JPH04104822A - Manufacture of inorganic porous body - Google Patents
Manufacture of inorganic porous bodyInfo
- Publication number
- JPH04104822A JPH04104822A JP22221290A JP22221290A JPH04104822A JP H04104822 A JPH04104822 A JP H04104822A JP 22221290 A JP22221290 A JP 22221290A JP 22221290 A JP22221290 A JP 22221290A JP H04104822 A JPH04104822 A JP H04104822A
- Authority
- JP
- Japan
- Prior art keywords
- porous
- porous body
- solid product
- base material
- cvd
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 239000012265 solid product Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000010409 thin film Substances 0.000 claims abstract description 6
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 19
- 238000000151 deposition Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims 2
- 239000011148 porous material Substances 0.000 abstract description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 239000010954 inorganic particle Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 10
- 239000012528 membrane Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- -1 etc. Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は濾過、ガス分離等に使用される無機多孔体の製
造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for manufacturing an inorganic porous body used for filtration, gas separation, etc.
（従来の技術）
精密濾過や限外濾過に用いる孔径か５０Å以下の微細多
孔質膜として、従来から特開平２−６８２９号に示され
るような有機材料からなる中空糸状膜、或いは特開平１
−２９９６１１号に示されるように、ゾル液を多孔質支
持体表面に塗布し、これを乾燥した後焼成するデイツプ
コート法により得られる無機多孔質膜か知られている。(Prior Art) As microporous membranes with pore diameters of 50 Å or less used for precision filtration and ultrafiltration, hollow fiber membranes made of organic materials as shown in JP-A-2-6829, or JP-A-1
As shown in Japanese Patent Application No. 299611, an inorganic porous membrane is known which is obtained by a dip coating method in which a sol solution is applied to the surface of a porous support, dried and then fired.
（発明か解決しようとする課題）
上述した多孔質膜のうち有機材料からなる膜は薬品によ
る洗浄及び蒸気による高温洗浄かできないという本質的
な欠陥がある。(Problems to be Solved by the Invention) Among the above-mentioned porous membranes, membranes made of organic materials have an essential defect in that they can only be cleaned with chemicals and high-temperature cleaning with steam.
また、デイツプコート法により得られる無機多孔質膜は
、高温で使用すると孔径か大きくなって微細膜としての
性能か低下し、更に製造の際の孔径のコントロールか難
しい。Furthermore, when the inorganic porous membrane obtained by the dip coating method is used at high temperatures, the pore size becomes large and its performance as a fine membrane deteriorates, and furthermore, it is difficult to control the pore size during production.
（課題を解決するための手段）
上記課題を解決すべく本発明は、多孔質基材の１次側に
ＣＶ Ｄ （Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ ｄｅｐｏ
ｓｉｔｉｏｎ）またはプラズマＣＶＤにより固体を生成
する気体状物質の一方を、２次側に気体状物質の他方を
流すようにした。(Means for Solving the Problems) In order to solve the above problems, the present invention provides chemical vapor depot (CVD) on the primary side of a porous base material.
One of the gaseous substances that produce a solid by plasma CVD or plasma CVD was made to flow, and the other gaseous substance was made to flow to the secondary side.
（作用）
制御された雰囲気下で反応して固体生成物を析出する２
種類の気体状物質の一方を多孔質基材の１次側に、他方
の気体状物質を多孔質基材の２次側に流すと、これら２
種類の気体状物質が多孔質基材の内部に侵入して反応し
、この反応による固体生成物が多孔質基材を構成する粒
子表面に薄膜状に析出し、結果として多孔質基材の孔径
が小さくなる。(Function) Precipitates a solid product by reacting under a controlled atmosphere 2
When one of the two types of gaseous substances is flowed into the primary side of the porous substrate and the other gaseous substance is caused to flow into the secondary side of the porous substrate, these two
Gaseous substances of various types enter the inside of the porous substrate and react, and the solid products of this reaction are deposited in a thin film on the surface of the particles that make up the porous substrate, resulting in a change in the pore size of the porous substrate. becomes smaller.
（実施例） 以下に本発明方法の一例を添付図面に基いて説明する。(Example) An example of the method of the present invention will be explained below based on the accompanying drawings.
先ず、本発明にあっては第１図に示すような多孔質基材
１を用意する。多孔質基材１としては円筒状のものに限
らず、平板状等任意である。また、多孔質基材１はアル
ミナ、ジルコニア等の無機粉、子２・・・を構成材料と
し、各粒子２・・・の間隔つまり多孔質基材１の平均孔
径ｄ１は０１μｍ程度とする。First, in the present invention, a porous base material 1 as shown in FIG. 1 is prepared. The porous base material 1 is not limited to a cylindrical shape, but may be of any shape such as a flat plate. Further, the porous base material 1 is made of inorganic powder such as alumina, zirconia, etc., and particles 2..., and the interval between each particle 2..., that is, the average pore diameter d1 of the porous base material 1 is about 0.1 μm.
そして、上記の多孔質基材１の１次側に高温・高真空下
で反応して固体生成物を析出する２種類の気体状物質の
一方を圧力Ｐ１で、多孔質基材１の２次側に他方の気体
状物質を圧力Ｐ２で流す。Then, one of the two types of gaseous substances that react at high temperature and high vacuum to precipitate a solid product is applied to the primary side of the porous base material 1 at a pressure P1, and the secondary side of the porous base material 1 is heated at a pressure of P1. The other gaseous substance is caused to flow to the side at a pressure P2.
ここで、気体状物質の一例を挙げれば、１次側に流すも
のとしては０２ガス、Ｈ２０ガス或いはＨ２とＣＯ２と
の混合ガス等とし、２次側に流すものとしてはＺｒＣ１
，（塩化ジルコニウム）等とする。Here, to give an example of gaseous substances, those flowing to the primary side are 02 gas, H20 gas, or a mixed gas of H2 and CO2, etc., and those flowing to the secondary side are ZrC1.
, (zirconium chloride), etc.
すると、粒子２表面にＣＶＤにより固体生成物３（Ｚｒ
Ｏ２）の薄膜が析出し、その結果として微細な孔径を有
する多孔体か得られる。Then, a solid product 3 (Zr
A thin film of O2) is deposited, resulting in a porous body with fine pore sizes.
また温度、圧力、原料ガスの種類等を変化させることに
より、固体生成物３の種類、厚みを制御することができ
、更に圧力Ｐ１、Ｐ２をコントロールすることで、１次
側又は２次側の一方の孔径か小さくなった所謂非対称膜
の製造も可能である。In addition, by changing the temperature, pressure, type of raw material gas, etc., the type and thickness of the solid product 3 can be controlled.Furthermore, by controlling the pressures P1 and P2, the primary side or the secondary side can be controlled. It is also possible to manufacture so-called asymmetric membranes in which one of the pores has a smaller diameter.
また、多孔質基材の材料及び原料カスの種類については
任意であるか、多孔質基材の材料と原料ガスが反応して
生成する物質とか同種のものであれば、基材とのなじみ
の点で好ましい。例えば基材をジルコニアとし、原料ガ
スを塩化ンルコニウムとする組合せは好ましい。尚、１
次側、２／ｌ１１：側のガスを反応させ、多孔質基材に
蒸着させる際の駆動力として、一般に熱を用いるか、プ
ラズマや光を用いてもよい。プラズマや光を用いること
で低温での析出か可能となる。また温度条件としては、
１００〜１３００°Ｃ位とし圧力条件としては０１〜７
６０Ｔｏｒｒ位まで利用できる。In addition, the material of the porous base material and the type of raw material waste are optional, or if they are of the same type, such as a substance generated by the reaction between the material of the porous base material and the raw material gas, it will be compatible with the base material. This is preferable in this respect. For example, a combination in which the base material is zirconia and the raw material gas is ruconium chloride is preferred. Furthermore, 1
As a driving force for reacting the gas on the next side, 2/l11: side, and depositing it on the porous substrate, heat is generally used, or plasma or light may be used. Deposition at low temperatures is possible by using plasma or light. In addition, as for temperature conditions,
The temperature is about 100 to 1300°C and the pressure condition is 01 to 7.
Can be used up to about 60 Torr.
次に具体的な数値を挙げた実施例を以下に示す。Examples with specific numerical values are shown below.
［実施例１］
多孔質基材としては孔径か０１μｍの多孔質アルミナチ
ューブを用意し、多孔質基材の１次側に流すガスとして
はＨ２とＣＯ２との混合ガスとし、多孔質基材の２次側
に流す気体状物質としては、固体状ノＺ ｒＣ１４（塩
化ンルコニウム）をベーパライザ（圧力； ５ ｔｏｒ
ｒ）により２６０°Ｃて気化させ、これをＡｒをキャリ
ヤガスとして流す。[Example 1] A porous alumina tube with a pore diameter of 01 μm was prepared as the porous base material, and a mixed gas of H2 and CO2 was used as the gas flowing on the primary side of the porous base material. As the gaseous substance flowing to the secondary side, solid ZrC14 (ruconium chloride) was used in a vaporizer (pressure: 5 torr).
r) at 260°C, and flowed with Ar as a carrier gas.
また、流す圧力は１次側Ｐ１，２次側Ｐ２とも１ｔｏｒ
ｒとし、蒸着温度は１００００Ｃ，蒸着時間は１〜１０
時間とする。In addition, the pressure to flow is 1torr on both the primary side P1 and the secondary side P2.
r, the deposition temperature is 10000C, and the deposition time is 1 to 10
Time.
（効果）
第４図は上記した［実施例１］の蒸着時間を２時間とし
た場合の分画分子量のデータを示し、このデータより阻
止率９０％に相当する孔径か約５０人であるので、本発
明方法により超微細膜か作成できることを確認すること
かできる。(Effect) Figure 4 shows data on the molecular weight fraction when the vapor deposition time in Example 1 is set to 2 hours, and from this data, the pore size corresponding to a rejection rate of 90% is approximately 50. It can be confirmed that ultrafine films can be produced by the method of the present invention.
即ち本発明によれば、高温・高真空下で反応して固体生
成物を析出する２種類の気体状物質の一方を所定の圧力
で多孔質基材の１次側に、他力の気体状物質を所定の圧
力で多孔質基材の２次側に流すようにしたので、これら
２種類の気体状物質が多孔質基材の内部で反応して固体
生成物か多孔質基材を構成する粒子表面に薄膜状に析出
し、結果として多孔質基材の孔径か小さくなり、平均孔
径か５０Ａ以下の孔径て、しかも耐熱性と孔径のコント
ロールに優れた無機多孔体を得る二とができる。That is, according to the present invention, one of two types of gaseous substances that react at high temperature and high vacuum to precipitate a solid product is applied to the primary side of a porous substrate at a predetermined pressure, and the gaseous substance is Since the substances are allowed to flow to the secondary side of the porous substrate at a predetermined pressure, these two gaseous substances react inside the porous substrate to form a solid product or the porous substrate. It precipitates in the form of a thin film on the particle surface, and as a result, the pore size of the porous substrate becomes small, making it possible to obtain an inorganic porous body with an average pore size of 50A or less, and excellent heat resistance and pore size control.
第１図は本発明により製造される無機多孔体の一例の断
面図、第２図は同無機多孔体を構成する粒子の表面にＣ
ＶＤにより固体生成物を析出せしめる前の状態を示す拡
大図、第３図は同無機多孔体を構成する粒子の表面にＣ
〜′Ｄにより固体生成物を析出せしめた状態を示す拡大
図、第４図はエチレングリコール分子量と阻止率との関
係（分画分子量）を示すグラフである。
尚、図面中１は多孔質基材、２は多孔質基材の構成粒子
、３は固体生成物である。
願 人FIG. 1 is a cross-sectional view of an example of an inorganic porous material produced according to the present invention, and FIG.
Figure 3 is an enlarged view showing the state before the solid product is precipitated by VD.
An enlarged view showing the state in which the solid product was precipitated by ~'D, and FIG. 4 is a graph showing the relationship between ethylene glycol molecular weight and rejection rate (molecular weight cutoff). In the drawings, 1 is a porous base material, 2 is a constituent particle of the porous base material, and 3 is a solid product. wish person
Claims (1)
ｔｉｏｎ）またはプラズマＣＶＤによって固体生成物を
析出する２種類の気体状物質の一方を多孔質基材の１次
側に、他方の気体状物質を多孔質基材の２次側に流し、
これら２種類の気体状物質を多孔質基材の内部で反応せ
しめ、この反応による固体生成物を多孔質基材を構成す
る粒子表面に薄膜状に析出せしめることを特徴とする無
機多孔体の製造方法。CVD (Chemical vapor deposition)
tion) or plasma CVD to deposit a solid product, one of the two gaseous substances is flowed on the primary side of the porous substrate, and the other gaseous substance is flowed on the secondary side of the porous substrate,
Production of an inorganic porous body characterized by reacting these two types of gaseous substances inside a porous base material, and depositing a solid product from this reaction in the form of a thin film on the surface of particles constituting the porous base material. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22221290A JPH04104822A (en) | 1990-08-23 | 1990-08-23 | Manufacture of inorganic porous body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22221290A JPH04104822A (en) | 1990-08-23 | 1990-08-23 | Manufacture of inorganic porous body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04104822A true JPH04104822A (en) | 1992-04-07 |
Family
ID=16778892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22221290A Pending JPH04104822A (en) | 1990-08-23 | 1990-08-23 | Manufacture of inorganic porous body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04104822A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006239663A (en) * | 2005-03-07 | 2006-09-14 | Noritake Co Ltd | Production method of hydrogen gas separation membrane |
-
1990
- 1990-08-23 JP JP22221290A patent/JPH04104822A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006239663A (en) * | 2005-03-07 | 2006-09-14 | Noritake Co Ltd | Production method of hydrogen gas separation membrane |
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