WO2022209849A1 - Réacteur à membrane, installation chimique, et procédé de fabrication de fluide - Google Patents

Réacteur à membrane, installation chimique, et procédé de fabrication de fluide Download PDF

Info

Publication number
WO2022209849A1
WO2022209849A1 PCT/JP2022/011582 JP2022011582W WO2022209849A1 WO 2022209849 A1 WO2022209849 A1 WO 2022209849A1 JP 2022011582 W JP2022011582 W JP 2022011582W WO 2022209849 A1 WO2022209849 A1 WO 2022209849A1
Authority
WO
WIPO (PCT)
Prior art keywords
membrane
fibrous material
fluid separation
membrane reactor
fluid
Prior art date
Application number
PCT/JP2022/011582
Other languages
English (en)
Japanese (ja)
Inventor
柿山創
三原崇晃
Original Assignee
東レ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to JP2022517764A priority Critical patent/JPWO2022209849A1/ja
Publication of WO2022209849A1 publication Critical patent/WO2022209849A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers

Definitions

  • the present invention relates to membrane reactors.
  • a chemical process generally consists of a reaction process and a purification process.
  • a reaction process is a process of obtaining a product from a reactant, optionally using a catalyst.
  • the reaction rate has an upper limit governed by chemical equilibrium, and the reaction rate cannot be increased to suppress side reactions.
  • the purification process is a process of separating the product from unreacted substances and by-products after the reaction. Distillation, which is a typical refining process, requires temperature and pressure to fluctuate, resulting in a large energy loss.
  • a membrane reactor that integrates the reaction process and the purification process has been proposed.
  • a catalyst is placed on the surface of the separation membrane and between the separation membranes, and the reaction process proceeds in the space where the separation membrane exists.
  • products or by-products generated in the reaction process are removed from the reaction system via the separation membrane, thereby shifting the equilibrium to the product side and improving the reaction rate.
  • energy-saving refinement can be achieved.
  • a membrane reactor as a method of efficiently supplying the removed components to the separation membrane, a method of arranging a spacer or a rectifying plate in the reaction chamber is known (see, for example, Patent Documents 1 and 2).
  • WO 2005/010303 has at least at least one bundle of ceramic capillaries (9) and a housing surrounding the bundle, said capillaries being joined at their (both) ends by a perforated plate, and
  • the housing has an inlet tube and/or an outlet tube connected to the interior of the capillaries for the first material stream and connected to the gap between the capillaries for the second material stream.
  • a separation module is disclosed, having inlet and/or outlet tubes, characterized in that the distance between the capillaries is kept constant by spacers (6).
  • the spacers for generating forced flow become dead spaces in the separation module and partially cover the surfaces of the ceramic capillaries.
  • there was a problem of filling the storage space for the catalyst Due to the dead space, there is concern about a decrease in productivity and an increase in equipment size.
  • Patent Document 2 discloses a selectively permeable membrane reactor in which a raw material gas flowing from the inlet of the reactor reacts in a reaction chamber filled with a catalyst in the reactor, and the product gas produced is discharged into the reactor.
  • a selectively permeable membrane reactor in which the by-product gas is discharged from an outlet and is allowed to permeate the selectively permeable membrane and flow out of the reaction chamber, the reactor is provided with a porous tube having a selectively permeable membrane formed on its surface. a catalyst layer is provided in the gap between the inner wall of the reactor and the porous tube to form a reaction chamber;
  • a selectively permeable membrane reactor is disclosed, which is characterized in that it is provided in a reaction chamber.
  • the present invention has the following configuration. That is, the present invention is a membrane reactor comprising, in a vessel, fluid separation membranes for separating a fluid to be separated, and fibrous materials existing between the fluid separation membranes, wherein the fibrous materials contain a catalyst. It is a supported membrane reactor.
  • the fibrous material supports at least part of the catalyst, it is possible to supply the removed components to the fluid separation membrane while minimizing the dead space, thereby improving the productivity of the target product. It is possible to
  • FIG. 2 is a schematic diagram showing a cross section including a fluid inlet and outlet of one embodiment of the membrane reactor of the present invention.
  • Figure 2 is a schematic diagram showing two compartments of the membrane reactor of Figure 1; 1 is a schematic diagram showing one mode of arrangement of a fluid separation membrane and a fibrous material of the present invention.
  • FIG. FIG. 4 is a schematic diagram showing another aspect of the arrangement of the fluid separation membrane and fibrous material of the present invention.
  • the membrane reactor of the present invention is a membrane reactor comprising, in a vessel, a fluid separation membrane for separating a fluid to be separated and a fibrous material existing between the fluid separation membranes, wherein the fibrous material is characterized by carrying a catalyst.
  • FIG. 1 shows a schematic cross-sectional view of one embodiment of the membrane reactor of the present invention.
  • FIG. 1 is a schematic cross-sectional view of a membrane reactor in which fluid separation membranes, which are hollow fiber membranes, are housed, including fluid inlets and outlets.
  • the term "fluid” as used herein refers to a feed fluid, a fluid to be separated, a permeating fluid, or a non-permeating fluid.
  • a feed fluid is a fluid containing a reactant.
  • a fluid to be separated is a mixture of reactants, products, by-products, impurities, sweep gases, and the like.
  • a permeate fluid is a fluid that has permeated a fluid separation membrane.
  • Non-permeate fluid is fluid that exits the membrane reactor without permeating the fluid separation membrane.
  • FIG. 2 is a schematic diagram of FIG. 1 with the fibrous material removed.
  • the interior of the membrane reactor is divided into a compartment 1 (reference numeral 13) that is an outer compartment of the fluid separation membrane 1 and a compartment 2 (reference numeral 14) that is an inner compartment of the fluid separation membrane 1.
  • FIG. Compartment 1 has an inlet 8 for the feed fluid and an outlet 9 for the non-permeate fluid
  • compartment 2 has an outlet 10 for the permeate fluid that has permeated the fluid separation membrane 1 and an outlet 10 for the permeate fluid and a sweep gas for sweeping the permeate fluid. It has an inlet 11 .
  • the non-permeating fluid outlet 9 and the permeating fluid outlet 10 are connected to an external channel (not shown), and the non-permeating fluid and the permeating fluid are recovered.
  • a fibrous material 3 exists between the fluid separation membranes 1 in the compartment 1, and the fibrous material 3 carries a catalyst 4 (not shown).
  • the fibrous material 3 may be present in places other than between the fluid separation membranes 1 (for example, between the fluid separation membrane and the vessel), and the catalyst 4 may be present on the surfaces of the fluid separation membranes 1 and in the gaps 5 between the fluid separation membranes. may also exist.
  • the fibrous material 3 spirally covers the periphery of one fluid separation membrane 1, and the fluid separation membranes 1 bundled in parallel have both ends at potting sites 7. Fixed (potted) to each other and fixed to the vessel 12 , the fluid separation membrane 1 passes through the potting site 7 .
  • Chemical processes to which the membrane reactor of the present invention can be applied are not particularly limited. Examples include hydrogen production by steam reforming of methane, hydrogen production from methylcyclohexane, methane synthesis from carbon dioxide and hydrogen, and methanol synthesis and the like.
  • the cross-sectional shape of the vessel is preferably oval or circular, more preferably circular, from the viewpoint of improving the pressure resistance of the vessel.
  • the cross section of the vessel refers to the cross section of the vessel perpendicular to the length direction of the fluid separation membrane.
  • Materials for the vessel include, for example, metal, resin, fiber reinforced plastic (FRP), and the like, and can be appropriately selected according to the environment of the installation site and the usage situation. In applications where pressure resistance and heat resistance are required, metals having both strength and moldability are preferred, and stainless steel and the like are more preferred.
  • the supply fluid inlet of the vessel has the function of guiding the supply fluid into the membrane reactor.
  • the reactants contained in the feed fluid chemically react in the membrane reactor to form products, and the feed fluid becomes the fluid to be separated.
  • the compartment 1 may have an inlet for the feed fluid, and when used in a cross-flow filtration system, the compartment 1 serves as an inlet for the feed fluid.
  • each has an outlet for the non-permeating fluid.
  • a plurality of inlets for the feed fluid and outlets for the non-permeating fluid (hereinafter referred to as "outflow inlets”) may be provided within the range of maintaining the mechanical strength of the vessel.
  • the compartment 2 may have an outlet for the permeating fluid, but may also have an inlet for the sweep gas for actively entraining the permeating fluid.
  • the method of fixing the fluid separation membrane to the vessel includes a method of fixing the fluid separation membrane directly to the inner surface of the vessel with a potting material, and a separation membrane in which a plurality of fluid separation membranes are fixed with a potting material.
  • a method of fixing the element in the vessel via an adapter or the like capable of ensuring liquid tightness or airtightness can be used. Since only the separation membrane element can be replaced when the performance of the separation membrane element deteriorates over time, it is preferable to fix it in the vessel via an adapter or the like.
  • the potting portion of the membrane reactor or the separation membrane element may be at one or a plurality of locations, but from the viewpoint of sufficiently fixing the position of the fluid separation membrane and maintaining the effective surface area of the fluid separation membrane
  • two ends of a plurality of fluid separation membranes bundled in a substantially straight line are fixed with a potting material.
  • both ends of the fluid separation membranes may be fixed at one place with a potting material, or only one end of the fluid separation membranes may be fixed with a potting material, The other end may be sealed by means other than potting material.
  • the separation membrane element may have a casing (hereinafter referred to as "element casing") separate from the vessel.
  • the element casing preferably has an inlet and outlet for fluid.
  • the shape of the element casing is not particularly limited as long as it does not interfere with housing in the vessel.
  • Materials for the element casing include, for example, metals, resins, fiber reinforced plastics (FRP), and the like, and can be appropriately selected according to the conditions of use. For applications requiring high temperature operation, metals are preferred due to their high heat resistance.
  • Resin is preferable from the viewpoint of high followability to curing shrinkage of potting material, and since it has both moldability and chemical resistance, polyphenylene sulfide, polytetrafluoroethylene, polyethylene, polypropylene, polyether ether ketone, polyphenylene ether, polyether More preferred are imides, polyamideimides and polysulfones.
  • Potting materials include organic adhesives and inorganic adhesives. In applications requiring high-temperature operation, inorganic adhesives are preferred due to their high heat resistance.
  • organic adhesives examples include thermoplastic resins and thermosetting resins. Furthermore, the organic adhesive may contain other additives.
  • Thermoplastic resins suitable as organic adhesives include, for example, polyethylene, polyethersulfone, polystyrene, polyphenylene sulfide, polyarylate, polyester, liquid crystal polyester, polyamide, and polymethyl methacrylate.
  • thermosetting resins include epoxy resins, unsaturated polyester resins, urethane resins, urea resins, phenol resins, melamine resins, and silicone resins. You may use 2 or more types of these.
  • epoxy resins and urethane resins are preferable from the viewpoint of balance of moldability, curing time, adhesiveness, hardness, and the like.
  • Additives contained in organic adhesives include, for example, fillers, surfactants, silane coupling agents, and rubber components.
  • fillers include silica, talc, zeolite, calcium hydroxide, calcium carbonate, and the like, and have effects such as suppression of curing heat generation, strength improvement, and thickening.
  • the surfactant and the silane coupling agent provide effects such as improvement of handleability when mixing the potting material and improvement of infiltration between the fluid separation carbon films when the potting material is injected.
  • the rubber component has the effect of improving the toughness of the hardened and molded potting material.
  • the rubber component may be contained in the form of rubber particles.
  • Inorganic adhesives include, for example, ceramics and cement. You may use 2 or more types of these. Furthermore, other additives may be contained.
  • the membrane reactor of the present invention is characterized in that there are fibrous substances present between the fluid separation membranes, and the fibrous substances carry a catalyst.
  • the state in which the fibrous material supports the catalyst does not mean that the surface of the fibrous material and the catalyst particles, etc. are simply in contact with each other and can be easily removed with a brush or the like. represents the state in which the catalyst is chemically or physically fixed.
  • the membrane reactor in which the spacer for efficiently supplying the fluid to be separated to the separation membrane is arranged inside the membrane reactor, the spacer itself becomes a dead space in the membrane reactor, and the fluid separation membrane There was a problem of partially covering the surface of the catalyst and filling the storage space of the catalyst.
  • the fibrous material placed between the fluid separation membranes supports the catalyst, thereby minimizing the dead space while supplying the removed components to the fluid separation membranes.
  • Productivity can be improved.
  • the equipment can be made compact.
  • a fluid separation membrane is a membrane that has a higher permeability for specific components (permeable components) contained in the fluid to be separated than for other components (non-permeable components).
  • the shape of the fluid separation membrane is not particularly limited, and may be a flat membrane or a hollow fiber membrane.
  • the membrane is a hollow fiber membrane.
  • the inner diameter of the hollow fiber membrane is preferably 10 ⁇ m or more and 2,000 ⁇ m or less. Fluid permeability can be improved by setting the inner diameter of the hollow fiber membrane to 10 ⁇ m or more.
  • the inner diameter of the hollow fiber membrane is more preferably 20 ⁇ m or more, more preferably 50 ⁇ m or more.
  • the outer diameter of the hollow fiber membrane can be reduced, so that the membrane area of the fluid separation membrane per unit volume when used as a membrane reactor can be increased. can.
  • the inner diameter of the fluid separation membrane is more preferably 1,000 ⁇ m or less, and even more preferably 500 ⁇ m or less.
  • the inner diameter of the hollow fiber membrane which is the fluid separation membrane
  • the inner diameter of the hollow fiber membrane is 10 ⁇ m or more and 2,000 ⁇ m or less
  • a portion where the distance between the membranes is small occurs, and the flow of the fluid to be separated becomes uneven, and the surface utilization efficiency of the fluid separation membrane tends to decrease.
  • the fibrous material secures the inter-membrane distance, the fluid separation membrane can be highly filled while maintaining the membrane utilization efficiency.
  • the inner diameter of the hollow fiber membrane represents the diameter of the hollow portion of the hollow fiber membrane.
  • the shape of the hollow portion is not circular, the diameter of the maximum inscribed circle that fits in the hollow portion is regarded as the inner diameter of the hollow fiber membrane.
  • fluid separation membranes examples include zeolite membranes, metal organic framework (MOF) membranes, inorganic membranes such as carbon membranes, and polymer membranes.
  • MOF metal organic framework
  • inorganic membranes such as carbon membranes
  • polymer membranes polymer membranes.
  • the membrane reactor is operated under severe reaction conditions such as high temperature and acidity and basicity, an inorganic membrane with excellent heat resistance and chemical resistance is preferable, and the inorganic membrane is more preferably a zeolite membrane or a carbon membrane. preferable.
  • Zeolite membranes include membranes made of aluminosilicates such as NaX type (FAU), ZSM-5, MOR, silicalite, and A type. You may use 2 or more types of these.
  • the zeolite seeds preferably have a Si/Al ratio comparable to that of those secondary grown by hydrothermal synthesis reaction.
  • MOF films include, for example, Cu-BTC, MOF-5, IRMOF-3, MIL-47, MIL-53, MIL-96, MMOF, SIM-1, ZIF-7, ZIF-8, ZIF-22, ZIF -69, ZIF-90 and the like. You may use 2 or more types of these.
  • Examples of carbon films include polyphenylene oxide, polyvinyl alcohol, polyacrylonitrile, phenol resin, wholly aromatic polyester, unsaturated polyester resin, alkyd resin, melamine resin, urea resin, polyimide resin, diallyl phthalate resin, lignin resin, and urethane resin. etc. is carbonized. You may use 2 or more types of these.
  • Polymer membranes include, for example, aromatic polyimide, cellulose acetate, polysulfone, aromatic polyamide, polyetherimide, polyethersulfone, polyacrylonitrile, polyphenylene sulfide, polyetheretherketone, polytetrafluoroethylene, polyvinylidene fluoride, poly (1-trimethylsilylpropyne), polydimethylsiloxane, polyvinyltrimethylsilane, poly(4-methylpentene), ethylcellulose, natural rubber, poly(2,6-dimethylphenylene oxide), low-density polyethylene, high-density polyethylene, styrene, Examples include films made of polyethyl methacrylate, polycarbonate, polyester, aliphatic polyamide, polymethyl methacrylate, polyvinyl alcohol, silicone, and the like. You may use 2 or more types of these.
  • Nanoparticles and the like can be added to the fluid separation membrane to improve the permeability of permeable components.
  • examples of nanoparticles include silica, titania, zeolites, metal oxides, metal organic frameworks (MOF), carbon nanotubes (CNT), and the like.
  • the fluid separation membrane may contain a support. More preferably, when the fluid separation membrane of the present invention comprises a support, the support is located on only one surface of the fluid separation membrane.
  • the support examples include porous inorganic materials such as alumina, silica, cordierite, zirconia, titania, Vycor glass, zeolite, magnesia, sintered metals, polysulfone, polyethersulfone, polyamide, polyester, cellulose-based polymers, Porous organic materials containing at least one polymer selected from the group consisting of homopolymers and copolymers such as vinyl polymers, polyphenylene sulfides, polyphenylene sulfide sulfones, polyphenylene sulfones, and polyphenylene oxides; Examples include porous carbon materials obtained by carbonizing materials.
  • porous inorganic materials such as alumina, silica, cordierite, zirconia, titania, Vycor glass, zeolite, magnesia, sintered metals, polysulfone, polyethersulfone, polyamide, polyester, cellulose-based polymers, Porous organic materials containing at least one poly
  • Carbonizable resins include, for example, polyphenylene oxide, polyvinyl alcohol, polyacrylonitrile, phenol resin, wholly aromatic polyester, unsaturated polyester resin, alkyd resin, melamine resin, urea resin, polyimide resin, diallyl phthalate resin, lignin resin, urethane resin, Resin etc. are mentioned. You may use 2 or more types of these.
  • the bending radius of the fluid separation membrane is preferably 0.1 cm or more and 100 cm or less. By setting the bending radius to 100 cm or less, breakage of the fluid separation membrane during fabrication or operation of the membrane reactor can be suppressed.
  • the bending radius is more preferably 10 cm or less, and even more preferably 1 cm or less.
  • the lower limit of the bending radius of the fluid separation membrane is not particularly limited, it is preferably 0.1 cm or more because self-sustainability can be imparted to the fluid separation membrane when the bending radius is 0.1 cm or more.
  • a fluid separation membrane having a bending radius of 100 cm or less can be wound around a rigid fibrous material or conform to a complex shape of a vessel or fibrous material. This is preferable because the degree of freedom in reactor design can be improved.
  • the bending radius of the fluid separation membrane is such that when a fluid separation membrane of 10 cm or more is sampled from the membrane reactor and the sampled fluid separation membrane is wound 360° or more along the normal direction of the cylinder, the fluid separation membrane does not break. It can be obtained from the radius.
  • the bending radius of the fluid separation membrane is 1.5 cm or more, the angle at which the sampled fluid separation membrane is wound along the normal direction of the cylinder is appropriately reduced for evaluation, and the radius of the cylinder at which the fluid separation membrane does not break is determined. , can be regarded as the bending radius of the fluid separation membrane.
  • the bending radius of the fluid separation membrane supporting the catalyst is regarded as the bending radius of the fluid separation membrane.
  • the water permeability of the fluid separation membrane is preferably 100 ⁇ L/(hr ⁇ m 2 ⁇ Pa) or less.
  • a fluid separation membrane having a water permeability of 100 ⁇ L/(hr ⁇ m 2 ⁇ Pa) or less can be suitably used as a membrane reactor that requires gas separation because the pore size of the separation functional layer is small.
  • the water permeability of the fluid separation membrane is more preferably 10 ⁇ L/(hr ⁇ m 2 ⁇ Pa) or less, and even more preferably 1 ⁇ L/(hr ⁇ m 2 ⁇ Pa) or less.
  • the water permeability of the fluid separation membrane is determined by the amount of permeated water recovered from the permeate fluid outlet of the membrane reactor when pure water is supplied from the feed fluid inlet of the membrane reactor, and the following (Equation 1) can be calculated by
  • the fibrous substances are present between the fluid molecular membranes in the compartment 1 to secure the distance between the fluid separation membranes and guide the fluid to be separated to the fluid separation membranes. Examples of fibrous materials include fibers, nonwoven fabrics, woven fabrics, and knitted fabrics. You may combine 2 or more types of these.
  • Fiber refers to a form whose length is 100 times or more its diameter, and examples include organic fibers and inorganic fibers.
  • organic fibers include synthetic fibers, semi-synthetic fibers, and regenerated fibers
  • inorganic fibers include metal fibers, carbon fibers, glass fibers, and rock fibers.
  • Inorganic fibers are preferably used because of their high heat resistance.
  • non-woven fabric, woven fabric, and knitted fabric represent forms in which fibers are processed on a plane.
  • the fibrous material is preferably a fiber because it can be easily arranged between the fluid separation membranes.
  • a woven or knitted fabric is preferred.
  • the fibrous material may spirally cover one or more fluid separation membranes, or may be arranged in parallel with the fluid separation membranes. From the viewpoint of enabling the spacers to be arranged uniformly around the fluid separation membranes, it is preferable that the spacers spirally cover the circumference of one or more fluid separation membranes. A parallel arrangement is preferred.
  • the fiber length is preferably 0.1 to 2.0 times the length of the fluid separation membrane. When the fiber length is 0.1 times or more the length of the fluid separation membranes, it becomes easier to secure the distance between the fluid separation membranes.
  • the fiber length is preferably at least 0.5 times the length of the fluid separation membrane, more preferably at least 0.75 times. On the other hand, when the fiber length is 2.0 times or less the length of the fluid separation membrane, the volume occupied by the fiber in the membrane reactor can be suppressed and the membrane packing rate can be improved.
  • the length of the fibers is more preferably 1.5 times or less, and even more preferably 1.1 times or less, the length of the fluid separation membrane.
  • FIGS. 3 and 4 show schematic diagrams of one embodiment in which the fluid separation membrane is spirally coated with a fibrous material.
  • FIG. 3 is a schematic diagram of one embodiment in which one fluid separation membrane 1 is spirally coated with one fibrous material 3 at a pitch of 12
  • FIG. 2 is a schematic diagram of an embodiment in which two fibrous materials 3 are spirally coated on a separation membrane 1 with a pitch of 12 between them.
  • fibrous material 3 carries catalyst 4 (not shown).
  • the fibrous covering may be a single covering in which the fibrous material is wrapped around the fluid separation membrane, or a double covering in which the fibrous material is wrapped twice. Further, a multi-stage covering may be used in which a fibrous material is further spirally wound around a plurality of fluid separation membranes wrapped with a fibrous material.
  • fibrous substances include polyesters, nylons, polyolefins, fluororesins, polyacetals, thermoplastic elastomers, metal oxides, and metals. You may use 2 or more types of these.
  • the fibrous material when the fibrous material is a fiber, the fibrous material may be a monofilament or a multifilament. preferable. Further, it is more preferable to use a false-twisted textured yarn because it has high bulkiness and can easily secure the distance between the fluid separation membranes.
  • a catalyst increases the reaction rate of a chemical process in a membrane reactor by lowering the activation energy of the reaction.
  • the membrane reactor of the present invention is characterized in that the catalyst is supported on a fibrous material.
  • the catalyst may be coated on the surface of the fibrous material or attached to the surface of the fibrous material. It is more preferable to be supported. Any outer surface of the fibrous material includes the inner surface of pores when the fibrous material is porous and the outer surface of all single fibers when the fibrous material is multifilament.
  • the catalyst loading amount of the fibrous material of the present invention is preferably 0.01% by mass or more and 10% by mass or less with respect to 100% by mass of the fibrous material containing the catalyst.
  • the catalyst loading amount of the fibrous material is more preferably 0.1% by mass or more, further preferably 1% by mass or more.
  • the upper limit of the amount of catalyst supported on the fibrous material is not particularly limited, it is preferably 10% by mass or less because the surface area of the fibrous material can be effectively used.
  • the amount of catalyst supported on the fibrous material is expressed by the ratio of the weight of the catalyst supported on the fibrous material to the weight of the fibrous material containing the catalyst, and can be calculated from the weight of the fibrous material before and after supporting the catalyst. Also, the weight of the catalyst supported on the fibrous material can be estimated by completely eluting the catalyst from the fibrous material and measuring the obtained eluate by inductively coupled plasma mass spectrometry (ICP-MS). be.
  • ICP-MS inductively coupled plasma mass spectrometry
  • wet plating and dry plating are examples of methods for supporting catalysts on fibrous materials.
  • Examples of wet plating include electrolytic plating and electroless plating, and examples of dry plating include vapor deposition and sputtering.
  • the catalyst not supported on the fibrous material may be arranged on the surface of the fluid separation membranes or between the fluid separation membranes. It is preferably arranged on the surfaces of the fluid separation membranes from the viewpoint of not inhibiting passage of the fluid, and preferably arranged between the fluid separation membranes from the viewpoint of increasing the contact surface area of the catalyst.
  • the catalyst may be placed both on the surface of the fluid separation membranes and between the fluid separation membranes.
  • the type of catalyst is not particularly limited, and is appropriately selected according to the reaction that occurs within the membrane reactor.
  • the membrane reactor of the present invention has an electric circuit, and the electric circuit is arranged so that an electric current can flow through the fibrous material, but this aspect will be explained.
  • the fibrous material may be provided with individual electric circuits, or a plurality of fibrous materials may be incorporated into one electric circuit. From the viewpoint of simplifying the wiring, it is preferable to incorporate a plurality of fibrous materials into one electrical circuit. be done.
  • the fibrous material and the current collector, and the current collector and the power source may be directly connected, or may be connected via a conductor such as a lead wire.
  • the electrical resistivity of the fibrous material is preferably 0.1 ⁇ m or more and 1000 ⁇ m or less.
  • the electrical resistivity of the fibrous material is 0.1 ⁇ m or more
  • resistance heating occurs when an electric current is applied to the fibrous material, and the fibrous material can be used as a heating element, and the fibrous material can be used as a heating element.
  • the inside of the membrane reactor can be directly heated. In resistance heating, all the power consumed by the resistance is converted into heat, so the inside of the membrane reactor can be efficiently heated.
  • the electrical resistivity of the fibrous material is more preferably 0.5 ⁇ m or more, and still more preferably 1 ⁇ m or more.
  • the electrical resistivity of the fibrous material is 1000 ⁇ m or less, resistance heating can be generated even if the fibrous material is thinned, so that the volume of the fibrous material in the membrane reactor can be suppressed. can.
  • the electrical resistivity of the fibrous material is more preferably 100 ⁇ m or less, and even more preferably 10 ⁇ m or less.
  • fibrous materials having an electrical resistivity of 0.1 ⁇ m or more and 1000 ⁇ m or less include iron, chromium, aluminum, nickel, platinum, molybdenum, tantalum, tungsten, alloys thereof, and carbon.
  • the fibrous material preferably has an insulating layer on its surface. Since the insulating layer on the surface of the fibrous material suppresses corrosion of the fibrous material when the fibrous material is used as a heating element, it can be used as a heating element for a long time.
  • the membrane reactor of the present invention preferably has a heat source or a cooling source and is arranged so that the fibrous material and the heat source or the cooling source are in contact with each other, but this aspect will be explained.
  • the method of heating or cooling the fibrous material that is, the heating method or the cooling method of the heat source or the cooling source arranged so as to be in contact with the fibrous material is not particularly limited, and the fibrous material is directly connected to the heat source or the cooling source. may be connected via a heat conductor. From the viewpoint of simplifying wiring, it is preferable to connect a plurality of fibrous materials to a heat conductor before connecting them to a heat source or a cooling source. In this case, the fibrous materials are arranged so as to contact the heat conductor. and the heat conductor is connected with a heat source or a cooling source.
  • the thermal conductivity of the fibrous material is preferably 1 W/(m ⁇ K) or more and 1000 W/(m ⁇ K) or less.
  • the inside of the membrane reactor can be heated or cooled by heating or cooling the fibrous material. Whether the reaction is endothermic or exothermic, the temperature in the membrane reactor can be easily controlled.
  • the thermal conductivity of the fibrous material is more preferably 10 W/(m ⁇ K) or more, more preferably 100 W/(m ⁇ K) or more.
  • the fibrous material having a thermal conductivity of 1 W/(m ⁇ K) or more and 1000 W/(m ⁇ K) or less includes silver, copper, iron, chromium, aluminum, nickel, platinum, molybdenum, tantalum, tungsten, and These alloys etc. are mentioned.
  • the fibrous material preferably contains at least one selected from the group consisting of iron, chromium, aluminum, nickel, platinum, molybdenum, tantalum, tungsten, alloys thereof, and carbon.
  • the manufacturing method of the membrane reactor of the present invention is not particularly limited.
  • a manufacturing method (hereinafter referred to as manufacturing method 2) in which, after manufacturing a membrane reactor containing a fibrous material, the catalyst is charged into the membrane reactor to fill the space between the fluid separation membranes with the catalyst, and at the same time, the fibrous material supports the catalyst. It's okay.
  • Manufacturing method 1 is more preferable because the catalyst can be reliably supported on the fibrous material.
  • Chemical processes to which the membrane reactor of the present invention can be applied are not particularly limited. Examples include hydrogen production by steam reforming of methane, hydrogen production from methylcyclohexane, methane synthesis from carbon dioxide and hydrogen, and methanol synthesis and the like.
  • the chemical plant of the present invention (hereinafter sometimes simply referred to as "plant") is a plant including the membrane reactor of the present invention.
  • the plant preferably includes pretreatment equipment, purified fluid recovery equipment, by-product fluid recovery equipment, and the like.
  • the pretreatment equipment is equipment for adjusting the composition of the reaction fluid supplied to the membrane reactor.
  • Purified fluid recovery equipment is equipment for recovering a purified fluid that has permeated through a fluid separation membrane, further purifying the fluid if necessary, and supplying it to a pipeline or the like.
  • the by-product fluid recovery facility is a facility for recovering unreacted reaction fluids and by-product fluids, reusing the unreacted reaction fluids, and discharging the by-product fluids after rendering them harmless.
  • the membrane reactor, the pretreatment equipment, the purified fluid recovery equipment, and the by-product fluid recovery equipment are preferably connected by piping or the like so that the purified fluid is continuously produced from the reaction fluid.
  • the plant preferably includes multiple membrane reactors according to the throughput of the fluid to be separated.
  • a plurality of membrane reactors may be connected in series or in parallel with respect to the reaction fluid. From the viewpoint of production efficiency of the membrane reactor, the membrane reactors are preferably connected in series, and from the viewpoint of partial replacement of the membrane reactors, the membrane reactors are preferably connected in parallel.
  • a preferred embodiment of the plant of the present invention includes a mode in which the membrane reactors are connected in series, and the membrane reactors connected in series are further connected in parallel. By doing so, it is possible to achieve both the advantages of connecting the membrane reactors in series and the advantages of connecting them in parallel.
  • Chemical processes to which the plant of the present invention can be applied are not particularly limited, but examples include hydrogen production by steam reforming of methane, hydrogen production from methylcyclohexane, methane synthesis and methanol synthesis from carbon dioxide and hydrogen, and the like. is mentioned.
  • the fluid production method of the present invention is a fluid production method using the membrane reactor of the present invention and includes at least the following steps.
  • Step 1 where a catalyst present in the membrane reactor produces products from the reactants in the feed stream, and a fluid separation membrane present in the membrane reactor concentrates the products from the resulting fluid to be separated from step 1 above. Step 2 to do.
  • the product produced from the reactants may contain by-products in addition to the desired product, but the product produced in step 1 and the product concentrated in step 2 are both It refers to the desired product.
  • another purification step or an additional step may be included.
  • Alternative purification steps include, for example, distillation, adsorption, absorption, and the like.
  • component adjustment etc. which mix with another fluid are mentioned, for example.
  • the membrane reactor enables continuous production from a small scale.
  • Inner diameter of fluid separation membrane Five fluid separation membranes with a length of 10 cm or more were cut out from the produced membrane reactor and split in a direction orthogonal to the fiber axis direction. The fractured surface was observed with a digital microscope (VHX-D500 manufactured by Keyence Corporation), and the diameter of the maximum inscribed circle that fits in the hollow portion was measured. The average value of the diameters of the obtained inscribed circles was expressed with one significant digit as the inner diameter of the fluid separation membrane.
  • the electrical resistivity of fibrous materials was measured by a four-probe method.
  • the electrical resistivity was measured by measuring the potential difference between two points on the surface of the fibrous material while applying electricity to the fibrous material, and calculating the resistivity ⁇ by the following formula 1.
  • a DC power supply (PAD55-20L manufactured by Kikusui Electronics), a voltmeter (3878A multimeter manufactured by Hewlett-Packard) and an ammeter (DT4252 manufactured by Hioki Denki) were used for the measurement of electrical resistivity. The measurement was carried out three times, and the average value represented by two significant figures was taken as the electrical resistivity ( ⁇ m) of the fibrous material.
  • ⁇ U the measured potential difference
  • I the current flowing through the fibrous material
  • S the cross-sectional area of the fibrous material
  • d the distance between the two electrodes for measuring the potential.
  • Thermal conductivity of fibrous materials was measured by the laser flash method. The thermal conductivity was measured by molding the bundled fibrous material into a block and measuring the thermal conductivity with a thermal conductivity measuring device (TC-7000H manufactured by Avantek Riko Co., Ltd.). The measurement was carried out three times, and the average value represented by two significant figures was defined as the thermal conductivity (W/(m ⁇ K)) of the fibrous material.
  • Methylcyclohexane was supplied from the feed fluid inlet of the fabricated membrane reactor. Methylcyclohexane is decomposed into toluene and hydrogen using palladium in the membrane reactor as a catalyst, and hydrogen selectively permeates the fluid separation membrane. Hydrogen was recovered from the inlet and outlet of the permeated fluid of the membrane reactor, and the production amount of hydrogen as a product was evaluated from the flow rate measured with a soap film flow meter and the hydrogen composition ratio obtained by gas chromatography analysis. Regarding the membrane reactors of Examples 2 and 3, the amount of hydrogen produced was also evaluated in a state in which an electric current was passed through the fibrous material and a state in which the fibrous material was heated. The measurement was performed 3 times, and the average value was rounded off to the first decimal place to obtain the production amount of the product.
  • the obtained precursor of the porous carbon film was passed through an electric furnace at 250°C and heated in an air atmosphere for 1 hour to perform an infusibilization treatment to obtain an infusibilization thread.
  • the infusible yarn was carbonized at a carbonization temperature of 650° C. to obtain a fluid separation membrane of Production Example 1, which is an inorganic membrane (carbon membrane) having an outer diameter of 300 ⁇ m, an inner diameter of 100 ⁇ m, and a bending radius of 5 mm.
  • Example 1 One fluid separation membrane of Production Example 2 was used as a core thread, and the catalyst-supported fibrous material of Production Example 3 was wound in the Z direction at a pitch of 10 mm.
  • 10 fluid separation membranes of Production Example 2 around which the catalyst-supporting fibrous material was wound were bundled, housed in an acrylic pipe (inner diameter 3 mm) having a fluid inlet and outlet, and epoxy resin was applied to both ends of the acrylic pipe. were statically potted one by one. After curing the epoxy resin, the potting portion at one end was cut with a rotating saw to open the fluid separation membrane, and the membrane reactor of Example 1 was obtained.
  • the bending radius of the fluid separation membrane was 5 mm
  • the inner diameter of the fluid separation membrane was 100 ⁇ m
  • the ratio of the length of the fiber to the length of the fluid separation membrane was 1.0
  • the amount of product produced. was 33 mL/min.
  • Example 2 One fluid separation membrane of Production Example 2 was used as a core thread, and the catalyst-supported fibrous material of Production Example 4 was wound in the Z direction at a pitch of 10 mm.
  • 10 fluid separation membranes of Production Example 2 around which the catalyst-supporting fibrous material was wound were bundled, housed in an acrylic pipe (inner diameter 3 mm) having a fluid inlet and outlet, and epoxy resin was applied to both ends of the acrylic pipe. were statically potted one by one. After curing the epoxy resin, the potting portion at one end was cut with a rotating saw to open the fluid separation membrane.
  • Metal perforated plates were installed on the fluid separation membrane opening faces at both ends of the element, and a lead wire and a DC power source were arranged between the two perforated plates to obtain a membrane reactor of Example 2.
  • the membrane reactor of Example 2 has an electric circuit.
  • the bending radius of the fluid separation membrane was 5 mm
  • the inner diameter of the fluid separation membrane was 100 ⁇ m
  • the ratio of the length of the fiber to the length of the fluid separation membrane was 1.0
  • the amount of product produced. was 17 mL/min.
  • the production amount of the product was 41 mL/min in the state where the electric current was applied to the fibrous material.
  • Example 3 One fluid separation membrane of Production Example 2 was used as a core thread, and the catalyst-supported fibrous material of Production Example 4 was wound in the Z direction at a pitch of 10 mm.
  • 10 fluid separation membranes of Production Example 2 around which the catalyst-supporting fibrous material was wound were bundled, housed in an acrylic pipe (inner diameter 3 mm) having a fluid inlet and outlet, and epoxy resin was applied to both ends of the acrylic pipe. were statically potted one by one. After curing the epoxy resin, the potting portion at one end was cut with a rotating saw to open the fluid separation membrane. Metal perforated plates were placed on the fluid separation membrane opening faces at both ends of the element, and the two perforated plates were connected to respective heat sources to obtain the membrane reactor of Example 3.
  • the membrane reactor of Example 3 has a heat source.
  • the bending radius of the fluid separation membrane was 5 mm
  • the inner diameter of the fluid separation membrane was 100 ⁇ m
  • the ratio of the length of the fiber to the length of the fluid separation membrane was 1.0
  • the amount of product produced. was 17 mL/min.
  • the fibrous material was heated, the amount of product produced was 36 mL/min.
  • Example 4 A membrane reactor of Example 4 was obtained in the same manner as in Example 2 except that the catalyst-supported fibrous material of Production Example 5 was used instead of the catalyst-supported fibrous material of Production Example 4. rice field.
  • the membrane reactor of Example 4 has an electrical circuit.
  • the bending radius of the fluid separation membrane was 5 mm
  • the inner diameter of the fluid separation membrane was 100 ⁇ m
  • the ratio of the length of the fiber to the length of the fluid separation membrane was 1.0
  • the amount of product produced. was 16 mL/min.
  • the production amount of the product was 23 mL/min when the electric current was applied to the fibrous material.
  • Example 5 A membrane reactor of Example 5 was obtained in the same manner as in Example 3, except that the catalyst-supported fibrous material of Production Example 5 was used instead of the catalyst-supported fibrous material of Production Example 4. rice field.
  • the membrane reactor of Example 5 has a heat source.
  • the bending radius of the fluid separation membrane was 5 mm
  • the inner diameter of the fluid separation membrane was 100 ⁇ m
  • the ratio of the length of the fiber to the length of the fluid separation membrane was 1.0
  • the amount of product produced. was 16 mL/min.
  • the fibrous material was heated, the amount of product produced was 34 mL/min.
  • Example 6 The 10 fluid separation membranes of Production Example 2 and the 10 catalyst-supported fibrous materials of Production Example 5 are aligned and bundled so that the fluid separation membranes are not adjacent to each other as much as possible, and an acrylic pipe (inner diameter 3 mm), and each end of the acrylic pipe was statically potted using epoxy resin. After curing the epoxy resin, the potting portion at one end was cut with a rotary saw to open the fluid separation membrane, and the membrane reactor of Example 6 was obtained.
  • the bending radius of the fluid separation membrane was 5 mm
  • the inner diameter of the fluid separation membrane was 100 ⁇ m
  • the ratio of the length of the fiber to the length of the fluid separation membrane was 1.0
  • the amount of product produced. was 15 mL/min.
  • Comparative example 1 A membrane reactor of Comparative Example 1 was obtained in the same manner as in Example 1, except that a 170 dtex polyester textured yarn was used instead of the catalyst-supported fibrous material of Production Example 3. As a result of evaluation by the method described above, the production amount of the product was 11 mL/min.
  • Fluid separation membrane 2 Hollow part 3: Fiber material 4: Catalyst 5: Gap between fluid separation membranes 7: Potting part 8: Feed fluid inlet 9: Non-permeate fluid outlet 10: Permeate fluid flow Outlet 11: Sweep Gas Inlet 12: Vessel 13: Compartment 1 14: Compartment 2

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'un réacteur à membrane avec lequel une quantité de traitement et une vitesse de traitement sont obtenues simultanément, l'objet de la présente invention reposant sur un réacteur à membrane comprenant, dans un récipient, des membranes de séparation de fluide, et un matériau fibreux présent entre les membranes de séparation de fluide, le matériau fibreux supportant un catalyseur.
PCT/JP2022/011582 2021-03-30 2022-03-15 Réacteur à membrane, installation chimique, et procédé de fabrication de fluide WO2022209849A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2022517764A JPWO2022209849A1 (fr) 2021-03-30 2022-03-15

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021056864 2021-03-30
JP2021-056864 2021-03-30

Publications (1)

Publication Number Publication Date
WO2022209849A1 true WO2022209849A1 (fr) 2022-10-06

Family

ID=83458904

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/011582 WO2022209849A1 (fr) 2021-03-30 2022-03-15 Réacteur à membrane, installation chimique, et procédé de fabrication de fluide

Country Status (2)

Country Link
JP (1) JPWO2022209849A1 (fr)
WO (1) WO2022209849A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06327905A (ja) * 1993-05-21 1994-11-29 Toray Ind Inc 脱気膜モジュールおよびその運転方法
JP2001205097A (ja) * 2000-01-24 2001-07-31 Nitto Denko Corp 金属触媒付着担体及びその製造方法並びにそれを用いた活性酸素源含有液の処理方法
JP2004505417A (ja) * 2000-07-24 2004-02-19 マイクロセル・コーポレイション マイクロセルによる電気化学的装置およびアセンブリならびにその作成方法および使用方法
JP2005104831A (ja) * 2003-09-15 2005-04-21 Celgard Inc 金属水素化物から水素を発生させるための反応器および方法
JP2009286637A (ja) * 2008-05-27 2009-12-10 Nissan Motor Co Ltd 水素生成装置
JP2009292706A (ja) * 2008-06-09 2009-12-17 Tdk Corp 燃料改質モジュール及びその運転方法
JP2011195349A (ja) * 2010-03-17 2011-10-06 Tokyo Gas Co Ltd 水素製造装置

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06327905A (ja) * 1993-05-21 1994-11-29 Toray Ind Inc 脱気膜モジュールおよびその運転方法
JP2001205097A (ja) * 2000-01-24 2001-07-31 Nitto Denko Corp 金属触媒付着担体及びその製造方法並びにそれを用いた活性酸素源含有液の処理方法
JP2004505417A (ja) * 2000-07-24 2004-02-19 マイクロセル・コーポレイション マイクロセルによる電気化学的装置およびアセンブリならびにその作成方法および使用方法
JP2005104831A (ja) * 2003-09-15 2005-04-21 Celgard Inc 金属水素化物から水素を発生させるための反応器および方法
JP2009286637A (ja) * 2008-05-27 2009-12-10 Nissan Motor Co Ltd 水素生成装置
JP2009292706A (ja) * 2008-06-09 2009-12-17 Tdk Corp 燃料改質モジュール及びその運転方法
JP2011195349A (ja) * 2010-03-17 2011-10-06 Tokyo Gas Co Ltd 水素製造装置

Also Published As

Publication number Publication date
JPWO2022209849A1 (fr) 2022-10-06

Similar Documents

Publication Publication Date Title
KR101376082B1 (ko) 산화 반응기 및 산화 방법
CN102459066B (zh) 从反应混合物中电化学分离氢气的方法
CN102459067B (zh) 使天然气反应成芳族烃同时电化学分离氢气的方法
Wang et al. Catalytic mixed conducting ceramic membrane reactors for methane conversion
Hughes Composite palladium membranes for catalytic membrane reactors
CN102365252B (zh) 使天然气反应成芳族化合物同时电化学除去氢气并使氢气电化学反应成水的方法
CN102365251A (zh) 使天然气反应生成芳烃，同时电化学除氢且同时产生电力并产生氢气的方法
WO2006034100A1 (fr) Reformeur a la vapeur a membrane
CN111017875B (zh) 一种天然气直裂解制备H2与CNTs的催化渗透性一体化膜反应器及应用
US11814740B2 (en) System for managing fuel generation
WO2005070519A1 (fr) Reacteur du type membrane selectivement permeable
WO2022209849A1 (fr) Réacteur à membrane, installation chimique, et procédé de fabrication de fluide
WO2018004723A1 (fr) Éléments de réacteur-séparateur
JP2002505515A (ja) 合成ガスの製造方法および装置
US8357228B2 (en) Gas purification method
Ji et al. Vacuum-assisted continuous flow electroless plating approach for high performance Pd membrane deposition on ceramic hollow fiber lumen
Medrano et al. CO selective oxidation using catalytic zeolite membranes
Yu et al. SiC mesoporous membranes for sulfuric acid decomposition at high temperatures in the iodine–sulfur process
US20090108239A1 (en) Composite membrane
Morooka et al. Separation of hydrogen from an H2-H2O-HBr system with an SiO2 membrane formed in macropores of an α-alumina support tube
WO2013062217A1 (fr) Module de production d'hydrogène par un procédé intégré de réaction/séparation et réacteur de production d'hydrogène l'utilisant
Han et al. Zeolite proton conducting membrane for micro fuel cell applications
RU2638350C1 (ru) Интегрированный мембранно-каталитический реактор и способ совместного получения синтез-газа и ультрачистого водорода
JP2007270256A (ja) 水素製造装置、水素製造方法および燃料電池発電装置
Li et al. Enhancing the oxygen permeation rate of Ba0. 5Sr0. 5Co0. 8Fe0. 2O3− δ membranes by surface loading Co3O4 nanorod catalysts

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2022517764

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22780070

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22780070

Country of ref document: EP

Kind code of ref document: A1