZTなどが挙げられる。
触媒は、分極層12との結合力の観点から、金属を有することが好ましい。金属を有する触媒は、正電荷を有しており、負電荷に分極した分極層12の表面と静電相互作用によって結合させることができるため、分極層12から触媒層13が脱離し難くなる。
分極層12の形成方法としては、特に限定されず、公知の方法に準じて行うことができる。例えば、水熱合成法などを用いることによって分極層12を形成することができる。分極層12は、必要に応じて、分極の向きを揃えるために、高電圧を加える分極処理を行ってもよい。
触媒層13の形成方法としては、特に限定されず、公知の方法に準じて行うことができる。例えば、触媒を溶解又は分散した液を分極層12上に塗布して乾燥することよって触媒層13を形成することができる。
図2は、本発明の実施形態2に係る触媒部材の断面図である。なお、本発明の実施形態1に係る触媒部材10と同一の構成要素には同一符号を付し、重複する部分は説明を省略する。
上記のような構成とすることにより、支持体11を介して触媒層13側の反応状況を確認することが可能になる。
透光性を有する分極層12としては、特に限定されず、PLZT、窒化ガリウム、窒化アルミニウムなどの透明誘電体から形成される層が挙げられる。分極層12は、単結晶体であっても多結晶体であってもよいが、分極が大きい軸に結晶配向させることが好ましい。例示した上記3つの材料はいずれもc軸に分極を有するので、c軸配向させることが好ましいが、a軸に分極を有する材料を用いる場合はa軸配向させるとよい。
透光性を有する触媒層13としては、特に限定されず、透光性を有する触媒から形成され得る層としてもよいし、触媒の付着量を低減(すなわち、触媒層13の厚みを低減)することによって透光性を確保してもよい。
図3は、本発明の実施形態3に係る触媒部材の斜視図である。また、図4は、本発明の実施形態3に係る触媒部材の断面図(セルが延びる方向に垂直な断面図)である。なお、本発明の実施形態1及び2に係る触媒部材10,20と同一の構成要素には同一符号を付し、重複する部分は説明を省略する。また、図3では、外側表面から透過して観察される内部構造を点線で表している。
なお、ハニカム構造体の大きさは、特に限定されず、反応の種類やスケールなどに応じて適宜調整すればよい。
触媒部材30をバッチ法で用いる場合、流体流出端面31bのセル32を目封止することにより、原料をセル32内に収容して反応を行う。また、触媒部材30をフロー法で用いる場合、原料を流体流入端面31aから連続的に投入してセル32内で反応を行い、流体流出端面31bから反応生成物を連続的に排出させる。この触媒部材30は、分極層12から触媒層13が脱離し難いため、バッチ法又はフロー法のいずれにおいても反応生成物に触媒が混入することを抑制することができると共に、触媒機能も低下し難い。
同様に、隔壁33、分極層12及び触媒層13の少なくとも一部が透光性を有する構成とすることにより、反応器である触媒部材30の内部の様子を確認することが可能になる。
また、ハニカム構造体の隔壁33及び外周壁34は、反応に用いられる原料が液体である場合、液体を透過せず且つ気体を透過する材料から形成されていることが好ましい。このような構成とすることにより、反応中に発生する気体の分離を、外周壁34を介して行うことが可能になる。液体を透過せず且つ気体を透過する材料としては、セラミックスなどの多孔質材料が挙げられる。このような多孔質材料は、気孔径を制御することによって得ることができる。具体的には、多孔質材料の気孔径を、反応中に発生する気体の分子径よりも大きく、且つ反応に用いられる原料や反応生成物の分子径よりも小さくすればよい。多孔質材料の気孔径は、多孔質材料の調製に用いる成分(例えば、造孔剤)の種類や配合割合などを調整することによって制御することができる。
本発明の実施形態4に係る反応器は、本発明の実施形態1~3に係る触媒部材10,20,30を収容する容器をさらに備える。このような構成とすることにより、触媒部材10,20,30が外部から遮断されるため、触媒部材10,20,30が外部からの衝撃などによって破損する恐れを低減することができる。
容器としては、触媒部材10,20,30を収容することが可能であり、反応を阻害しないものであれば、特に限定されない。
容器は、例えば、金属、ガラス、セラミックス、プラスチックなどから作製することができる。
図5に示されるように、反応器40は、触媒部材30と、触媒部材30の外周壁34を被覆する管状容器41とを備える。反応器40をフロー法で用いる場合、原料を触媒部材30の流体流入端面31aから連続的に投入してセル32内で反応を行い、触媒部材30の流体流出端面31bから反応生成物を連続的に排出させる。なお、図5において、矢印は、原料の流れ方向を表している。この反応器40は、触媒部材30を用いているため、反応生成物に触媒が混入することを抑制することができると共に、触媒機能も低下し難い。
同様に、触媒部材30の隔壁33、分極層12及び触媒層13の少なくとも一部が透光性を有する場合、管状容器41の少なくとも一部が透光性を有することが好ましい。このような構成とすることにより、反応器40の内部の様子を確認することが可能になる。
11 支持体
12 分極層
13 触媒層
31a 流体流入端面
31b 流体流出端面
32 セル
33 隔壁
34 外周壁
40 反応器
41 管状容器
Claims (14)
- 支持体と、前記支持体上に設けられた分極層と、前記分極層上に設けられた触媒層とを有する触媒部材。
- 前記分極層は誘電体から形成されている、請求項1に記載の触媒部材。
- 前記触媒層は、金属を有する触媒を含む、請求項1又は2に記載の触媒部材。
- 前記触媒は金属錯体触媒である、請求項3に記載の触媒部材。
- 前記金属錯体触媒は不斉触媒である、請求項4に記載の触媒部材。
- 前記支持体はセラミックスから形成されている、請求項1~5のいずれか一項に記載の触媒部材。
- 前記支持体が透光性を有し、且つ前記支持体の一部に分極層及び触媒層が設けられていない、請求項1~6のいずれか一項に記載の触媒部材。
- 前記支持体、前記分極層及び前記触媒層の少なくとも一部が透光性を有する、請求項1~6のいずれか一項に記載の触媒部材。
- 前記支持体はハニカム構造体の隔壁である、請求項1~8のいずれか一項に記載の触媒部材。
- 請求項1~9のいずれか一項に記載の触媒部材を備える反応器。
- 前記触媒部材を収容する容器をさらに備える、請求項10に記載の反応器。
- 前記容器の少なくとも一部が透光性を有する、請求項11に記載の反応器。
- 前記触媒部材の支持体が、ハニカム構造体の隔壁であり、前記容器が、前記ハニカム構造体の外周壁を被覆する管状容器である、請求項11又は12に記載の反応器。
- フロー合成に用いられる請求項10~13のいずれか一項に記載の反応器。
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JPH01157398A (ja) * | 1987-09-18 | 1989-06-20 | Ngk Insulators Ltd | 光学活性体の合成法 |
US6544923B1 (en) * | 1999-08-25 | 2003-04-08 | Massachusetts Institute Of Technology | Surface-confined catalytic compositions |
JP2004105812A (ja) * | 2002-09-13 | 2004-04-08 | Toshiba Corp | 光触媒反応装置および光触媒反応方法 |
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