JP3911370B2 - Gas separation module and liquid deaerator - Google Patents

Description

【００４４】
表１の結果より、本発明に従い乱流発生部材を収束体内の複数のフィルタと接続して前記収束体間に介在させることにより、溶存酸素量が減少し、ガス分離性能が高いことがわかった。
【００４５】
これに対して、試料Ｎｏ．９の乱流発生部材を設けないガス分離モジュールは、ガス分離性能が低いものであった。
【００４６】
【発明の効果】
以上詳述したとおり、本発明のガス分離モジュールは、同一のハウジング内に該複数の収束体を平行に配置して収納し乱流発生部材を介在させることによって被処理物である気体または液体の乱流を促進し、ガス分離性能を高めることができる。
【図面の簡単な説明】
【図１】本発明のガス分離モジュールの一例を示す概略断面図である。
【図２】実施例のガス分離モジュールにおけるガス分離フィルタ管の分離膜の細孔分布を示す図である。
【符号の説明】
２０ ガス分離モジュール
２１，２１’ ガス分離フィルタ管（フィルタ）
２２，２２’ 収束体
２４ ハウジング
２３，２３’ 固定用部材
２５ 被処理物導入口
２６ 処理済物回収口
２７ 特定ガス回収口
３０ 乱流発生部材[0001]
BACKGROUND OF THE INVENTION
The present invention separates and recovers a specific gas from an object to be processed such as a specific gas separation filter for separating and recovering a specific gas from a mixed gas, or a degassing filter for removing the gas from a dissolved liquid. The present invention relates to a gas separation module and a liquid deaeration device using the same .
[0002]
[Prior art]
Conventionally, a gas separation module having a gas separation filter such as a specific gas separation filter for separating and recovering a specific gas from a mixed gas or a degassing filter for removing the gas from a liquid in which the gas is dissolved is known. ing.
[0003]
For example, cooling water used in various devices, deoxygenation and decarbonation have sought to prevent corrosion of the apparatus, also, ultrapure water used for semiconductor cleaning, suppress the generation of live bacteria In order to prevent oxidation of the silicon wafer, it is necessary to super-deaerate the dissolved oxygen concentration to 10 ppb or less.
[0004]
As such liquid degassing, for example, a heating boiling method, a decompression method, an ion exchange resin method, an inert gas replacement method, and the like are well known. However, the heating boiling method is highly dangerous due to high temperature operation, the depressurization method has poor degassing efficiency, the ion exchange resin method requires resin regeneration treatment, and the inert gas replacement method has a running cost. It was stuffy.
[0005]
On the other hand, many gas separation modules equipped with a filter capable of selectively permeating and separating only a specific gas have been adopted because of the advantage that the apparatus is small and the processing process is simple.
[0006]
The gas separation module having such a gas separation filter tube is composed of, for example, a polymer membrane using a so-called dissolution diffusion mechanism in which a specific gas is absorbed inside the filter and the gas permeates through the membrane by diffusion, In recent years, it has been studied to use a filter in which an inorganic separation membrane such as SiO ₂ is deposited on the surface of a porous ceramic support tube. Has been reported to improve the gas separation performance (see JP-A-10-5557, etc.).
[0007]
[Problems to be solved by the invention]
However, in the gas separation module having a gas separation filter tube disclosed in Japanese Patent Application Laid-Open No. 10-5557, etc., the material to be processed is supplied into the support tube and passes through the filter tube. Has a laminar flow state, and the ratio of contact of the specific gas in the object to be treated with the wall surface of the support tube is reduced, so that the gas separation performance is limited.
[0008]
Therefore, Japanese Patent Laid-Open No. 3-169304 proposes that a spiral tubular body is used as a filter to promote turbulent flow of the liquid to be treated and increase the deaeration efficiency.
[0009]
However, in the above spiral tubular body, a wasteful volume is generated inside the spiral and the module is enlarged, and a converging body is produced by bundling a plurality of like a long tubular body to reduce the surface area of the gas separation filter tube. In addition, there is a problem that the gas separation efficiency of the object to be processed cannot be increased.
[0010]
The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a gas separation module capable of enhancing gas separation performance by promoting turbulent flow of an object to be processed.
[0011]
[Means for Solving the Problems]
As a result of repeated research on the structure of the gas separation module, the present inventor has arranged two converging bodies formed by converging a plurality of gas separation filter tubes existing in the module in the same housing in parallel . Are connected to each other through a turbulent flow generating member formed by filling the end of the housing with a granular material , one of the two converging bodies being the forward path portion and the other being the return path As a result of the gas separation filter pipe being separated, the flow of the object to be processed in the filter can be promoted to a turbulent state at the end of the gas separation filter pipe. It has been found that the performance can be improved.
[0012]
That is, the gas separation module of the present invention, the converging member only certain gas comprising a gas separation filter tube having a permeable gas separation function to a plurality of convergence with comprising two, the convergence of the two The two converging bodies are arranged and stored in parallel in the same housing, provided with a turbulent flow generating member formed by filling the end of the housing with a granular material, and the two converging bodies are connected to each other. the connected via a turbulence generating member, while the forward portion of said two converging body, is characterized in that the other was used as a return unit.
[0013]
Here, it is also possible within the previous SL gas separation filter tube providing a second turbulators.
[0014]
In addition, the turbulent flow generating member is formed of a convergent body of a tubular body, and the inner diameter of the tubular body is smaller than the inner diameter of the gas separation filter tube, or the turbulent flow generating member is filled with a granular material. Alternatively, it is desirable that the turbulent flow generating member is made of a porous body having pores smaller than the inner diameter of the gas separation filter tube.
The liquid degassing apparatus of the present invention includes the gas separation module described above and a vacuum pump connected to a specific gas recovery port from which the specific gas is recovered in the gas separation module. Is.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
A schematic sectional view of an example of the gas separation module of the present invention is shown in FIG. The gas separation module 20 of FIG. 1 has an inorganic separation membrane (hereinafter abbreviated as “separation membrane”) deposited on the inner surface of a long support tube (hereinafter abbreviated as “support tube”) made of porous ceramics. A converging body 22 formed by converging a plurality of gas separation filter tubes (hereinafter abbreviated as filters) 21 is housed in a housing 24, and similarly, converging bodies 22 ′ of a plurality of filters 21 ′ are housing 24. It is housed in parallel with the converging body 22 .
[0016]
The separation membrane may be formed on the outer surface of the support tube. However, when the gas separation module 20 is used as a so-called degassing filter that separates the specific gas from the liquid in which the specific gas is dissolved, the liquid It is desirable that a separation membrane be formed on the inner surface of the support tube in order to prevent the leakage gas separation performance from deteriorating on the other surface of the filters 21 and 21 ′ .
[0017]
The support tube has a large number of pores having a porosity of 20 to 40% and an average pore diameter of 0.1 to 2 μm, and is made of α-alumina, cordierite, etc., and preferably has an inner diameter of 3.0 mm. In the following, the distance that the specific gas in the object to be processed diffuses to the filter surface is short and the gas separation performance is improved, and the flow in the support pipe of the object to be processed is turbulent. Desirable in terms of prompting.
[0018]
On the other hand, the separation membrane is an organic separation membrane made of a resin having an average pore size of 0.2 to 5 nm, particularly 0.5 to 1.0 nm, or alumina, titania, zirconia, silica, etc., particularly easily manufactured. An inorganic separation membrane made of amorphous alumina or silica can be used because it can be used, and it is desirable that the film thickness is 0.1 to 2 μm. Of the above-mentioned separation membranes, the inorganic separation membrane has high gas separation performance and is made of a stable inorganic material, so that it has excellent heat resistance and chemical resistance, and also has high gas separation performance.
[0019]
Furthermore, an intermediate layer having a pore diameter between the support tube and the separation membrane may be interposed between the support tube and the separation membrane in terms of improving the film formability of the separation membrane.
[0020]
The filter 21, 21 'can be a filter or a gas for a certain gas is separated and recovered from the mixed gas is used as the degassing filter or the like for removing the gas from the liquid was Dissolved, especially the It can utilize suitably for the deaeration filter which removes the said gas from the liquid with a slow diffusion speed among processed materials.
[0021]
Further, as the filters 21 and 21 ′ , gas separation filter tubes made of an organic substance such as a hollow fiber body made of a resin or the like can be used in addition to those described above.
[0022]
The housing 24 is preferably made of a metal such as stainless steel, a material having high rigidity and airtightness such as glass or ceramics, and has a polygonal columnar body shape such as a substantially circular shape, a substantially elliptical shape, or a substantially rectangular shape in cross section.
[0023]
Further, according to FIG. 1, the filters 21 and 21 ′ are formed on the inner wall of the housing 24 via fixing jigs 23 and 23 ′ made of, for example, donut-shaped resin, metal, dense ceramics, or the like. The support is fixed.
[0024]
Further, the end portion of the housing 24, with an object to be processed inlet 25 for introducing the object to be processed which specific gas is mixed or dissolved into the device, the treated product for discharging the processed product recovery port 26 And are formed respectively.
[0025]
Moreover, separation of specific gases of the processing object in the side wall surface of the housing 24, the specific gas recovery port 27 for recovering is made form. The specific gas recovery port 27 is preferably formed at a position close to the end surface of the housing 24 on the side of forming the workpiece introduction port 25 in terms of improving gas separation performance.
[0026]
Incidentally, housings 24 are hermetically sealed. Further, a gasket (not shown) can be provided on the housing 24 .
[0027]
According to the present invention , the converging bodies 22 and 22 ′ are arranged in parallel, and the turbulent flow generating member 30 is disposed between the converging bodies 22 and 22 ′.
[0028]
As a result, compared with the end portion of the filter 21 in which the specific gas concentration in the object to be processed is lowered at the contact portion with the filter 21 and the gas separation performance is deteriorated, the object introduction part of the filter 21 ′ is in a turbulent state. As a result of increasing the frequency with which the specific gas in the workpiece contacts the inner wall surface of the filter 21 ′ , the gas separation performance can be enhanced, and the gas separation performance as a whole module is improved.
[0029]
Further, according to FIG. 1, since the plurality of filters 21 , 21 ′ of the converging bodies 22 , 22 ′ are connected to one turbulent flow generation member 30 , the gas separation module 20 can be easily manufactured. When the workpiece is introduced from the turbulent flow generating member 30 to the filter 21 ′ , the turbulent flow state can be further promoted, and the specific gas separation performance can be further enhanced.
[0030]
The turbulent flow generating member 30 acts as a barrier to the flow of the object to be processed and promotes turbulent flow in the flow of the object to be processed by stirring the object to be processed, but is smaller than the inner diameters of the filters 21 and 21 ′ . Those having voids, desirably an average void diameter of 100 to 900 μm and a porosity of 40 to 80% are desirable.
[0031]
The specific configuration of the turbulent flow generating member 30 includes (1) a converging body of a tubular body, the inner diameter of the tubular body being smaller than the inner diameters of the filters 21 and 21 ′ , and (2) the turbulent flow generating member 30. (3) The turbulent flow generating member 30 is preferably made of a porous body having pores having an average pore diameter smaller than the inner diameters of the filters 21 and 21 ' , and the material thereof. Is made of ceramics, glass, resin, urethane or the like.
[0032]
The gas separation method in the gas separation module 20 having the above configuration is, for example, that a liquid in which a specific gas is dissolved is supplied from the workpiece inlet 25 and introduced into the tube of the filter 21 so that the workpiece is passed through the tube of the filter 21 . the housing 24 with passing through, i.e. either to decompress the outer peripheral portion of the filter 21, from the specific gas by flowing said specific gas concentration low gas on the outer peripheral portion of the filter 21 is dissolved liquid only the specific gas filter 21 It passes through the wall surface and is discharged out of the system from the specific gas recovery port 27 from within the housing 24 .
[0033]
Also, the treated product that has passed through the tubes of the filter 21, through the turbulent flow generating member inlet 31 is guided to the turbulence generator 30, passed through the filter 21 by passing through the turbulence generator 30 The turbulent state of the workpiece is promoted.
[0034]
Further, the object to be processed that has passed through the turbulent flow generating member 30 is introduced into the filter 21 ′ via the turbulent flow generating member discharge port 32, and the specific gas is passed through the outer periphery of the filter 21 ′ from the inside of the pipe by the same method as described above. , And is led out of the system via the specific gas recovery port 27 , and the remainder is discharged out of the system from the processed material recovery port 26 .
[0035]
Note that with respect to gas separation module 20 of FIG. 1, with intervening filters 21, 21 'the same configuration as the turbulent flow generating member as described above into the respective second turbulators (not shown) The gas separation performance can be enhanced by the same effect as described above.
[00 36 ]
In addition, according to the configuration of FIG. 1 , the module can be reduced in size, and the stirring efficiency can be increased to promote turbulent flow.
[00 37 ]
In FIG. 1, yield Tabatai may be not but 3 or more was two. In addition, when there are a plurality of sets of converging bodies, turbulent flow generating members, and converging bodies, two or more turbulent flow generating members may be used together.
[00 38 ]
【Example】
Example 1
First, after forming into a long tubular body by mixing alumina having an purity of 99.9% and an average particle size of 0.1 μm, an organic binder, a lubricant, a plasticizer and water, and extrusion molding. , Fired at 1200 ° C. in the atmosphere, an elongated support tube having an inner diameter of 2.0 mm, a wall thickness of 0.3 mm, and a support tube length of 250 mm, having an average pore diameter of 0.2 μm and a porosity of 39% An α-alumina porous support tube was prepared.
[00 39 ]
Next, 1 mol of aluminum secondary butoxide was added to 100 mol of water for hydrolysis, and further nitric acid was added, followed by refluxing for 16 hours to prepare a boehmite sol. A syringe is attached to the end of the α-alumina spiral porous support tube, the boehmite sol obtained using the syringe is sucked up, held for 3 minutes, discharged, dried at room temperature for 1 hour, A series of steps of baking at 0 ° C. was repeated 15 times to produce a gas separation filter tube in which γ-alumina having a film thickness of 0.1 μm was formed on the inner peripheral surface of the support.
[00 40 ]
On the other hand, when the pore size distribution measurement by the argon adsorption method was performed on the obtained filter, as shown in FIG. 2 , the average pore size was 0.8 nm and the pore size of 1 nm or less was a fine pore size of 80% or more in the total pore volume. It was found to occupy the pore volume.
[00 41 ]
Next, both ends of the obtained filter are inserted into a dense alumina fixing member, joined and sealed using glass, and further inside an approximately cylindrical stainless steel housing having an inner diameter of 60 mm and a length of 50 mm. It fixed with the fixing member which consists of resin. Then, two converging bodies are inserted into the same housing, and a turbulent flow generating member having a structure of Table 1 is connected to the end portion of the housing in a cylindrical shape of 60 mmφ × thickness 15 mm . A separation module 20 was produced.
[00 42 ]
The obtained gas separation module was deaerated by flowing pure water with a dissolved oxygen concentration of 8 ppm from the workpiece inlet at a flow rate of 7 l / min and reducing the specific gas recovery port to 100 torr with a vacuum pump. And the dissolved oxygen amount of the pure water collect | recovered from the processed material collection | recovery port was measured, and it showed in Table 1.
[00 43 ]
[Table 1]

[00 44 ]
From the results of Table 1, it was found that the amount of dissolved oxygen is reduced and the gas separation performance is high by connecting the turbulent flow generating member with a plurality of filters in the converging body and interposing them between the converging bodies according to the present invention. .
[00 45 ]
On the other hand, sample no . The gas separation module having no turbulent flow generating member 9 had a low gas separation performance.
[0046]
【The invention's effect】
As described above in detail, the gas separation module of the present invention has a plurality of converging bodies arranged in parallel in the same housing and accommodates a turbulent flow generating member, thereby interposing a gas or liquid as an object to be processed. It can promote turbulent flow and improve gas separation performance.
[Brief description of the drawings]
FIG. 1 is a schematic sectional view showing an example of a gas separation module of the present invention.
FIG. 2 is a diagram showing a pore distribution of a separation membrane of a gas separation filter tube in a gas separation module of an example.
[Explanation of symbols]
20 gas separation module
21 , 21 ' gas separation filter tube (filter)
22 and 22 ' convergent body
24 housing
23 , 23 ' fixing member
25 workpiece inlet
26 Processed product collection port
27 specific gas recovery port
30 turbulence generating members

Claims (6)

With only a specific gas comprises two convergent body a gas separation filter tube formed by a plurality of convergence with permeable gas separation function, converging the two convergence of the two on the same housing body was housed arranged in parallel, a turbulent flow generating member formed by filling the granules in the end portion in the housing is provided, and the converging bodies of the two connected through the turbulence generating member A gas separation module characterized in that one of the two converging bodies is an outward path portion and the other is a return path portion . The gas separation module according to claim 1, wherein a second turbulent flow generation member is provided inside the gas separation filter tube. Wherein the second turbulence generating member consists convergence of the tubular body, a gas separation module of claim 2, wherein the inner diameter of the tubular body is smaller than the inner diameter of the gas separation filter tube. Gas separation module of claim 2, wherein said second turbulence generating member is characterized by being filled with the granular material. Gas separation module according to claim 2, characterized by comprising a porous body having smaller pores than the inner diameter of the second turbulators said gas separation filter tubes. A liquid desorption comprising the gas separation module according to claim 1 and a vacuum pump connected to a specific gas recovery port from which the specific gas is recovered in the gas separation module. Qi device.

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