WO2011018919A1 - Membrane de séparation de mélange, procédé de modification de la composition d’un mélange utilisant celle-ci, et dispositif de séparation de mélange - Google Patents

Membrane de séparation de mélange, procédé de modification de la composition d’un mélange utilisant celle-ci, et dispositif de séparation de mélange Download PDF

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Publication number
WO2011018919A1
WO2011018919A1 PCT/JP2010/060126 JP2010060126W WO2011018919A1 WO 2011018919 A1 WO2011018919 A1 WO 2011018919A1 JP 2010060126 W JP2010060126 W JP 2010060126W WO 2011018919 A1 WO2011018919 A1 WO 2011018919A1
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mixture
separation membrane
membrane
separation
permeation
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PCT/JP2010/060126
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English (en)
Japanese (ja)
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直人 木下
応明 河合
明昌 市川
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日本碍子株式会社
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    • 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
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
    • B01D61/362—Pervaporation
    • 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
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0067—Inorganic membrane manufacture by carbonisation or pyrolysis
    • 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
    • B01D71/021—Carbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/11—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by dialysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness
    • 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 separation membrane for a mixture capable of changing the composition of a mixture containing an aromatic hydrocarbon and a non-aromatic hydrocarbon, a method for changing the composition of the mixture using the same, and a mixture separation apparatus.
  • Membrane separation technology has been used in various fields including the field of food and medicine and water treatment from the viewpoint of energy saving and low environmental load.
  • Conventional membrane separation techniques have been dominated by solid / liquid separation, for example, as used in the food field.
  • certain components in the mixture for example, water or alcohol in this case
  • Enrichment separation operations have been performed using membrane separation techniques to change the composition of the mixture.
  • Patent Document 1 discloses a polymer separation membrane used for changing the composition of a mixture containing an n-paraffin hydrocarbon liquid and an aromatic hydrocarbon liquid by a separation operation.
  • Patent Document 5 discloses an in-vehicle fuel separation device including a component adjustment unit that adjusts a fuel component composition by a separation membrane that selectively permeates a high octane component in a fuel.
  • Patent Document 6 linear hydrocarbons that are low-octane components in gasoline are separated and components other than the remaining low-octane components are supplied to the internal combustion engine, while linear chains that are separated low-octane components are supplied.
  • An oil supply device and an oil supply method for supplying an internal combustion engine after producing a high octane number component by isomerizing type hydrocarbons are disclosed.
  • Examples of separation means that use a mordenite membrane, a ZSM-5 membrane, or an MFI zeolite membrane as the separation membrane are disclosed.
  • an object of the present invention is to provide a separation membrane for a mixture having higher permeation performance than a conventional separation membrane, and to provide a method for changing the composition of a mixture using the separation membrane for a mixture, and a mixture separation device.
  • the following separation membrane for a mixture a method for changing the composition of the mixture, and a mixture separation apparatus are provided.
  • a separation membrane for a mixture capable of changing the composition of the mixture by permeating a mixture containing an aromatic hydrocarbon and a non-aromatic hydrocarbon, the carbon containing 50% or more by mass,
  • the permeation rate of SF 6 gas at room temperature before permeating the mixture is 1.0 ⁇ 10 ⁇ 8 mol / Pa ⁇ m 2 ⁇ s or more and 4.1 ⁇ 10 ⁇ 6 mol / Pa ⁇ m 2 ⁇ s.
  • Separation membrane for a mixture that is less than.
  • the separation membrane for a mixture according to any one of [1] to [7] is provided, and has a porous base material that supports the separation membrane, and the raw material side space and the permeation side space by the porous base material.
  • a component that permeates the separation membrane for the mixture from the permeation side space a separation unit that divides the raw material side space, a supply unit that supplies a mixture containing aromatic hydrocarbons and non-aromatic hydrocarbons to the raw material side space, A permeation recovery unit for recovery.
  • the separation membrane for a mixture of the present invention has a permeation rate of SF 6 (sulfur hexafluoride) gas of a predetermined value or more, an aromatic hydrocarbon having a molecular diameter close to that of SF 6 (0.55 nm).
  • SF 6 sulfur hexafluoride
  • excellent permeation performance is exhibited as compared with a separation membrane made of a conventional molecular sieve carbon membrane or the like, and a high permeation flux (Flux) is obtained while having selectivity.
  • the separation membrane for a mixture of the present invention is a separation membrane with few membrane defects by limiting the permeation rate of SF 6 gas to less than a predetermined value.
  • the composition change method and the mixture separator of the present invention use the separation membrane for a mixture having the above-described excellent permeation performance
  • the mixture includes an aromatic hydrocarbon and a non-aromatic hydrocarbon.
  • Aromatic hydrocarbons can be separated from the mixture with high permeation flux (Flux).
  • the separation membrane for a mixture of the present invention (hereinafter sometimes simply referred to as “separation membrane”) can change the composition of the mixture by permeating a mixture containing aromatic hydrocarbons and non-aromatic hydrocarbons.
  • a separation membrane comprising 50% or more of carbon by mass, and the permeation rate of SF 6 gas at room temperature before permeating the mixture is 1.0 ⁇ 10 ⁇ 8 mol / Pa ⁇ m 2 ⁇ s or more, And less than 4.1 ⁇ 10 ⁇ 6 mol / Pa ⁇ m 2 ⁇ s.
  • permeation performance in the case of separating (permeating) aromatic hydrocarbons from a mixture containing aromatic hydrocarbons and non-aromatic hydrocarbons by the separation membrane is SF of the separation membrane. It was found that there was a correlation with the permeation rate of 6 gases. This is because SF 6 has a molecular diameter (0.55 nm) close to the molecular diameter of the aromatic hydrocarbon having a larger molecular diameter than that of the non-aromatic hydrocarbon.
  • the present inventors to prepare a separation membrane variously changing the transmission rate of the SF 6 gas, for their separation membrane, the result of examining the permeability for various aromatic hydrocarbons, transmission of SF 6 gas Practical when a separation membrane having a speed of 1.0 ⁇ 10 ⁇ 8 mol / Pa ⁇ m 2 ⁇ s or more (preferably 1.0 ⁇ 10 ⁇ 7 mol / Pa ⁇ m 2 ⁇ s or more) is used. It was confirmed that high transmission performance was obtained.
  • the separation membrane of the present invention limits the permeation rate of SF 6 gas to less than 4.1 ⁇ 10 ⁇ 6 mol / Pa ⁇ m 2 ⁇ s. By limiting the permeation rate of SF 6 gas to such a value, the separation membrane has few membrane defects. When the permeation rate of SF 6 gas exceeds 4.1 ⁇ 10 ⁇ 6 mol / Pa ⁇ m 2 ⁇ s, the separation membrane has many membrane defects, and the mixture is separated at the defective portion. Since it permeates as it is, it does not function sufficiently as a separation membrane.
  • the separation membrane of the present invention contains 50% or more of carbon by mass ratio.
  • a separation membrane containing a high proportion of carbon in this way has a higher durability to a mixture containing aromatic hydrocarbons and non-aromatic hydrocarbons than a polymer separation membrane, and stable permeation performance over a long period of time. Can be maintained.
  • the thickness of the separation membrane of the present invention is preferably 0.01 to 1 ⁇ m, more preferably 0.05 to 0.5 ⁇ m. When the film thickness is less than 0.01 ⁇ m, defects may occur in the film. When the film thickness is greater than 1 ⁇ m, the permeation flux at the time of separating aromatic hydrocarbons from the liquid mixture may be lowered.
  • the carbon-containing layer as a precursor is heat-treated (thermal decomposition) in a temperature range of 600 to 800 ° C., preferably 650 to 750 ° C. in an oxygen inert atmosphere. ) And carbonized.
  • oxygen inert atmosphere refers to an atmosphere in which a precursor for forming a separation membrane (carbon membrane) is not oxidized even when heated in the above temperature range. Specifically, an inert atmosphere such as nitrogen or argon is used. An atmosphere such as in active gas or vacuum.
  • the thermal decomposition does not take place sufficiently, resulting in insufficient pore formation.
  • the separation membrane is thermally contracted and the pores are contracted and reduced. Therefore, when the temperature at which the precursor carbon-containing layer is heat-treated (pyrolysis) is less than 600 ° C. or more than 800 ° C., a separation membrane having the SF 6 gas permeation rate as described above is obtained. It is difficult to form a separation membrane with practical permeation performance.
  • the carbon-containing layer that is the precursor is not particularly limited as long as it is a layer containing carbon, but is preferably a resin layer, and the resin that forms the resin layer includes polyimide resins and phenols.
  • the resin is preferably at least one resin selected from the group consisting of a series resin.
  • the separation membrane of the present invention is usually formed on a porous substrate and used in the state of a separation membrane arrangement in which the separation membrane and the porous substrate that supports it are integrated.
  • the material of the porous substrate is not particularly limited as long as it has sufficient strength, permeation performance, corrosion resistance, etc.
  • metal, ceramics, etc. can be used.
  • a porous substrate made of ceramics alumina particles, silica particles, cordierite particles, zirconia particles, mullite particles and the like are preferable as the ceramic particles constituting the porous substrate.
  • the average pore diameter of the porous substrate is preferably 0.01 to 10 ⁇ m, and more preferably 0.05 to 5 ⁇ m.
  • the “average pore diameter” can be measured by a gas adsorption method.
  • the porosity of the porous substrate is preferably 30 to 70%, more preferably 40 to 60%. If the porosity of the porous substrate is less than 30%, the permeation flux when separating the aromatic hydrocarbon from the liquid mixture may decrease, and if it exceeds 70%, the strength of the porous substrate decreases. There is a case.
  • the “porosity” can be measured by the Archimedes method.
  • a suitable porous substrate is an average particle size of 0.3 to 0.3 on the inner wall surface of the through-hole of a monolithic alumina porous substrate having an average particle size of 10 to 100 ⁇ m and an average pore size of 1 to 30 ⁇ m.
  • 10 ⁇ m alumina particles are deposited by filtration and then fired to form a first surface dense layer having a thickness of 10 to 1000 ⁇ m and an average pore diameter of 0.1 to 3 ⁇ m.
  • Examples include alumina particles having a particle diameter of 0.03 to 1 ⁇ m deposited by filtration and then fired to form a second surface dense layer having a thickness of 1 to 100 ⁇ m and an average pore diameter of 0.01 to 0.5 ⁇ m.
  • the shape of the porous substrate is not particularly limited, and the shape may be determined according to the purpose, such as a disk shape, a polygonal plate shape, a cylinder shape such as a cylinder or a square tube, a column shape such as a column or a prism.
  • a monolithic porous substrate As shown in FIG. 1, the “monolith-shaped porous substrate” means a lotus-like or honeycomb-shaped porous substrate 1 having a plurality of through holes 2 formed in the longitudinal direction 60 (monolith-shaped substrate). Say 1a).
  • the size of the porous substrate is not particularly limited, and the size can be determined according to the purpose as long as the strength required for the support is satisfied and the permeability of the separation membrane is not impaired.
  • sticker part 12 is arrange
  • the seal portion 12 is disposed so as not to block the through-hole 2 over the entire end faces 4 and 4 of the porous substrate 1.
  • the seal portion 12 examples include a glass seal and a metal seal, and among these, a glass seal is preferable in that the thermal expansion coefficient with the porous substrate 1 can be easily matched. Although it does not specifically limit as a physical property of the glass used for a glass seal, It is preferable to have a thermal expansion coefficient near the thermal expansion coefficient of a porous base material.
  • the glass used for the glass seal is preferably lead-free glass that does not contain lead.
  • the method for producing a separation membrane of the present invention will be described by taking the case where the porous substrate forming the separation membrane is a monolith-shaped substrate as an example.
  • a monolith-shaped substrate 1a that is a support for forming a separation membrane is prepared.
  • the monolith-shaped substrate 1a can be produced by forming a molding raw material (kneaded material) made of a predetermined component into a monolith shape by a conventionally known extrusion molding method, and firing the obtained molded body.
  • a glass paste is applied to both end faces 4 and 4 of the monolith-shaped substrate 1a and heated at a predetermined temperature to form a seal portion 12 as shown in FIG.
  • a glass material applied to the monolithic substrate 1a as a glass paste lead-free glass containing no lead is preferable.
  • the glass material preferably has a softening point of 800 to 1000 ° C. If the softening point is lower than 800 ° C., the glass may melt during the heat treatment in the formation process of the separation membrane 11, and if higher than 1000 ° C., the particles constituting the monolithic substrate 1a are sintered more than necessary. It may make you progress.
  • the glass paste can be produced by dispersing powdered glass in a solvent such as water. Alternatively, the polymer may be added in addition to a solvent such as water.
  • membrane which consists of a precursor solution for setting it as the separation membrane 11 with respect to the monolith-shaped base material 1a is performed.
  • the method of passing the precursor solution through the through-hole 2 of the monolith-shaped substrate 1a may be any method that makes the film thickness uniform, and is not particularly limited.
  • dip film formation can be given.
  • the film formation may be performed while pressurizing with a gas such as N 2 from the side surface 3 of the monolith-shaped base material 1a toward the film formed on the inner peripheral surface of the through-hole 2. It is possible to prevent the precursor solution from penetrating and to form a flat film having a uniform thickness.
  • a solution obtained by dissolving a polyimide resin and / or a phenol resin in an appropriate organic solvent such as N-methyl-2-pyrrolidone (NMP) is used. It is preferable.
  • concentration of the polyimide resin and / or phenol resin in the precursor solution is not particularly limited, but is preferably 1 to 15% by mass from the viewpoint of making the solution easy to form a film.
  • a drying process for drying the film (coat layer) made of the precursor solution is performed.
  • the coat layer is air-dried while passing hot air from the opening 51 of one end face 4 to the opening 51 of the other end face 4.
  • a heat treatment step (carbonization) of the resin layer (carbon-containing layer) obtained by drying the coat layer is performed in a vacuum or an inert atmosphere such as a nitrogen atmosphere or an argon atmosphere.
  • the resin layer is carbonized by pyrolysis in a temperature range of 600 to 800 ° C., whereby a separation membrane (carbon membrane) 11 as shown in FIG. 3 is obtained.
  • carbonization is performed at a temperature lower than 600 ° C., the resin layer is not sufficiently carbonized, and the selectivity as a molecular sieve membrane and the permeation rate are lowered.
  • the permeation rate decreases due to shrinkage of the pore diameter.
  • the composition changing method of the mixture of the present invention is a method of changing the composition of the mixture using the separation membrane of the present invention. Specifically, a mixture containing an aromatic hydrocarbon and a non-aromatic hydrocarbon is brought into contact with one side surface (supply side surface) of the separation membrane as a supply mixture, and the other side surface (permeation side surface) of the separation membrane. ) To permeate (discharge) aromatic hydrocarbons to change the composition in the mixture.
  • the mixture that can be used in this composition change method includes an aromatic hydrocarbon and a non-aromatic hydrocarbon.
  • aromatic hydrocarbons include benzene, toluene, xylene and the like.
  • Non-aromatic hydrocarbons include n-hexane, n-heptane, n-octane, cyclohexane, dimethylbutane, i-octane, 2,2-dimethylbutane, 2,3-dimethylbutane, and the like.
  • the mixture is preferably supplied in a heated state.
  • the permeation method may be a method in which the mixture is supplied in a liquid state and permeated in a gas state (pervaporation, pervaporation), or a method in which the liquid is once vaporized by heating or bubbling and permeated in a gas state (vapor). Permeation). Further, heating or bubbling may be performed until a part of the liquid is vaporized.
  • Aromatic hydrocarbons in the mixture pass through the separation membrane and are discharged from the permeation side surface.
  • the permeation side of the separation membrane needs to be decompressed using a known vacuum device such as a vacuum pump or a pressure controller.
  • the specific degree of vacuum in the transmission side space is preferably 1.0 Torr or less, and more preferably 0.5 Torr or less.
  • the fragrance in the mixed vapor on the membrane permeation side of the separation membrane Separation is possible such that the mass fraction of the aromatic hydrocarbon is higher than the mass fraction of the aromatic hydrocarbon in the feed mixture (mixed steam).
  • the mixture is a liquid
  • the mass fraction of aromatic hydrocarbons in the mixed vapor on the membrane permeation side of the separation membrane is reduced when the mixture is permeated to the separation membrane from the membrane supply side as a supply mixture. It is possible to achieve a separation that exceeds the mass fraction of aromatic hydrocarbons in the mixed vapor that is in equilibrium with the feed mixture, that is, exceeding the vapor-liquid equilibrium.
  • the mixture separator of the present invention is for carrying out the composition changing method of the mixture of the present invention.
  • the mixture separation apparatus includes a separation unit that partitions a raw material side space and a permeation side space, a supply unit that supplies a mixture containing aromatic hydrocarbons and non-aromatic hydrocarbons to the raw material side space, and a permeation side space. And a permeate recovery unit that recovers permeate and / or permeate gas that has permeated through the separation membrane.
  • FIG. 5 is a schematic view showing an embodiment of the mixture separation device of the present invention, in which the separation unit is provided with the separation membrane of the present invention and has a porous substrate that supports the SUS.
  • the module 37 is made up of.
  • the supply unit is constituted by a raw material tank 35 and a circulation pump 36, and the permeation recovery unit is constituted by a cooling trap 38 and a vacuum pump 39 which are cooling devices.
  • the raw material tank 35 heats and holds a mixture (raw material (supplied component)) containing aromatic hydrocarbons and non-aromatic hydrocarbons placed in the tank at a predetermined temperature (for example, 50 ° C.).
  • the SUS module 37 is formed with a supply component introduction port 37 a and a supply component discharge port 37 b so as to communicate with the raw material side space 31.
  • a permeated vapor recovery port 37c for discharging is formed.
  • the mixture in the raw material tank 35 is configured to be supplied to the raw material side space 31 of the SUS module 37 by the circulation pump 36.
  • the SUS module 37 is configured such that the porous base material 1 (monolithic base material 1a) on which the separation membrane 11 is formed can be installed at predetermined positions on both ends of the outer periphery through o-rings 33. Yes.
  • the SUS module 37 is partitioned into a raw material side space 31 and a permeation side space 32 by an o-ring 33, a glass seal (seal part 12), and the separation membrane 11.
  • a cooling trap (liquid nitrogen trap) 38 and a vacuum pump 39 are provided on the permeate vapor recovery port 37c side of the SUS module 37, and the permeate vapor discharged from the permeate vapor recovery port 37c is liquefied by the cooling trap 38. It is configured to collect.
  • the supply component heating means 40 for heating the mixture supplied to the raw material side space 31, and to supply the mixture in a heated state.
  • the supply component heating means 40 can be disposed upstream of the SUS module 37, but may be disposed so as to heat the entire SUS module 37 to indirectly heat the mixture. Further, it may be integrated with the SUS module 37, and the SUS module 37 itself may also serve as the supply component heating means 40.
  • the mixture (raw material) is supplied from the supply component introduction port 37 a to the raw material side space 31 of the SUS module 37 by the circulation pump 36, and the mixture discharged from the supply component discharge port 37 b is returned to the raw material tank 35. Circulate the mixture.
  • the base material side of the separation membrane 11 is depressurized by the vacuum pump 39, so that the permeated vapor recovery port passes through the membrane permeation side 11b of the separation membrane 11.
  • the permeated vapor discharged from 37c is recovered by the cooling trap 38.
  • the degree of vacuum in the transmission side space 32 is controlled by a pressure controller under a predetermined reduced pressure (for example, about 0.5 Torr).
  • the mixture separation apparatus of the present invention uses the separation membrane of the present invention having excellent permeation performance, a high permeate flow of aromatic hydrocarbons from a mixture containing aromatic hydrocarbons and non-aromatic hydrocarbons. It can be separated and collected in a bundle (Flux).
  • the mixture separation apparatus of the present invention may be a batch method in which the mixture is circulated as described above, or a continuous method in which the mixture that has permeated the separation membrane is continuously circulated without being circulated.
  • Example 1 A porous alumina columnar substrate (monolithic substrate) having a diameter of 30 mm and a length of 160 mm provided with 55 through-holes having a diameter of 2.5 mm along the longitudinal direction was produced by extrusion molding and firing. The both ends were sealed by melting glass.
  • a solution obtained by dissolving a commercially available polyimide resin (U varnish S manufactured by Ube Industries Co., Ltd.) in a solvent was dip coated on the inner wall surface of the through-hole of the monolith-shaped substrate to form a coating layer.
  • the dip coating was performed while pressurizing at 100 kPa with N 2 gas from the monolith substrate side (side surface of the monolith substrate) in order to prevent the solution from penetrating into the monolith substrate.
  • hot air was blown into the through-hole in which the coat layer was formed on the inner wall surface, and the solvent was roughly dried, followed by further drying in the atmosphere at 300 ° C. for 1 hour.
  • This process was repeated four times to form a resin layer on the inner wall surface of the through hole of the monolith-shaped substrate.
  • the resin layer is evacuated with a commercially available rotary vacuum pump. The degree of vacuum was 160 Pa.
  • the monolith-shaped substrate on which the resin layer is formed is heat-treated at 600 ° C. for 1 hour in a nitrogen atmosphere (temperature increase rate: 300 ° C./h) to carbonize the resin layer, thereby penetrating the monolith-shaped substrate.
  • a carbon membrane (separation membrane) formed on the inner wall surface of the hole was obtained.
  • the carbon content of the carbon film produced in the same process without using the monolith-shaped substrate was measured by CHN coder MT-5 manufactured by Yanaco Analytical Co., Ltd. and found to be 70% by mass. Moreover, when the film thickness of this carbon film was confirmed by SEM, it was about 0.5 ⁇ m.
  • Example 2 Carbon film formed on the inner wall surface of the through hole of the monolith-shaped substrate in the same manner as in Example 1 except that the heat treatment temperature (carbonization temperature) for carbonizing the resin layer was changed from 600 ° C. to 650 ° C. (Separation membrane) was obtained. In addition, after forming the resin layer, the degree of vacuum measured in the same manner as in Example 1 was 232 Pa.
  • Example 3 The resin used as a raw material for the resin layer is a commercially available phenolic resin (Bellpearl S899 manufactured by Air Water Co., Ltd.) instead of a commercially available polyimide resin, and a heat treatment temperature (carbonization temperature) for carbonizing the resin layer. ) was changed from 600 ° C. to 650 ° C., and a carbon membrane (separation membrane) formed on the inner wall surface of the through hole of the monolith-shaped substrate was obtained in the same manner as in Example 1. The degree of vacuum measured in the same manner as in Example 1 after forming the resin layer was 20 Pa.
  • Example 4 Carbon film formed on the inner wall surface of the through hole of the monolith-shaped substrate in the same manner as in Example 3 except that the heat treatment temperature (carbonization temperature) for carbonizing the resin layer was changed from 650 ° C. to 700 ° C. (Separation membrane) was obtained.
  • the vacuum degree measured similarly to the said Example 1 after resin layer formation was 83 Pa.
  • Example 5 Carbon film formed on the inner wall surface of the through hole of the monolith-shaped substrate in the same manner as in Example 3 except that the heat treatment temperature (carbonization temperature) for carbonizing the resin layer was changed from 650 ° C. to 750 ° C. (Separation membrane) was obtained. In addition, after forming the resin layer, the degree of vacuum measured in the same manner as in Example 1 was 115 Pa.
  • Example 6 Carbon film formed on the inner wall surface of the through hole of the monolith-shaped substrate in the same manner as in Example 3 except that the heat treatment temperature (carbonization temperature) for carbonizing the resin layer was changed from 650 ° C. to 800 ° C. (Separation membrane) was obtained. Note that after the resin layer was formed, the degree of vacuum measured in the same manner as in Example 1 was 51 Pa.
  • Example 1 Carbon film formed on the inner wall surface of the through hole of the monolith-shaped substrate in the same manner as in Example 1 except that the heat treatment temperature (carbonization temperature) for carbonizing the resin layer was changed from 600 ° C. to 550 ° C. (Separation membrane) was obtained. In addition, after forming the resin layer, the degree of vacuum measured in the same manner as in Example 1 was 30 Pa.
  • Example 2 Carbon film formed on the inner wall surface of the through hole of the monolith-shaped substrate in the same manner as in Example 1 except that the heat treatment temperature (carbonization temperature) for carbonizing the resin layer was changed from 600 ° C. to 850 ° C. (Separation membrane) was obtained. In addition, the vacuum degree measured similarly to the said Example 1 after resin layer formation was 141 Pa.
  • Example 3 Carbon film formed on the inner wall surface of the through hole of the monolith-shaped substrate in the same manner as in Example 3 except that the heat treatment temperature (carbonization temperature) for carbonizing the resin layer was changed from 650 ° C. to 550 ° C. (Separation membrane) was obtained. Note that after the resin layer was formed, the degree of vacuum measured in the same manner as in Example 1 was 35 Pa.
  • Example 5 The monolith-shaped substrate penetrates in the same manner as in Example 1 except that the number of repetitions of the step of forming and drying the coating layer on the inner wall surface of the through-hole of the monolith-shaped substrate is changed from 4 times to 1 time. A carbon membrane (separation membrane) formed on the inner wall surface of the hole was obtained. The vacuum degree measured in the same manner as in Example 1 after forming the resin layer was 612 Pa.
  • SF 6 gas was supplied to the supply-side space 131 of the SUS module 137 from the cylinder connected to the supply gas introduction port 137a at room temperature. Since the gas supply side space 131 is closed at the rear stage (supply gas discharge port 137 b) of the SUS module 137, the SF 6 gas supplied to the supply side space 131 gives a predetermined pressure to the separation membrane 11. In this test, the gas supply side space 131 was 0.05 MPa in gauge pressure, and the permeation side space 132 was atmospheric pressure. After confirming that the gas permeation flow rate was stable, the permeation rate of SF 6 gas measured with a dry gas meter or soap film flow meter provided on the gas recovery port 137c side for a certain time was determined. This is shown in FIG.
  • a monolith-shaped substrate 1a on which the separation membrane 11 is formed is stored in a SUS casing (SUS module 37) at both outer peripheral portions via o-rings 33. It was installed in the position.
  • the SUS module 37 is partitioned into a raw material side space 31 and a permeation side space 32 by an o-ring 33, a glass seal (seal part 12), and the separation membrane 11.
  • the SUS module 37 is provided with a supply component introduction port 37a and a supply component discharge port 37b so as to communicate with the raw material side space 31, and the permeation side space 32 transmits permeated vapor to the outside.
  • a steam recovery port 37c is formed.
  • the supply liquid (liquid mixture) is supplied from the supply component introduction port 37a to the raw material side space 31 of the SUS module 37 by the supply pump 36, and the supply liquid discharged from the supply component discharge port 37b is supplied to the raw material tank 35.
  • the feed liquid was circulated by returning to.
  • the linear velocity during circulation is 1.4 m per second.
  • the base material side of the separation membrane 11 is depressurized by the vacuum pump 39, whereby the permeated vapor that permeates the separation membrane 11 and is discharged from the permeated vapor recovery port 37c is cooled by a trap ( Liquid nitrogen trap) 38 was used.
  • the degree of vacuum of the transmission side space 32 was controlled to 0.5 Torr by a pressure controller.
  • the mass of the permeate liquefaction (permeate) collected in the cooling trap 38 is measured in this way, and the composition of the permeate vapor is quantified by gas chromatography analysis, and the permeate flux of the total permeate, aromatic hydrocarbons.
  • the permeation flux and separation factor of the system liquid and the non-aromatic hydrocarbon liquid were calculated.
  • the SF 6 gas permeation rate is 1.0 ⁇ 10 ⁇ 8 mol / Pa ⁇ m 2 ⁇ s or more and less than 4.1 ⁇ 10 ⁇ 6 mol / Pa ⁇ m 2 ⁇ s.
  • the separation membranes of Examples 1 to 6 all showed a high separation factor of 2 or more, and the permeation flux (permeated vapor amount) of benzene, which is an aromatic hydrocarbon-based liquid, was 0.5 kg / m 2 ⁇ A large value of h or more was shown.
  • the SF 6 gas permeation rate is 1.0 ⁇ 10 ⁇ 8 mol / Pa ⁇ m 2 ⁇ s or more and less than 4.1 ⁇ 10 ⁇ 6 mol / Pa ⁇ m 2 ⁇ s.
  • the separation membranes of Examples 1 to 6 all showed a high separation factor of 2 or more, and the permeation flux (permeated vapor amount) of toluene, which is an aromatic hydrocarbon-based liquid, was 0.2 kg / m 2 ⁇ A large value exceeding h was shown.
  • the permeation rate of SF 6 gas is 1.0 ⁇ 10 ⁇ 8 mol / Pa ⁇ m 2 ⁇ s or more and less than 4.1 ⁇ 10 ⁇ 6 mol / Pa ⁇ m 2 ⁇ s.
  • the separation membranes of Examples 1 to 6 all showed a high separation factor of 2.5 or more, and the permeation flux (permeated vapor amount) of benzene, which is an aromatic hydrocarbon-based liquid, was 0.4 kg / m. An extremely large value of 2 ⁇ h or more was exhibited.
  • the separation membrane of Example 3 showed the largest benzene permeation flux of 3.569 kg / m 2 ⁇ h, and the separation membrane of Example 4 showed the largest separation factor of 16.5.
  • the permeation rate of SF 6 gas is 1.0 ⁇ 10 ⁇ 8 mol / Pa ⁇ m 2 ⁇ s or more and less than 4.1 ⁇ 10 ⁇ 6 mol / Pa ⁇ m 2 ⁇ s.
  • the separation membrane of Example 4 has a high separation factor of 8 or more, and the permeation flux (permeated vapor amount) of benzene, which is an aromatic hydrocarbon-based liquid, is as extremely large as 5 kg / m 2 ⁇ h or more. showed that.
  • the separation membrane for a mixture, the composition changing method of the mixture, and the mixture separating apparatus of the present invention can be used for changing the composition of a mixture containing aromatic hydrocarbons and non-aromatic hydrocarbons.
  • 1 porous substrate, 1a: monolith-shaped substrate, 2: through-hole, 3: side surface, 4: end surface, 5: inner wall surface, 11: separation membrane, 11a: membrane supply side, 11b: membrane permeation side, 12 : Seal part, 31: raw material side space, 32: permeate side space, 33: o-ring, 35: raw material tank, 36: circulation pump, 37: SUS module, 37a: supply component inlet, 37b: supply component discharge Outlet, 37c: permeate vapor recovery port, 38: cooling trap, 39: vacuum pump, 40: feed component heating means, 51: opening, 60: longitudinal direction, 101: mixture separator, 131: gas supply side space, 132 : Permeation side space, 133: o-ring, 137: SUS module, 137a: supply gas introduction port, 137b: supply gas discharge port, 137c: gas recovery port.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention a pour objet une membrane de séparation de mélange qui peut modifier la composition d’un mélange qui contient des hydrocarbures aromatiques et des hydrocarbures non aromatiques par la perméation du mélange susmentionné à travers ladite membrane, qui contient au moins 50 % de carbone en masse, et qui possède une vitesse de transmission du gaz SF6 à température ambiante avant perméation du mélange susmentionné d’au moins 1,0 x 10-8 mol/Pa·m2·s et inférieure à 4,1 x 10-6 mol/Pa·m2·s.
PCT/JP2010/060126 2009-08-13 2010-06-15 Membrane de séparation de mélange, procédé de modification de la composition d’un mélange utilisant celle-ci, et dispositif de séparation de mélange WO2011018919A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013145863A1 (fr) * 2012-03-30 2013-10-03 日本碍子株式会社 Membrane de carbone, ainsi que procédé de fabrication de celle-ci, et filtre à membrane de carbone
JP2014520999A (ja) * 2011-06-30 2014-08-25 コーニング インコーポレイテッド 交換式燃料分離ユニット
US10478778B2 (en) 2015-07-01 2019-11-19 3M Innovative Properties Company Composite membranes with improved performance and/or durability and methods of use
US10618008B2 (en) 2015-07-01 2020-04-14 3M Innovative Properties Company Polymeric ionomer separation membranes and methods of use
US10737220B2 (en) 2015-07-01 2020-08-11 3M Innovative Properties Company PVP- and/or PVL-containing composite membranes and methods of use

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001232156A (ja) * 2000-02-23 2001-08-28 Kanebo Ltd 分子ふるい炭素膜を用いた浸透気化分離方法または蒸気分離方法
JP2001276554A (ja) * 2000-03-29 2001-10-09 Kyocera Corp ガス分離フィルタおよびガス分離モジュール
JP2003286018A (ja) * 2002-03-27 2003-10-07 Ngk Insulators Ltd 炭素膜及びその製造方法
JP2007533432A (ja) * 2004-01-13 2007-11-22 ビーエーエスエフ　アクチェンゲゼルシャフト 膜の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001232156A (ja) * 2000-02-23 2001-08-28 Kanebo Ltd 分子ふるい炭素膜を用いた浸透気化分離方法または蒸気分離方法
JP2001276554A (ja) * 2000-03-29 2001-10-09 Kyocera Corp ガス分離フィルタおよびガス分離モジュール
JP2003286018A (ja) * 2002-03-27 2003-10-07 Ngk Insulators Ltd 炭素膜及びその製造方法
JP2007533432A (ja) * 2004-01-13 2007-11-22 ビーエーエスエフ　アクチェンゲゼルシャフト 膜の製造方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014520999A (ja) * 2011-06-30 2014-08-25 コーニング インコーポレイテッド 交換式燃料分離ユニット
WO2013145863A1 (fr) * 2012-03-30 2013-10-03 日本碍子株式会社 Membrane de carbone, ainsi que procédé de fabrication de celle-ci, et filtre à membrane de carbone
US10478778B2 (en) 2015-07-01 2019-11-19 3M Innovative Properties Company Composite membranes with improved performance and/or durability and methods of use
US10618008B2 (en) 2015-07-01 2020-04-14 3M Innovative Properties Company Polymeric ionomer separation membranes and methods of use
US10737220B2 (en) 2015-07-01 2020-08-11 3M Innovative Properties Company PVP- and/or PVL-containing composite membranes and methods of use

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