JP6683365B2 - Method for manufacturing gas separation filter - Google Patents
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- 238000000926 separation method Methods 0.000 title claims description 67
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 238000000034 method Methods 0.000 title claims description 20
- 239000007789 gas Substances 0.000 claims description 123
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 230000035699 permeability Effects 0.000 description 18
- 239000000463 material Substances 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 108010004350 tyrosine-rich amelogenin polypeptide Proteins 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、気体分離フィルタの製造方法に関する。 The present invention relates to a method for manufacturing a gas separation filter.
混合ガスから特定のガスを透過させて分離する気体分離フィルタがある。気体分離フィルタとして、例えば、多孔質支持層の上に中間層が形成され、さらにその上に分離層が形成された構造が挙げられる。分離層としてシリカ系分離層が注目されており、種々の手法により形成される。 There is a gas separation filter that allows a specific gas to pass through and be separated from a mixed gas. Examples of the gas separation filter include a structure in which an intermediate layer is formed on a porous support layer and a separation layer is further formed on the intermediate layer. A silica-based separation layer has attracted attention as a separation layer, and is formed by various methods.
分離層の形成手法として、ゾルゲル法を用いた製膜手法のほか、大気圧プラズマＣＶＤ（Chemical Vapor Deposition）法による製膜手法がある（非特許文献１）。大気圧プラズマＣＶＤ法は、常温、常圧下で製膜できること、真空設備が不要なため、連続処理による大面積製膜が可能なことなどの利点がある。 As a method for forming the separation layer, there is a film forming method using a sol-gel method and a film forming method using an atmospheric pressure plasma CVD (Chemical Vapor Deposition) method (Non-Patent Document 1). The atmospheric pressure plasma CVD method is advantageous in that a film can be formed at room temperature and atmospheric pressure, and since a vacuum facility is not required, a large area film can be formed by continuous processing.
非特許文献１では、放電ガスの流量等、具体的な膜の製造条件が開示されておらず、また、開示されている膜の気体の透過率、透過率比からみても更に優れた気体選択性を備えた気体分離フィルタを製造できる余地がある。 Non-Patent Document 1 does not disclose specific manufacturing conditions of the film such as the flow rate of the discharge gas, and the gas selection of the disclosed film is further excellent from the viewpoint of gas permeability and transmittance ratio. There is room to manufacture a gas separation filter with good properties.
本発明は上記事項に鑑みてなされたものであり、その目的とするところは、気体選択性に優れた気体分離フィルタの製造方法を提供することにある。 The present invention has been made in view of the above matters, and an object thereof is to provide a method for manufacturing a gas separation filter having excellent gas selectivity.
本発明に係る気体分離フィルタの製造方法は、
多孔質基材の上に大気圧プラズマ化学気相成長法で分離層を形成する気体分離フィルタの製造方法であって、
放電ガスとして窒素及びアルゴンの混合ガスを放電部に導入して大気圧プラズマを発生させ、
揮発性有機ケイ素化合物を放電部の下方に導入して前記大気圧プラズマに混合させ、前記多孔質基材の上に分離層を形成し、
前記放電ガス中の窒素が０体積％より高く５．０体積％以下である、
ことを特徴とする。
A method for manufacturing a gas separation filter according to the present invention,
A method for producing a gas separation filter, which comprises forming a separation layer on a porous substrate by atmospheric pressure plasma chemical vapor deposition,
As a discharge gas, a mixed gas of nitrogen and argon is introduced into the discharge part to generate atmospheric pressure plasma,
A volatile organosilicon compound is introduced below the discharge part and mixed with the atmospheric pressure plasma to form a separation layer on the porous substrate,
Nitrogen in the discharge gas is higher than 0 volume% and 5.0 volume% or less,
It is characterized by
また、前記混合ガス中の窒素が０．２５体積％以下であることが好ましい。 Further, it is preferable that nitrogen in the mixed gas is 0.25% by volume or less.
また、前記揮発性有機ケイ素化合物がヘキサメチルジシロキサンであることが好ましい。 Further, it is preferable that the volatile organosilicon compound is hexamethyldisiloxane.
また、前記多孔質基材上に前記多孔質支持層よりも細孔径が小さい中間層を形成し、
前記中間層上に前記分離層を形成することが好ましい。
Further, an intermediate layer having a smaller pore size than the porous support layer is formed on the porous substrate,
It is preferable to form the separation layer on the intermediate layer.
また、前記分離層を形成した後、３００℃で熱処理を行うことが好ましい。 Further, it is preferable to perform heat treatment at 300 ° C. after forming the separation layer.
本発明にかかる気体分離フィルタの製造方法では、気体選択性に優れた気体分離フィルタを製造することができる。 With the method for manufacturing a gas separation filter according to the present invention, a gas separation filter having excellent gas selectivity can be manufactured.
本実施の形態に係る気体分離フィルタの製造方法は、図１（Ａ）、（Ｂ）に示すように、支持層（support layer）となる多孔質基材と、中間層（medium layer）と、分離層（top layer）を備えた気体分離フィルタを製造する方法である。気体分離フィルタは、支持層、中間層、分離層の順に配置されており、分子径の異なる気体が混合する混合気体から、分子径の小さい気体を透過させるとともに、分子径の大きい気体の透過を阻害して分離する機能を有する。 As shown in FIGS. 1 (A) and 1 (B), the method for manufacturing a gas separation filter according to the present embodiment includes a porous base material serving as a support layer, an intermediate layer (medium layer), A method of manufacturing a gas separation filter having a top layer. The gas separation filter is arranged in the order of the support layer, the intermediate layer, and the separation layer, and from a mixed gas in which gases having different molecular diameters are mixed, a gas having a small molecular diameter is permeated and a gas having a large molecular diameter is permeated. It has the function of inhibiting and separating.
本実施の形態に係る気体分離フィルタの製造方法では、まず、支持層となる多孔質基材を準備する。分離層は薄く耐久性、強度が低いので、支持層は、気体分離フィルタに耐久性、強度をもたらす機能を果たす。また、支持層は、気体の透過を阻害しないよう通気性を維持する機能を果たす。これらの機能を果たし得る限り、支持層は、多孔質の無機多孔体、有機多孔体のいずれでもよい。支持層の細孔径及び空隙率は、気体の透過性を損なわないよう大きいことが好ましく、例えば、平均細孔径が０．０５μｍ〜１０μｍ程度、より好ましくは、０．１μｍ〜５μｍである。 In the method for manufacturing the gas separation filter according to the present embodiment, first, the porous base material to be the support layer is prepared. Since the separation layer is thin and has low durability and strength, the support layer functions to provide the gas separation filter with durability and strength. The support layer also has a function of maintaining air permeability so as not to impede gas permeation. The support layer may be a porous inorganic porous material or an organic porous material as long as it can fulfill these functions. The pore diameter and porosity of the support layer are preferably large so as not to impair the gas permeability, and for example, the average pore diameter is about 0.05 μm to 10 μm, and more preferably 0.1 μm to 5 μm.
支持層として、アルミナ（α−Ａｌ２Ｏ３（α−アルミナ）、γ−Ａｌ２Ｏ３（γ−アルミナ））、ムライト、ジルコニア、チタニア、或いはこれらの複合物からなるセラミックスなどが挙げられる。 Examples of the support layer include alumina (α-Al 2 O 3 (α-alumina), γ-Al 2 O 3 (γ-alumina)), mullite, zirconia, titania, or a ceramic composed of a composite thereof.
支持層の表面を均質化して、中間層を形成することが好ましい。均質化に用いる素材には、支持層と同素材の微粒子を用いるとよく、支持層としてアルミナを用いる場合、これと同素材のアルミナ微粒子を支持層表面に担持させて均質化を行えばよい。支持層上へのアルミナ微粒子の担持は、バインダーにアルミナ微粒子を分散させ、これを支持層表面に塗布、乾燥、焼成することにより行える。バインダーとしては、後述する中間層形成用のゾルなどを用いればよい。 It is preferable to homogenize the surface of the support layer to form an intermediate layer. As the material used for homogenization, fine particles of the same material as the support layer may be used. When alumina is used for the support layer, alumina fine particles of the same material may be supported on the surface of the support layer for homogenization. The alumina fine particles can be supported on the support layer by dispersing the alumina fine particles in a binder, coating the support on the surface of the support layer, and drying and firing. As the binder, a sol or the like for forming an intermediate layer described later may be used.
均質化された支持層の上に、中間層を形成する。中間層の平均細孔径は、支持層よりも小さく、分離層よりも大きく、例えば、１〜６ｎｍである。中間層の形成は、例えば、支持層の上にシリカゾルを塗布し、焼成することで形成できる。シリカゾルの塗布は、スピンコート法や、ホットコーティング法など、種々の方法により行えばよい。なお、中間層を複数層形成してもよい。例えば、ＴｉＯ２ゾルを塗布、焼成してＴｉＯ２層（平均細孔径４〜６ｎｍ）を形成し、その上にＳｉＯ２−ＺｒＯ２ゾルを塗布、焼成してＳｉＯ２−ＺｒＯ２層（平均細孔径１〜２ｎｍ）を形成することで、２層の中間層を形成できる。 An intermediate layer is formed on the homogenized support layer. The average pore diameter of the intermediate layer is smaller than that of the support layer and larger than that of the separation layer, and is, for example, 1 to 6 nm. The intermediate layer can be formed, for example, by applying silica sol on the support layer and firing it. The silica sol may be applied by various methods such as spin coating and hot coating. A plurality of intermediate layers may be formed. For example, a TiO 2 sol is applied and fired to form a TiO 2 layer (average pore size 4 to 6 nm), and a SiO 2 —ZrO 2 sol is applied and fired on it to form a SiO 2 —ZrO 2 layer (average fineness). By forming a pore size of 1 to 2 nm), two intermediate layers can be formed.
中間層を形成した後、中間層の上に分離層を形成する。分離層は、中間層の細孔径よりも小さい細孔径（例えば、平均細孔径０．２〜０．５ｎｍ）を有する多孔体である。分離層は、分子径の異なる気体が混合する混合気体から、分子径の小さい気体を透過させるとともに、分子径の大きい気体の透過を阻害して分離する機能を有する層である。 After forming the intermediate layer, the separation layer is formed on the intermediate layer. The separation layer is a porous body having a pore size (for example, an average pore size of 0.2 to 0.5 nm) smaller than that of the intermediate layer. The separation layer is a layer having a function of allowing a gas having a small molecule diameter to permeate from a mixed gas in which gases having different molecular diameters are mixed, and having a function of inhibiting the permeation of a gas having a large molecule diameter to be separated.
分離層の形成は、大気圧プラズマＣＶＤ（Chemical Vapor Deposition）法により形成する。例えば、図２、図３に示す分離層製膜装置１を用いて、分離層を形成することができる。 The separation layer is formed by an atmospheric pressure plasma CVD (Chemical Vapor Deposition) method. For example, the separation layer can be formed by using the separation layer film forming apparatus 1 shown in FIGS.
Ｎ２ガスボンベ１０、Ａｒガスボンベ１１には、それぞれＮ２ガス、Ａｒガスが充填されており、Ｎ２ガス、Ａｒガスはガス混合装置２０を介し、所定の割合に調整された混合ガス（放電ガス）となり、プラズマ発生装置５０へと供給される。また、Ａｒガスは、シールガス、キャリヤガスとしても用いられる。シールガスは、Ａｒガスボンベ１１から流量計３０、ストップバルブ３１を介して、所定の流量でプラズマ発生装置５０へと供給される。また、キャリヤガスは、Ａｒガスボンベ１１から圧力調整バルブ４０、圧力計４１、流量計４２、ストップバルブ４３、バブラー４４、トラップ４５、ストップバルブ４６を介して、バブラー４４内の分離層の原料である揮発性有機ケイ素化合物をプラズマ発生装置５０へと供給する。 The N 2 gas cylinder 10 and the Ar gas cylinder 11 are filled with N 2 gas and Ar gas, respectively, and the N 2 gas and the Ar gas are mixed gas (discharge gas) adjusted to a predetermined ratio through the gas mixing device 20. ) And supplied to the plasma generator 50. Ar gas is also used as a seal gas and a carrier gas. The seal gas is supplied from the Ar gas cylinder 11 through the flow meter 30 and the stop valve 31 to the plasma generator 50 at a predetermined flow rate. Further, the carrier gas is a raw material of the separation layer in the bubbler 44 from the Ar gas cylinder 11 via the pressure adjusting valve 40, the pressure gauge 41, the flow meter 42, the stop valve 43, the bubbler 44, the trap 45, and the stop valve 46. The volatile organosilicon compound is supplied to the plasma generator 50.
放電ガスが放電部に導入され、電源５１によりプラズマヘッド５２が印加されると、放電ガスの分子が電離し、大気圧プラズマが発生する。 When the discharge gas is introduced into the discharge part and the plasma head 52 is applied by the power supply 51, the molecules of the discharge gas are ionized, and atmospheric pressure plasma is generated.
また、放電部の下方にて、原料供給ヘッド５３から揮発性有機ケイ素化合物が導入される。揮発性有機ケイ素化合物の導入は、液体状の揮発性有機ケイ素化合物の入れられたバブラー４４にキャリヤガスとしてＡｒガスを通じることで、蒸気或いはミスト状の揮発性有機ケイ素化合物が原料供給ヘッド５３から放電部の下方に導入される。 Further, a volatile organosilicon compound is introduced from the raw material supply head 53 below the discharge part. The volatile organosilicon compound is introduced by passing Ar gas as a carrier gas through the bubbler 44 containing the liquid volatile organosilicon compound, so that the vapor or mist volatile organosilicon compound is supplied from the raw material supply head 53. It is introduced below the discharge part.
これにより、放電部で発生した大気圧プラズマに揮発性有機ケイ素化合物が混合される。そして、揮発性有機ケイ素化合物が分解され、多孔質基材に化学気相蒸着により分離層が形成される。本実施の形態のように円筒状の多孔質基材を用いる場合、多孔質基材を回転（例えば、２００ｒｐｍ）させながら行うと厚みの均質な分離層が得られる。以上のようにして、支持層、中間層、分離層の３層構造である気体分離フィルタが得られる。 As a result, the volatile organosilicon compound is mixed with the atmospheric pressure plasma generated in the discharge part. Then, the volatile organosilicon compound is decomposed, and the separation layer is formed on the porous substrate by chemical vapor deposition. When a cylindrical porous substrate is used as in this embodiment, a separation layer having a uniform thickness can be obtained by rotating the porous substrate (for example, 200 rpm). As described above, a gas separation filter having a three-layer structure including a support layer, an intermediate layer, and a separation layer is obtained.
原料の揮発性有機ケイ素化合物として、大気圧プラズマにより化学気相蒸着可能であればいずれを用いてもよく、例えば、ヘキサメチルジシロキサン、トリメチルエトキシシラン、メチルトリエトキシシラン等が挙げられる。また、キャリヤガス（Ａｒガス）に対する揮発性有機ケイ素化合物の割合は任意の割合（例えば、Ａｒガスに対して揮発性有機ケイ素化合物を１ｖｏｌ％）とすることができる。 Any volatile organosilicon compound as a raw material may be used as long as it can be chemically vapor deposited by atmospheric pressure plasma, and examples thereof include hexamethyldisiloxane, trimethylethoxysilane, and methyltriethoxysilane. Further, the ratio of the volatile organosilicon compound to the carrier gas (Ar gas) can be any ratio (for example, 1 vol% of the volatile organosilicon compound to the Ar gas).
放電ガス中におけるＮ２ガスの割合は、Ａｒガスに対して５．０ｖｏｌ％以下であることが好ましく、より好ましくは０．２５ｖｏｌ％以下である。後述の実施例に示すように、上記Ｎ２の割合であれば、混合ガスから特定ガスの分離能が優れた気体分離フィルタを製造することができる。また、放電ガスの流量についても任意の流量（例えば、５．０Ｌ／ｍｉｎ）とすることができる。 The proportion of N 2 gas in the discharge gas is preferably 5.0 vol% or less, and more preferably 0.25 vol% or less with respect to Ar gas. As shown in Examples described later, if the ratio of N 2 is the above, it is possible to manufacture a gas separation filter having an excellent ability to separate a specific gas from a mixed gas. Further, the flow rate of the discharge gas can be set to an arbitrary flow rate (for example, 5.0 L / min).
更に、分離層を形成した後、熱処理（アニーリング）することが好ましい。たとえば、減圧条件で３００℃、１時間程度の熱処理を行う。熱処理により、更に気体透過率が向上した気体分離フィルタが得られる。 Further, it is preferable to perform heat treatment (annealing) after forming the separation layer. For example, heat treatment is performed under reduced pressure at 300 ° C. for about 1 hour. By the heat treatment, a gas separation filter having a further improved gas permeability can be obtained.
上記では、円筒状の気体分離フィルタの製造例について説明したが、平板状等の多孔質基材を用いて製造してもよい。また、上記では支持層の上に中間層を形成して分離層を形成する例について説明したが、中間層の形成を行わず、分離層を形成する形態であってもよい。 In the above, the manufacturing example of the cylindrical gas separation filter has been described, but it may be manufactured using a flat plate-shaped porous substrate. Moreover, although the example in which the intermediate layer is formed on the support layer to form the separation layer has been described above, the formation of the separation layer may be performed without forming the intermediate layer.
種々の条件で気体分離フィルタを作製し、気体選択性について評価した。 Gas separation filters were prepared under various conditions and evaluated for gas selectivity.
基材としてα−アルミナ多孔質管（外径３ｍｍ、内径２ｍｍ、細孔径１５０ｎｍ）を用いた。この基材表面に、以下のようにして中間層を形成した。ＴｉＯ２ゾルを基材表面にスピンコーティング法により塗布して５５０℃で焼成し、細孔径４〜６ｎｍのＴｉＯ２層を形成した。更に、ＳｉＯ２−ＺｒＯ２ゾルをＴｉＯ２層上にホットコーティング法（２００℃）により塗布して５５０℃で焼成し、細孔径１〜２ｎｍのＳｉＯ２−ＺｒＯ２層を形成し、２層構造の中間層を形成した。 As the base material, an α-alumina porous tube (outer diameter 3 mm, inner diameter 2 mm, pore diameter 150 nm) was used. An intermediate layer was formed on the surface of this substrate as follows. The TiO 2 sol was applied to the surface of the base material by a spin coating method and baked at 550 ° C. to form a TiO 2 layer having a pore size of 4 to 6 nm. Further, a SiO 2 —ZrO 2 sol is applied onto the TiO 2 layer by a hot coating method (200 ° C.) and baked at 550 ° C. to form a SiO 2 —ZrO 2 layer having a pore diameter of 1 to 2 nm, and a two-layer structure is formed. Was formed.
図２に示した装置を用い、中間層を形成した基材上に、大気圧プラズマＣＶＤ法により分離層を形成し、気体分離フィルタ（フィルタ１、フィルタ２、フィルタ３、フィルタ４）を作製した。 Using the apparatus shown in FIG. 2, a separation layer was formed by atmospheric pressure plasma CVD on the base material on which the intermediate layer was formed, and a gas separation filter (filter 1, filter 2, filter 3, filter 4) was produced. .
原料の揮発性有機ケイ素化合物として、ヘキサメチルジシロキサン（ＨＭＤＳＯ）を用いた。また、放電ガスとして、Ａｒ、Ｏ２／Ａｒ（Ｏ２及びＡｒの混合ガス）、Ｎ２／Ａｒ（Ｎ２及びＡｒの混合ガス）を用いた。また、シールガスとして、Ａｒを用いた。 Hexamethyldisiloxane (HMDSO) was used as a volatile organosilicon compound as a raw material. Further, Ar, O 2 / Ar (mixed gas of O 2 and Ar) and N 2 / Ar (mixed gas of N 2 and Ar) were used as the discharge gas. Ar was used as the seal gas.
表１に、作製した各気体分離フィルタ（フィルタ１〜フィルタ４）の前駆体、放電ガス、シールガスの条件をまとめた。 Table 1 summarizes the conditions of the precursor, discharge gas, and seal gas of each of the produced gas separation filters (filter 1 to filter 4).
得られた４種の気体分離フィルタ（フィルタ１〜フィルタ４）を用いて、気体透過特性の評価を行った。気体透過特性の評価は、以下のようにして行った。図４に示す装置を用い、各気体（Ｈｅ、Ｈ２、ＣＯ２、Ｎ２、ＣＨ４、ＳＦ６）の気体透過率をドライ条件にて測定した。即ち、図４に示す装置の水に通じるバルブを閉鎖して行った。測定ガスはＨｅ、Ｈ２、ＣＯ２、Ｎ２、ＣＨ４、ＳＦ６の６種類（市販の高純度ガス）を用いた。なお、スイープガスとしてＮ２を用いた。なお、測定は５０℃で行った。 The gas permeation characteristics were evaluated using the obtained four types of gas separation filters (filter 1 to filter 4). The gas permeability characteristics were evaluated as follows. Using the apparatus shown in FIG. 4, the gas permeability of each gas (He, H 2 , CO 2 , N 2 , CH 4 , SF 6 ) was measured under dry conditions. That is, it was carried out by closing the valve communicating with water in the apparatus shown in FIG. As the measurement gas, six kinds of He, H 2 , CO 2 , N 2 , CH 4 , and SF 6 (commercially available high-purity gas) were used. N 2 was used as the sweep gas. The measurement was performed at 50 ° C.
その結果を図５に示す。フィルタ１、フィルタ２に比べ、Ｎ２及びＡｒの混合ガスを放電ガスに用いたフィルタ３、フィルタ４の気体選択性が良好（ＣＯ２／Ｎ２透過比率が良好）であることがわかる。すなわち、ＣＯ２及びＮ２を含有する混合ガスから、ＣＯ２を選択的に透過させて分離させ得ることがわかる。 The result is shown in FIG. It can be seen that the gas selectivity of the filters 3 and 4 using the mixed gas of N 2 and Ar as the discharge gas is better (the CO 2 / N 2 permeation ratio is better) than the filters 1 and 2. That is, it is understood that CO 2 can be selectively permeated and separated from the mixed gas containing CO 2 and N 2 .
続いて、最も良好な気体選択性を示したフィルタ４を減圧条件にて１時間、３００℃で熱処理し、フィルタ４’を作製した。そして、上記と同様に気体透過特性の評価を行った。 Then, the filter 4 showing the best gas selectivity was heat-treated at 300 ° C. for 1 hour under a reduced pressure condition to prepare a filter 4 ′. Then, the gas permeability characteristics were evaluated in the same manner as above.
その結果を図６に示す。熱処理前（フィルタ４）に比べ、熱処理後（フィルタ４’）では、ＣＯ２／Ｎ２透過比率が４６、ＣＯ２／ＣＨ４透過比率が１６０と、気体選択性に優れていることがわかる。 The result is shown in FIG. Compared to before heat treatment (filter 4), after heat treatment (filter 4 ′), the CO 2 / N 2 permeation ratio is 46 and the CO 2 / CH 4 permeation ratio is 160, which shows excellent gas selectivity.
続いて、熱処理温度による気体透過特性への影響について検証した。上記のフィルタ４について、減圧条件にて、１００℃、２００℃、３００℃、４００℃のそれぞれの温度で１時間熱処理を行った。そして、それぞれについて、上記と同様に気体透過特性の評価を行った。その結果を図７に示す。 Subsequently, the effect of the heat treatment temperature on the gas permeability was verified. The filter 4 was heat-treated under reduced pressure at 100 ° C., 200 ° C., 300 ° C., and 400 ° C. for 1 hour. Then, for each of them, the gas permeability characteristics were evaluated in the same manner as above. The result is shown in FIG. 7.
熱処理温度が高くなるにつれ、ＣＯ２透過率が高くなっている。一方、ＣＯ２／Ｎ２透過比率については、３００℃までは高くなっているが、４００℃では低下する結果となった。 As the heat treatment temperature becomes higher, the CO 2 transmittance becomes higher. On the other hand, the CO 2 / N 2 transmission ratio was high up to 300 ° C., but decreased at 400 ° C.
また、放電ガスをＮ２／Ａｒ：１．０ｖｏｌ％とした以外、上記フィルタ４の作製手法と同様にして、フィルタ５を作製した。そして、得られたフィルタ５を減圧条件にて１００℃、２００℃、３００℃、４００℃、５００℃のそれぞれの温度で１時間熱処理した。そして、それぞれについて、上記と同様に気体透過特性の評価を行った。その結果を図８に示す。 Further, a filter 5 was produced in the same manner as the filter 4 was produced, except that the discharge gas was N 2 / Ar: 1.0 vol%. Then, the obtained filter 5 was heat-treated at a temperature of 100 ° C., 200 ° C., 300 ° C., 400 ° C. and 500 ° C. for 1 hour under a reduced pressure condition. Then, for each of them, the gas permeability characteristics were evaluated in the same manner as above. The result is shown in FIG.
図８を見ると、ＣＯ２透過率は３００℃までは高くなる一方、３００℃を超えると低くなっている。また、ＣＯ２／ＣＨ４透過比率及びＣＯ２／Ｎ２透過比率についても、３００℃を超えると低下する傾向が見られる。 As shown in FIG. 8, the CO 2 transmittance increases up to 300 ° C., but decreases above 300 ° C. Further, the CO 2 / CH 4 permeation ratio and the CO 2 / N 2 permeation ratio also tend to decrease when the temperature exceeds 300 ° C.
これらのことから、分離層を形成後、気体分離フィルタを３００℃で熱処理することが好ましいと言える。 From these, it can be said that it is preferable to heat-treat the gas separation filter at 300 ° C. after forming the separation layer.
また、フィルタ４’について、気体透過率の温度依存性について検証した。Ｈｅ、ＣＯ２、Ｎ２、ＳＦ６について、透過温度を５０℃、１００℃、２００℃、２５０℃とし、上記と同様にして気体透過率を測定した。 Further, the temperature dependency of the gas permeability of the filter 4 ′ was verified. Regarding He, CO 2 , N 2 and SF 6 , the permeation temperature was 50 ° C., 100 ° C., 200 ° C. and 250 ° C., and the gas permeability was measured in the same manner as above.
その結果を図９に示す。なお、非特許文献１では、Ｈｅ、Ｎ２及びＳＦ６の透過率の温度依存性が示されているが、フィルタ４’の気体透過率は、これらの透過率と比べて１０倍程度良好であることがわかる。非特許文献１ではプラズマ生成条件等が開示されていないが、本実施例の条件と異なっており、本実施例の条件により、非特許文献１よりも良好な透過特性を備えた気体分離フィルタを製造できることがわかる。 The result is shown in FIG. Although Non-Patent Document 1 shows the temperature dependence of the transmittance of He, N 2, and SF 6 , the gas transmittance of the filter 4 ′ is about 10 times better than these transmittances. I know there is. Non-Patent Document 1 does not disclose plasma generation conditions and the like, but is different from the conditions of the present embodiment, and a gas separation filter having better transmission characteristics than that of Non-Patent Document 1 is provided according to the conditions of the present embodiment. It turns out that it can be manufactured.
本発明に係る分離フィルタの製造方法では、上述したように、気体選択性に優れた気体分離フィルタを製造することができる。 In the method for manufacturing a separation filter according to the present invention, as described above, a gas separation filter having excellent gas selectivity can be manufactured.
１ 分離層製膜装置
１０ Ｎ２ガスボンベ
１１ Ａｒガスボンベ
２０ ガス混合装置
３０ 流量計
３１ ストップバルブ
４０ 圧力調整バルブ
４１ 圧力計
４２ 流量計
４３ ストップバルブ
４４ バブラー
４５ トラップ
４６ ストップバルブ
５０ プラズマ発生装置
５１ 電源
５２ プラズマヘッド
５３ 原料供給ヘッド
５４ カバー
Ｂ 多孔質基材
Ｆ 気体分離フィルタ
1 Separation Layer Film Forming Device 10 N 2 Gas Cylinder 11 Ar Gas Cylinder 20 Gas Mixing Device 30 Flow Meter 31 Stop Valve 40 Pressure Adjustment Valve 41 Pressure Gauge 42 Flow Meter 43 Stop Valve 44 Bubbler 45 Trap 46 Stop Valve 50 Plasma Generator 51 Power Supply 52 Plasma head 53 Raw material supply head 54 Cover B Porous base material F Gas separation filter
Claims (5)
放電ガスとして窒素及びアルゴンの混合ガスを放電部に導入して大気圧プラズマを発生させ、
揮発性有機ケイ素化合物を放電部の下方に導入して前記大気圧プラズマに混合させ、前記多孔質基材の上に分離層を形成し、
前記放電ガス中の窒素が０体積％より高く５．０体積％以下である、
ことを特徴とする気体分離フィルタの製造方法。 A method for producing a gas separation filter, which comprises forming a separation layer on a porous substrate by atmospheric pressure plasma chemical vapor deposition,
As a discharge gas, a mixed gas of nitrogen and argon is introduced into the discharge part to generate atmospheric pressure plasma,
A volatile organosilicon compound is introduced below the discharge part and mixed with the atmospheric pressure plasma to form a separation layer on the porous substrate,
Nitrogen in the discharge gas is higher than 0 volume% and 5.0 volume% or less,
A method of manufacturing a gas separation filter, comprising:
ことを特徴とする請求項１に記載の気体分離フィルタの製造方法。 Nitrogen in the mixed gas is 0.25% by volume or less,
The method for manufacturing a gas separation filter according to claim 1, wherein
ことを特徴とする請求項１又は２に記載の気体分離フィルタの製造方法。 The volatile organosilicon compound is hexamethyldisiloxane,
The method for manufacturing a gas separation filter according to claim 1 or 2, characterized in that.
前記中間層上に前記分離層を形成する、
ことを特徴とする請求項１乃至３のいずれか一項に記載の気体分離フィルタの製造方法。 An intermediate layer having a smaller pore size than the porous substrate is formed on the porous substrate,
Forming the separation layer on the intermediate layer,
The method for manufacturing a gas separation filter according to any one of claims 1 to 3, wherein:
ことを特徴とする請求項１乃至４のいずれか一項に記載の気体分離フィルタの製造方法。 After forming the separation layer, heat treatment is performed at 300 ° C.
The method for manufacturing a gas separation filter according to any one of claims 1 to 4, wherein:
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