Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/24—Stationary reactors without moving elements inside
  • B01J19/2415—Tubular reactors
  • B01J19/2425—Tubular reactors in parallel
• • 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
  • B01D69/14—Dynamic membranes
  • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
  • B01D69/145—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing embedded catalysts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D19/00—Degasification of liquids
  • B01D19/0031—Degasification of liquids by filtration
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
  • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific 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
  • B01D63/06—Tubular membrane modules
  • B01D63/066—Tubular membrane modules with a porous block having membrane coated passages
• • 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
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/02—Inorganic material
  • B01D71/028—Molecular sieves
  • B01D71/0281—Zeolites
• • 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
  • B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
• • 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
  • B01J19/2475—Membrane reactors
• • 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
  • B01J8/009—Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
  • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
  • C07C29/152—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the reactor used
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
  • C07C31/02—Monohydroxylic acyclic alcohols
  • C07C31/04—Methanol
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2311/00—Details relating to membrane separation process operations and control
  • B01D2311/13—Use of sweep gas
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2313/00—Details relating to membrane modules or apparatus
  • B01D2313/08—Flow guidance means within the module or the apparatus
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2313/00—Details relating to membrane modules or apparatus
  • B01D2313/10—Specific supply elements
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2313/00—Details relating to membrane modules or apparatus
  • B01D2313/12—Specific discharge elements
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2313/00—Details relating to membrane modules or apparatus
  • B01D2313/19—Specific flow restrictors
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2319/00—Membrane assemblies within one housing
  • B01D2319/04—Elements in parallel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2325/00—Details relating to properties of membranes
  • B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2325/00—Details relating to properties of membranes
  • B01D2325/20—Specific permeability or cut-off range

Definitions

• the present invention relates to a reactor module and a separation membrane module.
• reactor modules have been developed that are used for conversion reactions from raw material gases containing hydrogen and carbon oxides to liquid fuels (methanol, ethanol, etc.).
• Patent Document 1 discloses a reactor module comprising a plurality of reactors housed in a housing. Each reactor is a tubular reactor.
• each reactor is placed in a non-uniform thermal environment because the distance between the reactor and the housing is different for each reactor. Therefore, among the plurality of reactors, some reactors are overheated or supercooled, and the conversion efficiency of the reactor is relatively low, or the service life of the reactor is shortened.
• the separation filter when heating or cooling the separation membrane for permeating the desired component contained in the mixed fluid, the separation filter is not sufficiently heated or cooled, or the separation filter is excessively heated or cooled. If a filter exists, the separation performance will be lowered and the service life will be shortened.
• the purpose of the present invention is to provide a reactor module and a separation membrane module that can equalize the thermal environment.
• a reactor module includes a housing and a plurality of reactors arranged around a predetermined axis in the housing.
• the shortest distances between the housing and each of the plurality of reactors are equal to each other in a cross section along the radial direction perpendicular to the predetermined axis.
• a reactor module according to a second aspect of the present invention relates to the first aspect, wherein the plurality of reactors are arranged on a line of similarity that resembles the contour of the inner peripheral surface of the housing.
• a reactor module according to a third aspect of the present invention relates to the first aspect, wherein the housing is hollow, and the plurality of reactors are arranged on a first similarity line similar to the inner peripheral surface of the housing. It includes a first reactor and a plurality of second reactors arranged on a second line of similarity that resembles the inner peripheral surface of the housing and surrounds the first line of similarity.
• a reactor module according to a fourth aspect of the present invention relates to any one of the first to third aspects, wherein the outer shape of the housing is cylindrical or cylindric centered on a predetermined axis, and each of the plurality of reactors The outer shape is cylindrical or cylindric.
• a reactor module relates to any one of the first to fourth aspects, wherein the reactor permeates a product of a conversion reaction from a raw material gas containing hydrogen and carbon oxide to a liquid fuel.
• the first opening communicates with the non-outflow space in the housing, the second opening communicates with the outflow space in the housing, and the non-outflow space is isolated from the outflow space.
• a reactor module relates to the fifth aspect, and includes a first airflow resistance member disposed in the non-outflow side space and surrounding the first opening of the reactor, wherein the first airflow resistance member is , provide ventilation resistance to the sweep gas flowing into the first opening from the non-outflow side space.
• a reactor module relates to the sixth aspect, and includes a second airflow resistance member disposed in the outflow-side space and surrounding the second opening of the reactor, the second airflow resistance member comprising: A ventilation resistance is applied to the sweep gas flowing out of the second opening into the outflow side space, and the ventilation resistance of one of the first and second ventilation resistance members is greater than the ventilation resistance of the other of the first and second ventilation resistance members. .
• a separation membrane module comprises a housing and a plurality of separation filters that are arranged around a predetermined axis in the housing and require heating or cooling.
• the shortest distances between the housing and each of the plurality of separation filters are equal to each other in a cross section along the radial direction perpendicular to the predetermined axis.
• FIG. 1 is a see-through side view of a reactor module according to a first embodiment
• FIG. XX sectional view of FIG. 1 is a perspective view of a reactor according to a first embodiment
• Sectional view of the reactor module according to the second embodiment Sectional view of a reactor module according to modification 6
• Side view of airflow resistance member according to modification 6 Top view of a discharge pipe according to Modification 6
• FIG. 1 is a transparent side view of the reactor module 2.
• the reactor module 2 includes a plurality of reactors 1, a housing 3, a first sealing portion 4, a second sealing portion 5, and a flow stop portion 6.
• Reactor 1 is housed within housing 3 .
• the outer shape of the reactor 1 is cylindrical.
• the reactor 1 is a so-called membrane reactor for converting raw material gas into liquid fuel.
• the source gas contains at least hydrogen and carbon dioxide.
• the source gas may contain carbon monoxide.
• the source gas may be a so-called synthesis gas (Syngas).
• the liquid fuel is a fuel that is liquid at room temperature and pressure, or a fuel that can be liquefied at room temperature and pressure. Examples of fuels in a liquid state at normal temperature and normal pressure include methanol, ethanol, liquid fuels represented by C n H 2 (m-2n) (m is an integer less than 90, n is an integer less than 30), and these mixtures. Fuels that can be liquefied at room temperature and under pressure include, for example, propane, butane, and mixtures thereof.
• reaction formula (1) for synthesizing methanol by catalytically hydrogenating a raw material gas containing hydrogen and carbon dioxide in the presence of a catalyst is as follows.
• the above reaction is an equilibrium reaction, and reactor 1 can shift the reaction equilibrium to the product side by separating water vapor, which is one of the products of the conversion reaction.
• the conversion reaction is preferably carried out at high temperature and high pressure (for example, 180° C. or higher, 2 MPa or higher).
• the liquid fuel is in a gaseous state when it is synthesized and remains in a gaseous state at least until it flows out of the reactor 1 .
• the reactor 1 preferably has heat resistance and pressure resistance suitable for the desired conditions for synthesizing the liquid fuel.
• the housing 3 is mainly made of a metal material (such as stainless steel).
• a housing 3 accommodates a plurality of reactors 1 .
• the outer shape of the housing 3 is cylindrical with the central axis AX as the center.
• the central axis AX is an example of a "predetermined axis" according to the invention.
• the interior of the housing 3 is partitioned into first to fourth spaces P1 to P4 by the first sealing portion 4, the second sealing portion 5 and the flow stop portion 6.
• the housing 3 has a source gas supply port 3a, a liquid fuel discharge port 3b, a sweep gas supply port 3c and a sweep gas discharge port 3d.
• the raw material gas is supplied to the first space P1 from the raw material gas supply port 3a.
• the raw material gas flows into the reactor 1 from the first space P1.
• Liquid fuel flows out of the reactor 1 into the second space P2.
• the liquid fuel that has flowed out to the second space P2 is discharged to the outside from the liquid fuel discharge port 3b.
• the sweep gas is supplied to the third space P3 from the sweep gas supply port 3c.
• the sweep gas flows into the reactor 1 from the third space P3.
• the sweep gas that has taken in water vapor in the reactor 1 flows out of the reactor 1 into the fourth space P4.
• the sweep gas that has flowed out to the fourth space P4 is discharged to the outside from the sweep gas outlet 3d.
• the third space P3 is an example of a "non-outflow side space" where the water vapor separated in the reactor 1 does not flow out.
• the fourth space P4 is an example of an "outflow side space” from which water vapor separated in the reactor 1 flows out.
• the third space P3 is isolated from the fourth space P4 by the flow stopper 6.
• the water vapor separated in the reactor 1 can be recovered.
• water vapor is collected using a sweep gas, but water vapor can also be collected without using a sweep gas by reducing the pressure in the fourth space P4 from that in the third space P3.
• a vacuum pump may be installed on the side of the sweep gas discharge port 3d.
• the first sealing portion 4 seals between the housing 3 and the first end 1 a of the reactor 1 .
• the first sealing portion 4 holds the first end portion 1 a of the reactor 1 .
• the first sealing portion 4 has an insertion hole through which the first end portion 1a of the reactor 1 is inserted.
• Examples of materials constituting the first sealing portion 4 include glass, silver solder, solder, inorganic adhesives, rubber, and plastic.
• the second sealing portion 5 seals between the housing 3 and the second end 1 b of the reactor 1 .
• the second sealing portion 5 holds the second end portion 1 b of the reactor 1 .
• the second sealing portion 5 has an insertion hole through which the second end portion 1b of the reactor 1 is inserted.
• the resistance to the chemical load of the high-temperature liquid fuel and the resistance to water vapor are the constituent materials of the second sealing portion 5.
• the constituent material of the second sealing portion 5 include glass, silver solder, solder, inorganic adhesives, and the like. Rubber and plastic are not suitable materials for the second sealing portion 5 .
• a flow stop 6 is arranged between the reactor 1 and the housing 3 .
• the flow stopper 6 is arranged between the third space P3 and the fourth space P4.
• the flow stopper 6 isolates the third space P3 from the fourth space P4.
• the flow stop portion 6 has an insertion hole through which the central portion of the reactor 1 is inserted.
• the flow stopper 6 prevents the sweep gas from flowing from the third space P3 to the fourth space P4.
• the flow stopper 6 only needs to be able to suppress the flow of the sweep gas, and does not have to seal the space between the reactor 1 and the housing 3 .
• the flow stopper 6 can be made of, for example, expanded graphite, rubber, resin, or the like.
• FIG. 2 is a cross-sectional view taken along line XX of FIG.
• FIG. 2 shows a cross section along the radial direction perpendicular to the central axis AX of the housing 3 .
• a plurality of reactors 1 are housed in a housing 3. Although the number of reactors 1 may be two or more, the case where six reactors 1 are provided as shown in FIG. 2 will be described in this embodiment.
• the six reactors 1 are arranged around the central axis AX within the housing 3 .
• Each reactor 1 is arranged on a line of similitude CL that resembles the contour of the inner peripheral surface T0 of the housing 3 .
• the center C1 of the circular cross section of each reactor 1 is positioned on the line of similarity CL.
• the similarity line CL is an example of "one similarity line” according to the present invention.
• Each reactor 1 is preferably arranged at equal intervals on the line of similitude CL. Since six reactors 1 are provided in this embodiment, the interval in the circumferential direction between the centers C1 of the reactors 1 is 60 degrees.
• the shortest distances D1 between the housing 3 and each reactor 1 are equal to each other. That is, all reactors 1 are each separated from the housing 3 by the same distance. Therefore, the reaction heat generated by the conversion reaction can be evenly released from each reactor 1 to the outside through the housing 3, so that the thermal environment of each reactor 1 can be made uniform. Therefore, it is possible to suppress the difference in the conversion efficiency in each reactor 1 and the lifetime of each reactor 1 .
• the shortest distance D1 is the distance between the inner peripheral surface T0 of the housing 3 and the outer peripheral surface T1 of each reactor 1.
• the inner peripheral surface T0 of the housing 3 is circular, and the outer peripheral surface T1 of each reactor 1 is also circular.
• the shortest distances D1 are equal to each other not only when all the shortest distances D1 have the same value, but also when the difference between the maximum value and the minimum value included in all the shortest distances D1 is 30% or less of the distance D0. It is a concept that also includes certain cases. If the difference between the maximum value and the minimum value of the shortest distance D1 is 30% or less of the distance D0, it can be considered that the thermal environment of each reactor 1 is substantially uniform.
• the value of the distance D0 from the central axis AX to the line of similarity CL is not particularly limited, it can be, for example, 81 mm or more and 874 mm or less.
• the value of the diameter of the inner peripheral surface T0 of the housing 3 is not particularly limited, it can be, for example, 351 mm or more and 2468 mm or less.
• the value of the diameter of the outer peripheral surface T1 of each reactor 1 is not particularly limited, it can be, for example, 90 mm or more and 360 mm or less.
• the value of the shortest distance D1 is not particularly limited, it can be, for example, 50 mm or more and 180 mm or less.
• FIG. 3 is a perspective view of the reactor 1.
• FIG. 4 is a cross-sectional view taken along line AA of FIG. 3.
• FIG. 5 is a cross-sectional view taken along line BB of FIG. 3.
• FIG. 6 is a cross-sectional view taken along line CC of FIG. 4.
• FIG. 3 is a perspective view of the reactor 1.
• FIG. 4 is a cross-sectional view taken along line AA of FIG. 3.
• FIG. 5 is a cross-sectional view taken along line BB of FIG. 3.
• FIG. 6 is a cross-sectional view taken along line CC of FIG. 4.
• the reactor 1 is formed in a monolithic shape.
• a monolith means a shape having a plurality of holes penetrating in the longitudinal direction, and is a concept including a honeycomb.
• the longitudinal direction is a direction parallel to the central axis AX of the housing 3 described above.
• the reactor 1 has a first end 1a and a second end 1b.
• the first end 1a is a portion extending from one end of the reactor 1 to 2/5 when the reactor 1 is equally divided into 5 in the longitudinal direction.
• the second end portion 1b is a portion extending from the other end portion of the reactor 1 to 2/5 when the reactor 1 is equally divided into 5 in the longitudinal direction.
• the first end 1a of the reactor 1 is the source gas inflow side
• the second end 1b of the reactor 1 is the liquid fuel outflow side.
• the reactor 1 has a first end face S1, a second end face S2 and a side face S3.
• the first end surface S1 is an end surface on the side of the first end portion 1a.
• the second end face S2 is the end face on the second end portion 1b side.
• the first end surface S1 is provided on the opposite side of the second end surface S2.
• the side surface S3 continues to the outer edges of the first end surface S1 and the second end surface S2.
• the reactor 1 includes a porous support 10, a catalyst 20, a separation membrane 30, a first sealing portion 40 and a second sealing portion 50.
• the porous support 10 is a cylindrical body extending in the longitudinal direction of the reactor 1.
• the porous support 10 is composed of a porous material.
• a ceramic material As the porous material, a ceramic material, a metal material, a resin material, or the like can be used, and a ceramic material is particularly suitable.
• aggregates for ceramic materials include alumina (Al 2 O 3 ), titania (TiO 2 ), mullite (Al 2 O 3 SiO 2 ), cerven and cordierite (Mg 2 Al 4 Si 5 O 18 ). At least one of them can be used. At least one of titania, mullite, sinterable alumina, silica, glass frit, clay mineral, and sinterable cordierite can be used as the inorganic binder for the ceramic material.
• the ceramic material need not contain inorganic binders.
• the porous support 10 has multiple first channels 11 and multiple second channels 12 .
• Each first flow path 11 is formed along the longitudinal direction of the reactor 1, as shown in FIG.
• Each first channel 11 is a space on the non-permeate side of the separation membrane 30 .
• a raw material gas is caused to flow through each of the first flow paths 11 .
• Each first channel 11 is a through hole.
• Each first flow path 11 opens to the first end surface S ⁇ b>1 and the second end surface S ⁇ b>2 of the reactor 1 .
• Each first flow path 11 has an inlet e1 for the source gas formed in the first end surface S1 and an outlet e2 for the liquid fuel formed in the second end surface S2.
• a catalyst 20 is arranged in each first channel 11 .
• the number, position, shape, and the like of the first flow paths 11 can be changed as appropriate.
• Each second channel 12 is a space on the permeate side of the separation membrane 30 .
• a sweep gas for sweeping the water vapor that has permeated the separation membrane 30 is flowed through each of the second flow paths 12 .
• An inert gas for example, nitrogen
• air can be used as the sweep gas.
• the number, position, shape, and the like of the second flow paths 12 can be changed as appropriate.
• each second channel 12 is composed of a plurality of cells 13, an inflow slit 14 and an outflow slit 15, as shown in FIGS.
• a plurality of cells 13 are arranged in a row along the short direction of the reactor 1 (the direction perpendicular to the longitudinal direction). Each cell 13 is formed along the longitudinal direction of the reactor 1, as shown in FIG. Both ends of each cell 13 are sealed with first and second plugging portions 17 and 18 .
• the first and second plugging portions 17 and 18 can be made of the porous material described above.
• the inflow slit 14 is formed at the second end 1b of the reactor 1, as shown in FIG.
• the inflow slit 14 is formed along the lateral direction of the reactor 1, as shown in FIG.
• the inflow slit 14 penetrates the plurality of cells 13 . Both ends of the inflow slit 14 open to the side surface S3.
• the inflow slit 14 has a pair of inflow ports d1 that open on the side surface S3.
• the pair of inlets d1 is one end of the second channel 12 in the longitudinal direction.
• Each of the pair of inlets d1 continues to the third space P3.
• Each of the pair of inlets d1 is an example of the "first opening" according to the present invention.
• the outflow slit 15 is formed in the first end 1a of the reactor 1, as shown in FIG.
• the outflow slit 15 is formed along the lateral direction of the reactor 1, as shown in FIG.
• Outflow slits 15 pass through the plurality of cells 13 . Both ends of the outflow slit 15 are opened to the side surface S3.
• the outflow slit 15 has a pair of discharge ports d2 that open on the side surface S3.
• a pair of discharge ports d2 is the other end of the second flow path 12 in the longitudinal direction.
• Each of the pair of discharge ports d2 continues to the fourth space P4.
• Each of the pair of discharge ports d2 is an example of the "second opening" according to the present invention.
• a catalyst 20 is arranged in each first channel 11 .
• the catalyst 20 is preferably filled in each first channel 11 , but may be arranged in layers on the surface of the separation membrane 30 .
• the catalyst 20 accelerates the conversion reaction from the raw material gas shown in the above formula (1) to liquid fuel.
• a known catalyst suitable for the conversion reaction to the desired liquid fuel can be used for the catalyst 20 .
• the catalyst 20 include metal catalysts (copper, palladium, etc.), oxide catalysts (zinc oxide, zirconia, gallium oxide, etc.), and composite catalysts thereof (copper-zinc oxide, copper-zinc oxide-alumina , copper-zinc oxide-chromium oxide-alumina, copper-cobalt-titania, and catalysts obtained by modifying these with palladium).
• the separation membrane 30 is supported by the porous support 10. Separation membrane 30 surrounds first channel 11 . Separation membrane 30 is arranged between first channel 11 and second channel 12 .
• the separation membrane 30 allows water vapor, which is one of the products of the conversion reaction from the source gas to the liquid fuel, to permeate. As a result, the equilibrium shift effect can be used to shift the reaction equilibrium of the above formula (1) to the product side.
• the separation membrane 30 preferably has a water vapor permeability coefficient of 100 nmol/(s ⁇ Pa ⁇ m 2 ) or more.
• the water vapor permeability coefficient can be determined by a known method (see Ind. Eng. Chem. Res., 40, 163-175 (2001)).
• the separation membrane 30 preferably has a separation factor of 100 or more.
• the higher the separation factor the easier it is for water vapor to permeate, and the less it is for components other than water vapor (hydrogen, carbon dioxide, liquid fuel, etc.) to permeate.
• the separation factor can be determined by a known method (see Fig. 1 of "Separation and Purification Technology 239 (2020) 116533").
• An inorganic membrane can be used as the separation membrane 30 .
• An inorganic film is preferable because it has heat resistance, pressure resistance, and water vapor resistance.
• inorganic membranes include zeolite membranes, silica membranes, alumina membranes, and composite membranes thereof.
• an LTA-type zeolite membrane in which the molar ratio (Si/Al) of silicon element (Si) and aluminum element (Al) is 1.0 or more and 3.0 or less is preferable because it has excellent water vapor permeability. be.
• the first seal portion 40 covers the first end surface S1 and part of the side surface S1 of the porous support 10, as shown in FIG.
• the first seal portion 40 prevents the raw material gas from entering the porous support 10 .
• the first seal portion 40 is formed so as not to block the inlet e1 of the first flow path 11, as shown in FIG.
• the first sealing portion 40 covers the first plugging portion 17 .
• the first seal portion 40 can be made of glass, metal, rubber, resin, or the like.
• the second seal portion 50 covers the second end surface S2 and part of the side surface S1 of the porous support 10, as shown in FIG.
• the second seal portion 50 prevents liquid fuel from entering the porous support 10 .
• the second seal portion 50 is formed so as not to block the outlet e2 of the first flow path 11, as shown in FIG.
• the second sealing portion 50 covers the second plugging portion 18 .
• the second seal portion 50 can be made of glass, metal, rubber, resin, or the like.
• the raw material gas flows into the first channel 11 from the inlet e1 of the first channel 11 .
• water vapor is generated together with the liquid fuel according to the above formula (1).
• the synthesized liquid fuel flows out from the outlet e2 of the first channel 11 .
• Water vapor which is one of the products, sequentially permeates the separation membrane 30 and the porous support 10 and moves to the second channel 12 .
• the sweep gas flows into the cell 13 from the inflow slit 14 after flowing in from the inflow port d1 of the inflow slit 14 .
• the sweep gas that has flowed into the cell 13 from the inflow slit 14 takes in the water vapor that has permeated the separation membrane 30, absorbs the reaction heat generated in the conversion reaction, and moves toward the outflow slit 15 into the cell 13. flowing.
• the sweep gas that has reached the outflow slit 15 is discharged from the discharge port d2 of the outflow slit 15 .
• the direction of the sweep gas flowing through the second channel 12 is opposite to the direction of the source gas flowing through the first channel 11 when the separation membrane 30 is viewed from the side. That is, the sweep gas flowing through the second flow path 12 flows in a direction facing the raw material gas flowing through the first flow path 11 .
• the direction of the sweep gas flowing through the second channel 12 may be the same as the direction of the source gas flowing through the first channel 11 . That is, the sweep gas flowing through the second flow path 12 may flow in a direction parallel to the raw material gas flowing through the first flow path 11 .
• FIG. 7 is a cross-sectional view of the reactor module 2a.
• the reactor module 2a according to the second embodiment differs from the reactor module 2 according to the first embodiment in the configuration of the housing and the arrangement of the reactors, the differences will be mainly described below.
• the reactor module 2a comprises a plurality of reactors 1 and a housing 3a.
• a plurality of reactors 1 are housed in a housing 3a.
• the configuration of the reactor 1 is as described in the first embodiment.
• the multiple reactors 1 include multiple first reactors 1x and multiple second reactors 1y.
• the plurality of first reactors 1x are arranged inside the plurality of second reactors 1y in the radial direction.
• the number of the first reactors 1x may be two or more, but in this embodiment, as shown in FIG. 7, eight reactors 1x are provided.
• the number of the second reactors 1y may be two or more, but in this embodiment, as shown in FIG. 7, the case where 16 second reactors 1y are provided will be described.
• the eight first reactors 1x are arranged around the central axis AX within the housing 3a. Each first reactor 1x is arranged on a first similarity line CL1 that resembles the outline of the first inner peripheral surface T10 or the second inner peripheral surface T20 of the housing 3 . Specifically, the center C11 of the circular cross section of each first reactor 1x is positioned on the first similarity line CL1. The first reactors 1x are preferably arranged at equal intervals on the first similarity line CL1. Since eight first reactors 1x are provided in this embodiment, the interval in the circumferential direction between the centers C11 of the first reactors 1x is 45 degrees.
• the 16 second reactors 1y are arranged around the central axis AX inside the housing 3a. Each second reactor 1 y is arranged on a second similarity line CL 2 similar to the outline of the first inner peripheral surface T 10 or the second inner peripheral surface T 20 of the housing 3 . Specifically, the center C12 of the circular cross section of each second reactor 1y is positioned on the second similarity line CL2. The second reactors 1y are preferably arranged at equal intervals on the second similarity line CL2. Since 16 second reactors 1y are provided in this embodiment, the interval in the circumferential direction between the centers C12 of the second reactors 1y is 22.5 degrees.
• the outer shape of the housing 3a is cylindrical with the central axis AX as the center. However, the housing 3a is hollow. The housing 3a is therefore a hollow cylindrical body.
• the housing 3a has a first inner peripheral surface T10 and a second inner peripheral surface T20.
• the first inner peripheral surface T10 is located inside the second inner peripheral surface T20 in the radial direction.
• the second inner peripheral surface T20 surrounds the first inner peripheral surface T10.
• the shortest distances between the housing 3a and each reactor 1 are the same. Specifically, the first shortest distances D11 between the housing 3a and the first reactors 1x are the same, the second shortest distances D12 between the housing 3a and the second reactors 1y are the same, and the The first shortest distance D11 and the second shortest distance D12 are equivalent. That is, all reactors 1 are separated from the housing 3a by the same distance.
• the reaction heat generated by the conversion reaction can be evenly released from each reactor 1 to the outside through the housing 3a.
• the reaction heat of each first reactor 1x is released into the hollow space of the housing 3a through the first inner peripheral surface T10, and the reaction heat of each second reactor 1y is released through the second inner peripheral surface T20. It is released to the outer space of the housing 3a through the.
• the thermal environment of each reactor 1 can be made uniform, so that differences in the conversion efficiency and lifetime of each reactor 1 can be suppressed.
• the first shortest distance D11 is the distance between the first inner peripheral surface T10 of the housing 3a and the outer peripheral surface T11 of each first reactor 1x.
• the first inner peripheral surface T10 of the housing 3a is circular, and the outer peripheral surface T11 of each first reactor 1x is also circular.
• the second shortest distance D12 is the distance between the second inner peripheral surface T20 of the housing 3a and the outer peripheral surface T12 of each second reactor 1y.
• the second inner peripheral surface T20 of the housing 3a is circular, and the outer peripheral surface T12 of each second reactor 1y is also circular.
• that the shortest distances are equal to each other means not only when all the first and second shortest distances D11 and 12 have the same value, but also when all the first and second shortest distances D11 and 12 have the same value.
• the concept also includes the case where the difference between the included maximum value and minimum value is 15% or less of the distance D20. If the difference between the maximum value and the minimum value of the first and second shortest distances D11 and D12 is 30% or less of the distance D20, it is assumed that the thermal environment of each reactor 1 is substantially uniform. can be done.
• the value of the distance D10 from the central axis AX to the first similarity line CL1 is not particularly limited, it can be, for example, 140 mm or more and 874 mm or less.
• the value of the distance D20 from the central axis AX to the second similarity line CL2 is not particularly limited, it can be, for example, 280 mm or more and 1414 mm or less.
• the value of the diameter of the first inner peripheral surface T10 of the housing 3a is not particularly limited, it can be, for example, 90 mm or more and 360 mm or less.
• the value of the diameter of the second inner peripheral surface T20 of the housing 3a is not particularly limited, it can be, for example, 750 mm or more and 3548 mm or less.
• the values of the first and second shortest distances D1 and D2 are not particularly limited, they can be, for example, 50 mm or more and 180 mm or less.
• the outer shape of the reactors 1 and 1a is columnar, but may be elliptical columnar.
• the outer shape of the housings 3 and 3a is columnar, but may be elliptical columnar.
• the inner peripheral surfaces of the housings 3 and 3a have circular cross sections, but they may have elliptical cross sections. If the cross section of the inner peripheral surface of the housing is elliptical, the line of similarity is also elliptical.
• the outer peripheral surface of the reactor 1 has a circular cross section, but it may have an elliptical cross section.
• the configuration of the reactor is not limited to this.
• the reactor may be a non-monolithic reactor.
• a tube type reactor for example, Japanese Unexamined Patent Application Publication No. 2018-008940
• the first flow path 11 and the second flow path 12 each open on the surface (including both end surfaces and side surfaces) of the reactor.
• the third space P3, which is an example of the "non-outflow side space” and the fourth space P4, which is an example of the "outflow side space” are separated by the flow stopper 6.
• the isolation structure of the "non-outflow side space” and the "outflow side space” is not particularly limited.
• an "outflow-side space" isolated from a “non-outflow-side space” may be provided for each reactor 1.
• the reactor module 2a includes a plurality of reactors 1, a housing 3, a first sealing portion 4, a second sealing portion 5, a flow stopper 6, a first airflow resistance member 7, a second airflow resistance member 8, and a discharge pipe 9.
• members functionally similar to those in FIG. 1 are assigned the same numbers.
• the configuration of the reactor 1 is as described in the above embodiment.
• the housing 3 is partitioned into first to fourth spaces P1 to P4 by the first sealing portion 4, the second sealing portion 5 and the flow stop portion 6.
• the housing 3 has a source gas supply port 3a, a liquid fuel discharge port 3b, a sweep gas supply port 3c and a sweep gas discharge port 3d.
• the first sealing part 4 seals between the housing 3 and the first end 1 a of the reactor 1 .
• the first sealing portion 4 separates the third and fourth spaces P3 and P4 from the first space P1.
• the first sealing portion 4 is composed of a fixed plate 41 , a flange 42 and a sealing member 43 . Note that the flange 42 and the seal member 43 are provided for each reactor 1 .
• the fixed plate 41 is connected to the inner peripheral surface of the housing 3 .
• the fixing plate 41 is formed with an opening for attaching the flow stopper 6 .
• the flange 42 is an annular member fixed to the opening of the fixing plate 41 .
• the sealing member 43 is formed in an annular shape and surrounds the first end 1a of the reactor 1 .
• the seal member 43 seals the gap between the flange 42 and the first end portion 1a of the reactor 1 .
• an O-ring can be used as the sealing member 43.
• the second sealing portion 5 seals between the housing 3 and the second end portion 1 b of the reactor 1 .
• the second sealing portion 5 separates the third and fourth spaces P3 and P4 from the second space P2.
• the second sealing portion 5 is composed of a fixing plate 51 , a flange 52 and a sealing member 53 . Note that the flange 52 and the sealing member 53 are provided for each reactor 1 .
• the fixed plate 51 is connected to the inner peripheral surface of the housing 3 .
• the fixing plate 51 has an opening for attaching the flange 52 .
• the flange 52 is an annular member fixed to the opening of the fixing plate 51 .
• the seal member 53 is formed in an annular shape and surrounds the second end portion 1b of the reactor 1 .
• the sealing member 53 seals the gap between the flange 52 and the second end portion 1b of the reactor 1 .
• an O-ring can be used as the sealing member 53.
• the flow stop part 6 is arranged between the third space P3 and the fourth space P4.
• the flow stopper 6 isolates the third space P3 from the fourth space P4.
• the flow stop portion 6 is composed of a partition tube 61 , a partition plate 62 , a packing 63 and a seal member 64 . Note that the flow stop portion 6 is provided for each reactor 1 .
• the partition pipe 61 is a tubular member attached to the opening of the fixing plate 41 .
• Partition pipe 61 is arranged to surround outlet d2 of reactor 1 .
• the partition plate 62 is an annular member arranged between the reactor 1 and the partition pipe 61 .
• the packing 63 is an annular elastic member fixed to the outer circumference of the partition plate 62 .
• the packing 63 seals the gap between the partition tube 61 and the partition plate 62 .
• the seal member 64 seals the gap between the reactor 1 and the partition plate 62 .
• As the sealing member 64 for example, an O-ring can be used.
• the first airflow resistance member 7 is a cylindrical member surrounding the inlet d1 of the reactor 1. Both ends of the first airflow resistance member 7 are fixed to the partition plate 62 and the flange 52 .
• the first ventilation resistance member 7 provides ventilation resistance to the sweep gas flowing into the inlet d1 of the reactor 1 from the third space P3. As a result, pressure loss occurs in the sweep gas supplied from the third space P3, so that the flow rate of the sweep gas flowing into the inlet d1 of each reactor 1 is made uniform regardless of the distance from the sweep gas supply port 3c. be able to. As a result, each reactor 1 can be evenly cooled, so that the thermal environment of each reactor 1 can be made more uniform.
• the second airflow resistance member 8 is a cylindrical member surrounding the outflow port d2 of the reactor 1. Both ends of the second airflow resistance member 8 are fixed to the partition plate 62 and the flange 42 .
• the second ventilation resistance member 8 provides ventilation resistance to the sweep gas (including water vapor) flowing out from the outlet d2 of the reactor 1 into the fourth space P4.
• pressure loss occurs in the sweep gas flowing out of the outlet d2, so the flow rate of the sweep gas flowing through the second flow path 12 of each reactor 1 should be made uniform regardless of the distance from the collecting pipe 93, which will be described later. can be done.
• each reactor 1 can be evenly cooled, so that the thermal environment of each reactor 1 can be made more uniform.
• FIG. 9 is a side view of the first airflow resistance member 7 and the second airflow resistance member 8.
• the first ventilation resistance member 7 has a cylinder body 71 and a plurality of ventilation holes 72 . Each vent 72 functions as an orifice. The ventilation resistance of the first ventilation resistance member 7 can be adjusted by the total opening area determined by the size and number of the ventilation holes 72 .
• the second ventilation resistance member 8 has a cylinder body 81 and a plurality of ventilation holes 82 . Each vent 82 functions as an orifice. The airflow resistance of the second airflow resistance member 8 can be adjusted by the total open area determined by the size and number of the air holes 82 .
• the total opening area of the first ventilation resistance member 7 is smaller than the total opening area of the second ventilation resistance member 8. Therefore, the airflow resistance of the first airflow resistance member 7 is greater than the airflow resistance of the second airflow resistance member 8 . Therefore, the sweep gas flowing into the inflow port d1 from the third space P3 can be given a large ventilation resistance. can be made more uniform. As a result, each reactor 1 can be evenly cooled, so that the thermal environment of each reactor 1 can be further uniformed.
• the reactor module 2a may not include one or both of the first airflow resistance member 7 and the second airflow resistance member 8. Also, the airflow resistance of the second airflow resistance member 8 may be greater than the airflow resistance of the first airflow resistance member 7 .
• the discharge pipe 9 is connected to each partition pipe 61 .
• the discharge pipe 9 discharges the sweep gas (including water vapor) that has flowed out from the outlet d2 of the reactor 1 into the fourth space P4 to the outside.
• FIG. 10 is a top view schematically showing the configuration of the discharge pipe 9.
• the discharge pipe 9 has a plurality of small pipes 91 , annular pipes 92 and collection pipes 93 .
• Each small tube 91 communicates with each partition tube 61 and annular tube 92 .
• the annular pipe 92 communicates with each small pipe 91 and the collecting pipe 93 .
• the collecting pipe 93 penetrates the housing 3 .
• a sweep gas discharge port 3 d is formed at the tip of the collecting pipe 93 . In this manner, the sweep gas flowing out from each reactor 1 is gathered into one collecting pipe 93 and discharged to the outside, so that the sealing performance of the housing 3 can be easily maintained.
• the configuration of the discharge pipe 9 is not limited to that shown in FIG.
• the reactor module 2a may include a packing support PS.
• the packing support PS suppresses the outflow of the catalyst 20 from the first flow path 11 (see FIG. 6) of the reactor 1 .
• the packing support PS covers the second end face S2 of the reactor 1 on the second end 1b side.
• the separation membrane 30 is made to permeate water vapor, which is one of the products of the conversion reaction from the source gas to the liquid fuel.
• the separation membrane 30 may permeate the liquid fuel itself produced by the conversion reaction from the source gas to the liquid fuel. Also in this case, the reaction equilibrium of the above formula (1) can be shifted to the product side.
• the separation membrane 30 is permeable to the liquid fuel, even when the liquid fuel is generated by a reaction that does not generate water vapor (for example, 2H 2 +CO ⁇ CH 3 OH), the reaction equilibrium is shifted to the product side. be able to.
• a reaction that does not generate water vapor for example, 2H 2 +CO ⁇ CH 3 OH
• Module 8 In the above embodiments, a reactor module including a reactor was described, but the present invention is also applicable to a separation membrane module including a plurality of separation filters that require heating or cooling.
• a separation filter has a separation membrane for separating a predetermined component from a mixed fluid.
• the separation membrane may be used at a temperature different from normal temperature by heating or cooling the separation membrane in order to develop or maintain the separation membrane performance.
• each separation filter by equalizing the shortest distance between the housing and each separation filter, each separation filter can be uniformly heated or cooled from the outside, so that the thermal environment of each separation filter can be made uniform. . Therefore, it is possible to suppress the occurrence of differences in the separation performance of each separation filter and the service life of each separation filter.
• non-patent literature (Microporous and Mesoporous Materials 132 (2010) 137-147) discloses that the gas permeation performance of DDR type zeolite membranes depends on temperature.
• a ceramic separation filter may generate thermal stress at the interface of the separation layer due to excessive heating or cooling, which may lead to material destruction. Therefore, if there are separation filters that are not sufficiently heated or cooled or excessively heated or cooled, the separation performance will be relatively low and the service life will be shortened. Therefore, it is important to homogenize the thermal environment of each separation filter to a desired temperature.
• Heating or cooling of each separation filter includes, but is not limited to, a method of heating or cooling the housing from the outside, a method of flowing a heated or cooled fluid into each separation filter, and the like.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Analytical Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Life Sciences & Earth Sciences (AREA)
• Geology (AREA)
• Inorganic Chemistry (AREA)
• Materials Engineering (AREA)
• Dispersion Chemistry (AREA)
• Physical Or Chemical Processes And Apparatus (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=87765408

Family Applications (1)

Country Status (6)

Citations (11)

Family Cites Families (6)

• 2022
  • 2022-11-01 CN CN202280092662.9A patent/CN118765212A/zh active Pending
  • 2022-11-01 JP JP2024502824A patent/JP7853401B2/ja active Active
  • 2022-11-01 WO PCT/JP2022/040915 patent/WO2023162352A1/ja not_active Ceased
  • 2022-11-01 AU AU2022443745A patent/AU2022443745A1/en active Pending
  • 2022-11-01 EP EP22928870.9A patent/EP4487945A4/en active Pending
• 2024
  • 2024-06-28 US US18/757,682 patent/US20240350983A1/en active Pending

Patent Citations (11)

Non-Patent Citations (4)

Also Published As

Similar Documents

Legal Events