JP2004033981A - Fluid separation filter and fluid separation module - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a small-sized fluid separation filter enhanced in the recovery efficiency of the permeated fluid through a separation layer, and a fluid separation module. <P>SOLUTION: The fluid separation filter is equipped with a plurality of fluid partition walls 1 wherein separation layers 6a and 6b are provided on the main surface 5a and opposed main surface 5b of a flat plate-shaped support 4 comprising a ceramic porous body, a plurality of spacers 2 provided between the fluid partition walls 1, fluid main flow channels 3a formed by the spacers 2 and the fluid partition walls 1, a sub-flow channels 3b for connecting two adjacent main flow channels 3a, a permeated fluid flow channel allowing the permeated fluid permeated through the separation layer to flow through the flat plate-shaped support 4 and a discharge part for discharging the permeated fluid from the side surface 7 of the flat plate-shaped support 4. <P>COPYRIGHT: (C)2004,JPO

Description

【００８２】
本発明の試料Ｎｏ．１〜４及び６〜２５は、ＣＯ_２とＣＨ_４との混合ガスのうち４６％以上のＣＯ_２を回収することができた。
【００８３】
これに対して、
【００８４】
【発明の効果】
本発明は、セラミック多孔質体からなる平板状支持体の主面及び対向主面に分離層を設けてなる流体隔壁を複数積層し、該流体隔壁間に流体が流れる流路を形成してなる積層体を作製することにより、流体処理量が大きく高圧領域に好適な流体分離フィルタを実現することができる。
【００８５】
特に、スペーサに緻密なセラミックスを用いることによって、耐食性と機械的信頼性が更に高い流体分離フィルタを実現でき、また、スペーサに多孔質セラミックスを用いて、流体と接する部位に分離層を形成することによって、分離効率のより高い流体分離フィルタを実現することができる。
【図面の簡単な説明】
【図１】本発明の流体分離フィルタを示す概略斜視図である。
【図２】本発明の図１の流体分離フィルタのａ−ａ′部の概略断面図である。
【図３】本発明の流体分離フィルタの一部を示す概略断面図である。
【図４】本発明の流路の一例を示す概略断面図で、（ａ）は平板形状の場合、（ｂ）は櫛型形状の場合である。
【図５】本発明の流体分離モジュールを示す概略断面図である。
【図６】従来の流体分離フィルタを示す概略断面図である。
【符号の説明】
１・・・流体隔壁
２・・・スペーサ
３・・・流路
３ａ・・・主流路
３ｂ・・・副流路
４・・・平板状支持体
５ａ・・・主面
５ｂ・・・対向主面
６、６ａ、６ｂ・・・分離層
７・・・側面[0001]
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plant for concentrating a specific gas represented by CO ₂ recovery from natural gas, a plant for concentrating a specific substance from a mixed solvent, a plant for dehydrating from alcohol, Water treatment plants and desalination plants that increase the purity of water, devices that separate specific gases such as oxygen and carbon dioxide from factory exhaust gas and power plants, food-related or medical-related separation devices, and hydrogen and oxygen gas as fuel The present invention relates to a fluid separation filter and a fluid separation module which can be suitably used as an oxygen separation layer and a hydrogen separation layer of a fuel cell for generating power, a PFC separation device discharged from a semiconductor manufacturing device, and a rare gas recovery device used in an exposure device.
[0002]
[Prior art]
Conventionally, porous materials have been used as filters for filtering and separating only specific fluids from mixed fluids in which various fluids are mixed, and porous materials are used as catalyst carriers and electrolytic partition walls. The range is expanded, and the separation and concentration technology of specific fluids using porous materials is used for various combustion engines, concentration plants, water treatment plants, fluid separation for the food industry and medical equipment, fuel cells, and waste treatment. Is attracting attention in various fields.
[0003]
Conventionally, a polymer membrane has been used as such a porous body, but in recent years, a ceramic separation layer having excellent heat resistance and chemical resistance has attracted attention. In particular, recently, gas treatment is often performed on-site, and thus a small ceramic separation module is required.
[0004]
Conventionally, a ceramic separation module in which a hollow fiber generally used in an organic polymer membrane or the like is applied to ceramics has been often used. Such a filter having a hollow fiber structure is formed by forming a separation layer having corrosion resistance and heat resistance on the surface of a tubular ceramic support, and bundling a large number of the separation layers. For example, Japanese Patent Application Laid-Open No. H11-156167 discloses the filter. Has been described.
[0005]
However, the hollow fiber structure described in Japanese Patent Application Laid-Open No. H11-156167 has a problem that when the diameter of the tube-shaped ceramic support is reduced, the strength is reduced, and the tube is easily broken at the time of handling. There is a problem that it is difficult, and it is difficult to secure the flow path by the close contact between the supports, and it is difficult to reduce the size.
[0006]
Therefore, as shown in FIG. 6, the ceramic flat plates 31 having the separation layer 32 formed on the main surface and the opposite main surface are laminated with the spacer 34 interposed therebetween, and a fluid flow path is provided between the ceramic flat plates 31. Japanese Patent Application Laid-Open No. 2-198611 discloses a fluid separation filter in which the path length is increased to reduce the size.
[0007]
[Problems to be solved by the invention]
However, in the fluid separation filter having a flat support structure described in Japanese Patent Application Laid-Open No. 2-198611, the fluid component transmitted through the separation layer 32 moves inside the ceramic flat plate 31 over a long distance, and the fluid component passes through each step. Each time it reaches the outlet member 35, it is collected after being collected at one location from the ventilation hole 36, and therefore, there is a problem that the collection efficiency is very poor, which hinders practical use.
[0008]
Accordingly, it is an object of the present invention to provide a small-sized fluid separation filter and a fluid separation module that improve the recovery efficiency of a permeated fluid that has passed through a separation layer.
[0009]
[Means for Solving the Problems]
The present invention shortens the passage distance in the plate-shaped support by discharging the permeated fluid transmitted through the separation layer provided on the surface of the plate-shaped support made of porous ceramics from the side surface of the plate-shaped support. Based on the finding that the recovery efficiency of the permeated fluid can be significantly increased, a small-sized fluid separation filter having improved recovery efficiency has been realized.
[0010]
That is, the fluid separation filter of the present invention includes a plurality of fluid partitions provided with a separation layer on a main surface and a facing main surface of a flat support made of a ceramic porous body, and a plurality of spacers provided between the fluid partitions. A main flow path of the fluid formed by the spacer and the fluid partition, a sub flow path for connecting two adjacent main flow paths, and a permeated fluid permeating through the separation layer inside the plate-shaped support. And a discharge portion for discharging the permeated fluid from the side surface of the flat support.
[0011]
In particular, it is preferable that the area of the ejection portion is 50% or more of the total area of all side surfaces. Thereby, the fluid separation efficiency can be further improved.
[0012]
Further, the main surface and the opposing main surface of the plate-shaped support are polygonal, and the permeate fluid flow path is equal to or less than the length of a side of the polygon, or the main surface of the plate-shaped support and It is preferable that the opposing main surface be circular and the permeate fluid flow path be smaller than the radius of the circular shape. As a result, the traveling distance of the permeated fluid that determines the permeation efficiency can be reduced, and the permeation speed can be further increased.
[0013]
Further, it is preferable that the main flow path has a comb shape. As a result, a so-called dead space in which the flow of gas is stagnated in the mainstream residence furnace can be suppressed, and the specific gas can be efficiently transmitted from the supply gas.
[0014]
Furthermore, it is preferable that the relative density of the spacer is 98% or more. This can prevent gas from escaping from the spacer.
[0015]
Preferably, the spacer is made of a porous material, and a separation layer is provided on a surface of the spacer forming the fluid flow path. Accordingly, the characteristic component is separated from the fluid containing the plurality of components by passing through the separation layer provided on the spacer, and is discharged to the outside of the separation filter, so that the efficiency of the filter can be further improved.
[0016]
Further, it is preferable that the thickness of the spacer is 0.2 to 20 mm. As a result, it is possible to secure a separation layer area per unit volume equal to or more than a certain value while maintaining mechanical strength, and to allow the permeated fluid to smoothly move in the porous material and recover the permeated fluid.
[0017]
Furthermore, it is preferable that the thickness of the flat support is 0.2 to 20 mm. This can contribute to further miniaturization of the fluid separation filter, and can secure a sufficient path for the permeated fluid flowing in the flat support.
[0018]
Further, it is preferable that the porosity of the plate-shaped support is larger inside than the surface portion. Thereby, the pressure loss in the porous body of the permeated fluid is reduced, and the permeated amount can be increased.
[0019]
Further, it is preferable that the average pore diameter of the flat support is larger inside than the surface portion. Thereby, the film forming property of the separation layer coated on the surface of the flat plate support can be improved without reducing the permeation amount of the permeated fluid, and the separation characteristics can be improved.
[0020]
Further, the fluid separation module of the present invention includes the above-described fluid separation filter, a container for holding the fluid separation filter, and a fluid that supports the fluid separation filter in the container and separates the fluid and the permeated fluid from the fluid. A fluid inlet for supplying a fluid to the fluid separation filter, an outlet for discharging the fluid through the fluid separation filter to the outside, and a permeate fluid. An outlet for recovery is provided, whereby a separation layer that selectively separates and permeates a specific fluid component from a mixed fluid can be used as a system.
[0021]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention will be described with reference to the drawings.
[0022]
In the fluid separation filter of the present invention, as shown in FIG. 1, a plurality of fluid partition walls 1 made of a porous ceramic material are alternately laminated with spacers 2 to form a flow path 3 through which a fluid flows.
[0023]
As shown in FIG. 2, which is a cross-sectional view taken along the line aa ′ in FIG. 1, the flow path 3 is provided between a main flow path 3a composed of a fluid partition wall 1 and a spacer 2 and between two adjacent main flow paths 3a. And a sub flow path 3b for connecting the two. A plurality of main channels 3a are provided between the fluid partitions 1, and are substantially parallel to each other. The sub flow path 3b is formed as a communication hole provided in the fluid partition 1. The fluid alternately flows through the main flow path 3a and the sub flow path 3b, as indicated by arrows in FIG.
[0024]
The fluid partition 1 is composed of a flat support 4, a separation layer 6 a provided on a main surface 5 a of the flat support 4, and a separation layer 6 b provided on an opposing main surface 5 b. 6b forms a main flow path 3a for the fluid, and a communication hole serving as a sub flow path 3b is provided in a part of the fluid partition 1.
[0025]
As shown in FIG. 3 which is a cross-sectional view of the fluid partition 1, a permeated fluid flow path formed by connecting pores is provided in the inside 4 a of the flat support 4, and at least a part of the side surface 7 is provided. Is provided with a discharge section for discharging a permeated fluid.
[0026]
As shown by arrows in FIG. 3, some of the components of the fluid flowing through the flow path 3 penetrate through the separation layers 6a and 6b, penetrate from the surface portion 4b of the flat support 4 to the inside 4a, and enter the inside 4a. It reaches the side surface 7 through the provided permeate fluid flow path. Then, the permeated fluid is discharged from the side surface 7.
[0027]
According to the present invention, as described above, it is important that the fluid separation filter includes the fluid partition 1, the spacer 2, the main channel 3a, the sub channel 3b, the permeated fluid channel, and the discharge unit. It is.
[0028]
Since the fluid separation filter of the present invention has a flat plate structure, it has a longer moving distance in the porous ceramic body than the hollow fiber structure. Therefore, in order to shorten the moving distance of the permeated fluid and increase the permeation efficiency, it is important to discharge the permeated fluid from the side surface 7 of the flat support 4. When the permeated fluid is discharged from the side surface 7, the permeated fluid channel can be shortened, the permeation flow rate can be increased, and the permeation efficiency can be increased.
[0029]
When the main surface 5a and the opposing main surface 5b of the flat support 4 are other polygons, it is preferable that the permeated fluid flow path is not more than the length of the sides of the polygon. For example, when the flat support 4 is a quadrangular prism (rectangular parallelepiped) as shown in FIG. 1, the shape of the main surface 5a and the opposing main surface 5b is rectangular, and the permeated fluid can be discharged in four directions (four side surfaces). In the case of a hexagonal prism (octahedron), the main surface 5a and the opposing main surface 5b are hexagonal, and can discharge from six directions (six side surfaces), and collect the discharged permeated fluid.
[0030]
In addition, when the flat support 4 is a column, and when the main surface 5a and the opposing main surface 5b of the flat support 4 are circular, it is preferable that the permeated fluid flow path has a radius equal to or less than the radius of the circle. With such a configuration, regardless of whether the main surface is polygonal or circular, in any case, the permeated fluid flow path until the permeated fluid reaches the side surface 7 is shortened, and the recovery efficiency is improved. Can be contributed to.
[0031]
In addition, the transmission efficiency can be easily increased by increasing the ratio of the area of the side surface 7 from which the permeated fluid is discharged to the total area of all the side surfaces 7. That is, the ratio _S f _{/ S all} sites of the area of the side surface 7 of the permeate to the total area of all the sides 7 _{(S all)} is discharged _{(S f)} 50% or more, particularly 70% or more, further 90% or more Is preferable. Further, there may be a case where a part of the side surface 7 cannot be used for fixing the flat support 4 or for other reasons, but the ratio S _f / S _all is preferably 100% or close to 100%.
[0032]
The plate-shaped support 4 forms a main flow path 3a of the fluid, and is in contact with a fluid composed of a plurality of components, and a permeated fluid of which some components have passed through the separation layer 6 passes through the inside of the plate-shaped support 4. In order to increase the amount of permeation and the permeation speed because of the flow, it is preferable that the porosity inside the plate-shaped support 4 is larger than the porosity near the surface portion 4b, that is, near the main surface 5a and the opposing main surface 5b. .
[0033]
Specifically, the average porosity of the entire plate-like support 4 is 15% or more, particularly 20% or more, and more preferably 25% or more, in order to make the permeated gas easily permeate the plate-like support 4. More preferably, the strength of the plate-shaped support 4 is ensured, and the plate-shaped support 4 is damaged when assembled into a housing or the like, or the particles constituting the plate-shaped support 4 are shed during operation. In order to prevent this, the porosity of the flat support 4 is preferably 60% or less, particularly preferably 50% or less, and more preferably 40% or less.
[0034]
In addition, the porosity of the inside 4a of the plate-shaped support 4 ensures the strength of the fluid partition wall 1, damages when assembling into a housing or the like, and particles that constitute the plate-shaped support 4 during operation, such as shedding of particles. In order to realize a large transmission coefficient while suppressing a decrease in mechanical strength as a support, the upper limit is preferably 60%, particularly 55%, and more preferably 50%. Further, in order to ensure a sufficient permeated fluid flow path for the permeated fluid and obtain higher permeation efficiency, the lower limit of the porosity of the flat support 4 is set to 20%, particularly 25%, and more preferably 30%. Is preferred.
[0035]
The surface portion 4b of the flat support 4 efficiently transmits a permeated fluid composed of a part of the fluid permeated through the separation layer and forms a separation layer having a pore diameter of about 1 nm on the surface. It is preferable to control the porosity and average pore diameter of the surface portion 4b so that pinholes and defects do not occur in the separation layer 6 described above. Specifically, the porosity is 8 to 30%, particularly 10 to 25%, more preferably 12 to 20%, and the average pore diameter is 0.05 μm to 1 μm, particularly 0.1 μm to 0.8 μm, and more preferably 0.1 μm to 0.8 μm. To 0.5 μm.
[0036]
In the inside 4a of the plate-shaped support 4, pores are connected to form a permeated fluid path, and the permeated fluid flows smoothly. Accordingly, in order to reduce the pressure loss of the permeated fluid in the inside 4a of the porous plate-shaped support 4 and to realize a high permeation rate, the porosity and the average pore diameter of the inside 4a must be larger than those of the surface portion 4b. Is preferred.
[0037]
The lower limit of the thickness of the plate-shaped support 4 is preferably 0.2 mm, particularly 0.4 mm, and more preferably 0.6 mm in order to increase the cross-sectional area of the permeate fluid flow path and increase the permeate fluid volume. In order to increase the area of the separation layer 6 included in the fluid separation filter per unit volume and to reduce the size while increasing the total length of the flow path 3, the upper limit may be 20 mm, particularly 15 mm, and even 10 mm. preferable.
[0038]
As the material of the flat support 4, ceramics containing α-alumina or stabilized zirconia as a main component, silica-based glass (phase-separated glass), Si ₃ N ₄ , SiC, or the like can be used, but heat resistance is low. Ceramics containing α-alumina as a main component are preferable in terms of high cost, easy production, and low cost.
[0039]
The separation layer 6 preferably contains at least one of Si, Ti, Zr, and Al. These form the separation layer 6 as an oxide. Among these, Si is more preferable in terms of low reactivity in the alkoxide state, which can suppress the progress of local reaction, and easy formation of a pore diameter of 1 nm or less by forming a Si-O-Si network. .
[0040]
It is preferable that the flat support 4 is pressurized by the fluid at that time. When pressure is applied to the plate-like support 4 in this manner, the transmission speed increases, and the transmission efficiency can be further increased. Specifically, in the case of a gas, it is preferably at least 1.5 atm, particularly preferably at least 2 atm, and more preferably at least 3 atm.
[0041]
Further, since the flat support 4 is thin, it is preferable that the pressure applied to the main surface 5a of the flat support 4 and the pressure applied to the opposing main surface 5b be substantially the same in order to prevent mechanical damage. That is, the pressure of the fluid in contact with the main surface 5a may be substantially the same as the pressure of the fluid in contact with the opposing main surface 5b. As described above, since the plate-like support 4 is supported by the upper and lower surfaces of the plate-like support 4 with uniform pressure, generation of special stress can be prevented, and cracks and breakage can be prevented.
[0042]
The spacer 2 is preferably at least 98%, particularly preferably at least 99% in order to enhance the sealing performance. Thereby, it is possible to prevent the supply gas of the flow path 3 from leaking out of the fluid separation layer filter.
[0043]
Further, the thickness of the spacer 2 is preferably 0.2 to 20 mm, particularly 0.5 to 15 mm, and more preferably 1 to 10 mm. By setting the thickness of the spacer 2 in such a range as described above, the contact area between the fluid and the separation layer 6 is increased, the recovery efficiency of the permeated fluid is increased, and the spacer 2 is used as a fluid separation filter. Can be prevented.
[0044]
The spacer 2 is preferably made of a desired ceramic in order to enhance corrosion resistance. For example, ceramics containing silica or stabilized zirconia as a main component, silica-based glass (phase-separated glass), Si ₃ N ₄ , SiC, or the like can be preferably used. Among them, ceramics containing α-alumina as a main component are preferable in terms of heat resistance, ease of production, and low cost.
[0045]
Further, in order to form a laminated body, the spacer 2 is made of substantially the same material as the plate-shaped support 4 so as to enhance the adhesion to the plate-shaped support 4 and effectively prevent cracks and peeling from occurring. Is preferred.
[0046]
According to the present invention, two types of material design can be performed for the spacer 2 depending on the use environment and required characteristics of the fluid separation filter. That is, first, mechanical reliability such as strength and reliability of fluid separation are required, and second, high characteristics are required as a filter.
[0047]
In the first case where mechanical reliability and reliability of fluid separation are required, it is preferable that the density of the spacer 2 be 98% or more, particularly 99% or more. When dense ceramics are used for the spacer 2 as described above, the skeleton of the fluid separation filter is made of dense ceramics having high mechanical reliability such as high strength, high toughness, and high impact resistance. Even if a relatively porous ceramic is used for 4a, the mechanical reliability of the fluid separation filter can be improved, and the fluid can be prevented from penetrating through the spacer 2 and being discharged from the side surface of the spacer 2. Reliability can be improved.
[0048]
In the second case where high characteristics as a filter are required, it is preferable to provide the separation layer 6 at least in a portion of the spacer 2 which is in contact with the fluid. Fluid separation can be performed through the spacer 2 in addition to the flat support 4. The permeate fluid separated by the flat support 4 moves a relatively long distance inside the flat support 4, while the permeate fluid separated by the spacer 2 moves a short distance corresponding to the thickness of the spacer 2. , The separation efficiency is high, and as a result, the separation efficiency can be further increased by 10 to 200%, depending on the area of the separation layer 6 provided in the spacer 2.
[0049]
The fluid only needs to be in contact with the separation layer 3 provided on the surface of the flat support 4, and there is no particular limitation on the flowing direction, flow rate, or flow rate. However, in order to allow a specific component to pass through efficiently, it is preferable that the fluid flows in all parts of the flow channel and that a fresh fluid is always supplied.
[0050]
Further, since the flat support 4 is thin, it is preferable that the pressure applied to the main surface 5a of the flat support 4 and the pressure applied to the opposing main surface 5b be substantially the same in order to prevent mechanical damage. That is, the pressure of the fluid in contact with the main surface 5a may be substantially the same as the pressure of the fluid in contact with the opposing main surface 5b. As described above, since the main surface 5a of the flat support 4 and the upper and lower surfaces of the opposing main surface 5b are supported by the uniform pressure, the stress applied to the flat support 4 can be suppressed low, and cracks and breakage can be prevented. can do.
[0051]
Although there is no particular limitation on the main flow path 3a, it is preferable that the fluid and the separation layer 6 come into contact with each other in a wide range, and that a fresh fluid without stagnation be supplied to the separation layer 6. For this reason, the main channel 3a may have a simple structure as shown in FIG. 4A, but it is desirable that the main channel 3a has a comb shape as shown in FIG. In this way, by increasing the distance of the flow path and forcing all the fluid to flow, it is possible to prevent the occurrence of large stagnation in the flow path and to supply fresh fluid to the separation layer 6 at all times. This is effective in further increasing the separation efficiency.
[0052]
The fluid separation filter having the above configuration has a feature of high pressure resistance, and is used in petrochemical processes such as separation of CO ₂ from natural gas used at high pressure and petroleum complex, and in a membrane area occupying a unit volume. Is used for applications where the area for installing a fluid separation filter cannot be large, specifically for PFC separators used in semiconductor manufacturing lines and rare gas separators used in exposure equipment. It can be suitably used as a separation device.
[0053]
Next, a method for manufacturing the fluid separation filter will be described.
[0054]
First, in order to produce the flat support 4, desired raw material powders are mixed and molded. As a molding method, known molding means such as press molding, extrusion molding, injection molding, and cold isostatic molding can be used. In consideration of cost and warpage of the substrate, it is preferable to produce the sheet by a powder rolling method. The obtained molded body was fired to obtain a sintered body.
[0055]
According to the present invention, the thickness of the flat support 4 is preferably adjusted so that the porosity and the average pore diameter are larger in the inside 4a than in the surface portion 4b, and the molding temperature and humidity are adjusted. good.
[0056]
Next, the separation layer 6 is formed. The separation layer 6 can be formed by a sol-gel method, a CVD method, a sputtering method, or the like, but the sol-gel method is preferable because of ease of manufacturing. In the following, when the sol-gel method is used, a method of manufacturing the separation layer 6 containing Si among elements of Si, Ti, Zr, and Al will be particularly described.
[0057]
As a raw material of the separation layer 6, a silicon alkoxide such as tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane is prepared.
[0058]
First, a precursor sol is prepared using this raw material. That is, silicon alkoxide is dissolved in a solvent such as alcohol, and water is added to perform hydrolysis.
[0059]
The obtained precursor sol is applied to the surface of the plate-shaped support 4 and then fired to form the separation layer 6. The baking is performed by heat treatment at 350 to 700 ° C., particularly 400 to 600 ° C. in the air, so that the siloxane bond of Si—O proceeds in the gel to form a strong film, and the organic functional groups are decomposed by the heat treatment. Removed to form pores.
[0060]
The firing temperature and the firing time vary depending on the size of the average pore diameter of the separation layer 6, but in the case of gas separation, the average pore diameter is 0.2 to 1.3 nm, particularly 0.3 to 1.0 nm, Further, it is preferable to adjust the above firing conditions so as to be 0.4 to 0.8 nm, whereby a film having high separation characteristics can be manufactured.
[0061]
In the firing, it is preferable to control the firing conditions so that the separation layer 6 does not generate a reaction product at the interface with the flat support 4. Specifically, it is carried out at a temperature of 400 to 800 ° C, preferably at a firing temperature of 450 to 600 ° C. It is desirable that the surface of the plate-like support 4 is coated in a layer form to form a smooth surface.
[0062]
The firing temperature and the firing time vary depending on the size of the average pore diameter of the separation layer 6, but in the case of a gas separation filter, the average pore diameter is 0.2 to 1.3 nm, particularly 0.3 to 1.0 nm, and furthermore, Is preferably adjusted to 0.4 to 0.8 nm. For example, 0.25-0.6 nm to separate hydrogen gas from other gases, 0.3-0.8 nm to separate CO ₂ and CH ₄ , N ₂ gas and CF ₄ gas Is preferably set to an average pore diameter of 0.35 to 1.0 nm, whereby the separation characteristics can be improved.
[0063]
In particular, the holding time at the firing temperature is shortened in order to make the porosity and the average pore diameter of the inside 4a larger than those of the surface portion 4b.
[0064]
The separation layer 6 is formed on the main surface 5a and the opposing main surface 5b of the flat support 4, and the thickness of the separation layer 6 is 0.01 to 5 μm, particularly 0.1 to 4 μm, and more preferably 0 to 5 μm. The particle size of the sol is adjusted so as to be 0.5 to 3 μm.
[0065]
In addition, an intermediate layer may be provided between the plate-shaped support 4 and the separation layer 6 to improve the adhesion of the separation layer 6. Titania, zirconia, alumina, or the like can be used for the intermediate layer. Therefore, these alkoxides may be prepared as raw materials.
[0066]
The spacer 2 is used for partitioning the flat support 4 and needs to be a dense body so that gas leakage from the spacer 2 does not occur. It is preferable that the spacer 2 is provided between the flat plate supports 4 and has a thermal expansion coefficient close to that of the flat plate support. Thus, a fluid separation layer module having high heat resistance is obtained.
[0067]
A laminate is produced by alternately stacking the plate-like supports 4 thus produced with the spacers 2. The number of the plate-like supports 4 and the spacers 2 to be laminated varies depending on the required film area. Dense flat plates are provided at both ends of the laminated body. For this flat plate, it is preferable to select a material having a thermal expansion coefficient close to that of the spacer 2. Specifically, when the spacer 2 is alumina, alumina is used. Further, glass connection using a glass paste having a thermal expansion coefficient close to that of alumina is preferable for connection between the flat support 4 and the spacer 2 and between the spacer 2 and the dense body at both ends. As a result, all the members can be made of ceramic, and a fluid separation filter having excellent heat resistance and corrosion resistance can be manufactured.
[0068]
As shown in FIG. 5, the fluid separation module of the present invention includes a plurality of the fluid separation filters 21 arranged inside a container 22, a fluid introduction port 23 for supplying a fluid to the inside of the container 22, An outlet 24 for discharging the fluid that has passed through the separation filter 21 to the outside, and an outlet 25 for collecting the permeated fluid are provided.
[0069]
A fluid having a plurality of components, for example, a mixed gas of H ₂ and CO ₂ is introduced from the fluid inlet 23 into the container 22, the fluid comes into contact with the fluid separation filter 21, and a part of the fluid is on the surface of the fluid separation filter 21. The permeated fluid that has passed through the provided separation layer and has passed through the separation layer in the fluid separation filter 21 moves to the side surface 27 and is taken out from the outlet 25.
[0070]
The fluid separation module of the present invention having the above configuration has a feature of high pressure resistance, and can be suitably used for petrochemical processes such as separation of CO ₂ from natural gas used at high pressure and petroleum complexes. . Further, both permeated and non-permeated gases can be recovered.
[0071]
【Example】
First, a flat support was prepared. That is, a desired organic binder, a lubricant, a plasticizer, and water are added to alumina powder, zirconia powder, glass powder, silicon nitride powder, and silicon carbide powder having a purity of 99.9% and an average particle size of 0.1 μm, respectively. After mixing and forming a tape by a powder rolling method, it was fired to produce a flat support made of a sintered body having a thickness of 0.8 mm, a length of 150 mm and a width of 50 mm. The flat support was processed to adjust the thickness to the value shown in Table 1, and the surface was polished so that the surface roughness (Ra) became 0.3 μm or less.
[0072]
The porosity and average pore diameter of the obtained sintered body were measured from observation by a scanning electron microscope (SEM).
[0073]
Next, a separation layer was formed. As raw materials, titanium tetraisopropoxide (TTP), tetraethoxysilane (TEOS), tetrapropoxyzirconium (TPZ), and aluminum secondary butoxide (ASBD) were prepared.
[0074]
Using the above raw materials, a separation layer was formed on a support by a sol-gel method. That is, when the raw materials of TTP, TEOS, TPZ and ASBD were used alone, an ethanol solution containing 1 mol of water and HCl was added to 1 mol of these metal alkoxides and mixed. When a plurality of raw materials are used, an ethanol solution containing 1 mol of water and HCl is added and mixed with 1 mol of TEOS to prepare a partial hydrolysis sol, and an ethanol solution of another metal alkoxide is added to the metal alkoxide. Was added so as to be 1 mol, and the mixture was stirred under a nitrogen stream to prepare a composite alkoxide.
[0075]
Next, a mixed solution of 9.3 mol of water and ethanol was added to the obtained solution, hydrolyzed, and stirred to prepare a precursor sol. Next, the side surface of the flat support is plugged, impregnated with the above sol, held for 60 seconds, taken out at a speed of 5 mm / sec, dried at room temperature for 2 hours to gel the sol, The step of baking at 550 ° C. was repeated four times to form a separation layer on the outer surface of the support.
[0076]
Note that an intermediate layer was formed as required before forming the separation layer. That is, the above raw materials were added to 110 mol of water for hydrolysis, nitric acid was further added, and the mixture was boiled and stirred for 16 hours to prepare a precursor sol. Next, an intermediate layer was formed by the same method as the separation layer.
[0077]
For the obtained sample, the average pore diameter of the separation layer was determined from the humidity and temperature of the water condensed in the pores using the Kelvin capillary condensation method.
[0078]
Further, the thickness of the separation layer was measured by a scanning electron microscope (SEM).
[0079]
In addition, 17 spacers are provided between the obtained 18 filters, two spacers are provided on both sides of the end filter, and a plate of a dense layer having the same shape as the filter is laminated on both ends in the form of a spacer, and each layer is made of glass paste. (YB519 manufactured by Yamamura Glass Co., Ltd.), and then placed inside a glass container, and attached with a fluid inlet, outlet, and outlet to produce a fluid separation module as shown in FIG. In addition, a part of the side surface was sealed with glass so that the area ratio of the ejection portion became the side surface ratio shown in Table 1. No. 13 has a structure in which an outlet member 35 is provided as shown in FIG.
[0080]
The inside of the obtained fluid separation module was heated to a temperature of 250 ° C., and 200 kPa (2 atm) of carbon dioxide was applied to the outside of the plate-like support while the inside of the plate-like support was opened to the atmosphere to 100 kPa (atmospheric pressure). At a flow rate of 20 l / min, the permeation flow rate of the gas collected at the permeate fluid outlet was measured, and the permeation rate represented by the permeation amount of carbon dioxide gas / (membrane area × differential pressure × time) was calculated. Calculated. The transmittance of methane gas was determined in the same manner as above, and the transmittance coefficient ratio α (transmittance of carbon dioxide / transmittance of methane) was determined. The recovery rate of carbon dioxide was determined by the ratio of the flow rate of carbon dioxide permeated and separated to the flow rate of supplied carbon dioxide. The results are shown in Table 1.
[0081]
[Table 1]

[0082]
Sample No. of the present invention 1 to 4 and 6 to 25 were able to recover 46% or more of CO ₂ in the mixed gas of CO ₂ and CH ₄ .
[0083]
On the contrary,
[0084]
【The invention's effect】
The present invention is obtained by laminating a plurality of fluid partitions provided with a separation layer on the main surface and the opposing main surface of a plate-shaped support made of a ceramic porous body, and forming a flow path through which a fluid flows between the fluid partitions. By producing a laminate, a fluid separation filter which has a large fluid throughput and is suitable for a high pressure region can be realized.
[0085]
In particular, by using dense ceramics for the spacer, a fluid separation filter with even higher corrosion resistance and mechanical reliability can be realized, and using porous ceramics for the spacer to form a separation layer at the part in contact with the fluid Thereby, a fluid separation filter having higher separation efficiency can be realized.
[Brief description of the drawings]
FIG. 1 is a schematic perspective view showing a fluid separation filter of the present invention.
FIG. 2 is a schematic cross-sectional view of an aa ′ portion of the fluid separation filter of FIG. 1 of the present invention.
FIG. 3 is a schematic sectional view showing a part of the fluid separation filter of the present invention.
FIGS. 4A and 4B are schematic cross-sectional views showing an example of a flow channel according to the present invention, wherein FIG. 4A shows a case of a flat plate shape, and FIG.
FIG. 5 is a schematic sectional view showing a fluid separation module of the present invention.
FIG. 6 is a schematic sectional view showing a conventional fluid separation filter.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Fluid partition 2 ... Spacer 3 ... Flow path 3a ... Main flow path 3b ... Sub flow path 4 ... Flat support 5a ... Main surface 5b ... Opposite main Surface 6, 6a, 6b ... separation layer 7 ... side surface

Claims (12)

Formed by a plurality of fluid partitions provided with separation layers on the main surface and the opposing main surface of a plate-shaped support made of a ceramic porous body, a plurality of spacers provided between the fluid partitions, and the spacers and the fluid partitions. A main flow path for the fluid to be processed, a sub flow path for connecting two adjacent main flow paths, a permeate fluid flow path through which the permeated fluid permeates the separation layer inside the flat support, A fluid separation filter, comprising: a discharge unit for discharging a fluid from a side surface of the flat support. The fluid separation filter according to claim 1, wherein the area of the discharge section is 50% or more of the total area of all side surfaces. The fluid separation filter according to claim 1, wherein a main surface and an opposing main surface of the plate-like support are polygonal, and the permeated fluid flow path is equal to or less than a length of a side of the polygon. . 3. The fluid separation filter according to claim 1, wherein the main surface and the opposing main surface of the flat support are circular, and the permeated fluid flow path has a radius equal to or smaller than the radius of the circle. The fluid separation filter according to any one of claims 1 to 4, wherein the main flow path has a comb shape. The fluid separation filter according to any one of claims 1 to 5, wherein the relative density of the spacer is 98% or more. The fluid separation filter according to any one of claims 1 to 6, wherein the spacer is formed of a porous body, and a separation layer is provided on a surface of the spacer that forms the flow path of the fluid. The fluid separation filter according to any one of claims 1 to 7, wherein the spacer has a thickness of 0.2 to 20 mm. The fluid separation filter according to any one of claims 1 to 8, wherein the thickness of the flat support is 0.2 to 20 mm. The fluid separation filter according to any one of claims 1 to 9, wherein the porosity of the flat support is larger inside than the surface portion. The fluid separation filter according to any one of claims 1 to 10, wherein the average pore diameter of the flat support is larger inside than the surface portion. A fluid separation filter according to any one of claims 1 to 11, a container for holding the fluid separation filter, and a permeate fluid supporting the fluid separation filter in the container and separating the fluid from the fluid. , A fluid inlet for supplying a fluid to the fluid separation filter, an outlet for passing the fluid separation filter to the outside, and a permeate fluid being recovered. A fluid separation module, comprising:

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