JP3304526B2 - Ceramic separation membrane - Google Patents
Ceramic separation membraneInfo
- Publication number
- JP3304526B2 JP3304526B2 JP20017893A JP20017893A JP3304526B2 JP 3304526 B2 JP3304526 B2 JP 3304526B2 JP 20017893 A JP20017893 A JP 20017893A JP 20017893 A JP20017893 A JP 20017893A JP 3304526 B2 JP3304526 B2 JP 3304526B2
- Authority
- JP
- Japan
- Prior art keywords
- ceramic porous
- test
- zirconia
- ceramic
- separation membrane
- 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.)
- Expired - Fee Related
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Compositions Of Oxide Ceramics (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、液体の分離、濃縮等に
使用されるセラミック分離膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ceramic separation membrane used for separating and concentrating a liquid.
【０００２】[0002]
【従来の技術】セラミック多孔質支持体の表面に、支持
体の平均細孔径より小さい平均細孔径を有するセラミッ
ク多孔質膜が形成されたセラミック分離膜が知られてい
る。2. Description of the Related Art There is known a ceramic separation membrane in which a ceramic porous membrane having an average pore diameter smaller than the average pore diameter of the support is formed on the surface of a ceramic porous support.
【０００３】[0003]
【発明が解決しようとする課題】セラミック多孔質支持
体に比べて、セラミック多孔質膜を構成する無機質材料
の粒径は遙に小さく、逆に比表面積は遙に大きい。この
ため、分離膜使用時のセラミック多孔質膜からの無機質
材料の濾過液への溶出による濾過液の汚染、及び分離膜
再生工程でのセラミック多孔質膜からの無機質材料の
酸、アルカリ洗浄液への溶出による分離膜の劣化が問題
となる。本発明は上記の問題点に鑑みてなされたもので
あり、１又は複数層のセラミック多孔質支持体の表面
に、支持体の平均細孔径より小さい平均細孔径を有する
セラミック多孔質膜が形成されたセラミック分離膜であ
って、耐食性に優れたセラミック分離膜を提供すること
を目的とする。The particle size of the inorganic material constituting the ceramic porous membrane is much smaller than that of the ceramic porous support, and the specific surface area is much larger. For this reason, the contamination of the filtrate by the elution of the inorganic material from the ceramic porous membrane into the filtrate when the separation membrane is used, and the conversion of the inorganic material from the ceramic porous membrane to the acid and alkali washing liquid in the separation membrane regeneration step in the separation membrane regeneration step. Degradation of the separation membrane due to elution poses a problem. The present invention has been made in view of the above problems, and a ceramic porous membrane having an average pore diameter smaller than the average pore diameter of a support is formed on the surface of one or more ceramic porous supports. It is an object of the present invention to provide a ceramic separation membrane having excellent corrosion resistance.
【０００４】[0004]
【課題を解決するための手段】上記課題を解決するため
に、本発明においては、１又は複数層のセラミック多孔
質支持体の表面に、支持体の平均細孔径より小さい平均
細孔径を有するセラミック多孔質膜が形成され、セラミ
ック多孔質膜は、97.0重量％以上のジルコニアを含むこ
とを特徴とするセラミック分離膜を提供する。セラミッ
ク多孔質膜の残余の成分は、ジルコニアの熱的安定性を
高めるために一般的に添加されるイットリウム、カルシ
ウム、マグネシウム等の酸化物、ケイ素、アルミニウム
の酸化物等の無機質材料である。本発明の好ましい態様
においては、セラミック多孔質膜の平均細孔径は0.06μ
m 以上0.2 μm 以下である。In order to solve the above-mentioned problems, in the present invention, a ceramic having a mean pore size smaller than the mean pore size of the support is provided on the surface of one or more layers of the ceramic porous support. A porous membrane is formed, wherein the ceramic porous membrane comprises 97.0% by weight or more of zirconia to provide a ceramic separation membrane. The remaining components of the ceramic porous membrane are inorganic materials such as oxides of yttrium, calcium, magnesium and the like, and oxides of silicon and aluminum which are generally added to enhance the thermal stability of zirconia. In a preferred embodiment of the present invention, the average pore size of the ceramic porous membrane is 0.06μ
m or more and 0.2 μm or less.
【０００５】[0005]
【作用】本発明に係るセラミック分離膜においては、セ
ラミック多孔質膜が97.0重量％以上のジルコニアを含む
ので、耐食性に優れている。分離膜の強度、流体透過抵
抗等を勘案すると、セラミック多孔質膜は、セラミック
多孔質膜の平均細孔径よりも大きな平均細孔径を有する
セラミック多孔質支持体の表面に形成されるのが望まし
い。セラミック多孔質支持体は１層でも良く、複数層で
も良い。セラミック分離膜を無菌濾過用フィルターとし
て使用する場合には、セラミック多孔質膜の平均細孔径
は0.2 μm 以下であることが望ましい。他方、分離膜の
透過流束値として実用的な値を確保するためには、セラ
ミック多孔質膜の平均細孔径は0.06μm 以上であること
が望ましい。The ceramic separation membrane according to the present invention is excellent in corrosion resistance because the ceramic porous membrane contains 97.0% by weight or more of zirconia. In consideration of the strength of the separation membrane, fluid permeation resistance, and the like, the ceramic porous membrane is desirably formed on the surface of the ceramic porous support having an average pore diameter larger than the average pore diameter of the ceramic porous membrane. The ceramic porous support may have a single layer or a plurality of layers. When a ceramic separation membrane is used as a filter for sterile filtration, the average pore diameter of the ceramic porous membrane is desirably 0.2 μm or less. On the other hand, in order to secure a practical value as the permeation flux value of the separation membrane, it is desirable that the average pore diameter of the ceramic porous membrane is 0.06 μm or more.
【０００６】[0006]
【実施例】本発明の実施例を以下に説明する。 （供試材）市販のジルコニア粉末を主原料とし、ジルコ
ニアの熱的安定性を高めるために一般的に添加されるイ
ットリアを主な不純物とする、表１に示す組成の原料粉
末を、３mm×５mm×４５mmの直方体にプレス成形し、焼
成温度１０００℃、焼成時間２時間で焼成し、ジルコニ
ア含有量の多い順に、供試材Ｚ０１〜Ｚ０６を得た。セ
ラミック多孔質膜の主原料として一般的に用いられるア
ルミナ及びチタニアを主原料とする、表１に示す組成の
原料粉末を上記と同様に処理して、供試材Ａ０１（主原
料アルミナ）と供試材Ｔ０１、Ｔ０２（主原料チタニ
ア）を得た。走査型電子顕微鏡を用いた観察による供試
材の平均一次粒子径は、表１に示すように、ジルコニア
を主成分とする供試材では、約 0.1μm であり、アルミ
ナを主原料とする供試材と、チタニアを主原料とする供
試材とでは、約 0.2 乃至約0.4 μm であった。Embodiments of the present invention will be described below. (Test Material) A raw material powder having a composition shown in Table 1 containing a commercially available zirconia powder as a main raw material and yttria generally added to improve the thermal stability of zirconia as a main impurity was 3 mm × It was press-molded into a 5 mm × 45 mm rectangular parallelepiped and fired at a firing temperature of 1000 ° C. for a firing time of 2 hours to obtain test materials Z01 to Z06 in descending order of zirconia content. A raw material powder having the composition shown in Table 1 containing alumina and titania, which are generally used as the main raw materials of the ceramic porous membrane, is treated in the same manner as described above to provide a test material A01 (main raw alumina). Test materials T01 and T02 (main raw material titania) were obtained. As shown in Table 1, the average primary particle diameter of the test material observed by using a scanning electron microscope is about 0.1 μm for the test material containing zirconia as the main component, and It was about 0.2 to about 0.4 μm between the test material and the test material mainly composed of titania.
【０００７】[0007]
【表１】 [Table 1]
【０００８】（溶出試験１）ジルコニアの含有量と耐ア
ルカリ性、耐酸性との関係を見るために、供試材Ｚ０
１、Ｚ０３、Ｚ０４、Ｚ０５、Ｚ０６を、65℃の2.0 ％
NaOH 水溶液又は65℃の3.6 ％ HCl水溶液中に所定時間
静置した後、ＩＣＰ発光分析により、不純物をも含む酸
化物の溶出量を測定した。また、ジルコニアを主原料と
する供試材の耐食性とアルミナを主原料とする供試材の
耐食性とを比較すべく、ジルコニアの含有量がほぼ100
％である供試材Ｚ０１に対応して、アルミナの含有量が
ほぼ100％である供試材Ａ０１についても、同様にして
不純物をも含む酸化物の溶出量を計測した。試験結果を
表２に示す。表中、◎は溶出量が0.010 ％未満であるこ
とを示し、○は溶出量が0.010 〜 0.200％であることを
示し、×は溶出量が 0.200％以上であることを示してい
る。表２から、ジルコニアを主原料とする供試材Ｚ０
１、Ｚ０３、Ｚ０４、Ｚ０５、Ｚ０６は全て良好な耐ア
ルカリ性を有していることが分かる。また、ジルコニア
の含有量が97％を超える場合には、良好な耐酸性を有す
るが（Ｚ０１、Ｚ０３）、ジルコニアの含有量が94％未
満の場合には耐酸性が低下する（Ｚ０４、Ｚ０５、Ｚ０
６）ことが分かる。また、ジルコニアを主原料とする供
試材Ｚ０１はアルミナを主原料とする供試材Ａ０１に比
べて、耐アルカリ性、耐酸性共に優れていることが分か
る。(Dissolution test 1) In order to see the relationship between the zirconia content and the alkali resistance and acid resistance, the test material Z0
1, Z03, Z04, Z05, Z06 were converted to 2.0% of 65 ° C.
After leaving still in a NaOH aqueous solution or a 3.6% HCl aqueous solution at 65 ° C. for a predetermined time, the elution amount of oxides including impurities was measured by ICP emission analysis. Further, in order to compare the corrosion resistance of the test material using zirconia as a main raw material and the test material using alumina as a main material, the content of zirconia was almost 100%.
%, The elution amount of oxides including impurities was measured in the same manner as for the test material A01 in which the content of alumina was almost 100%, corresponding to the test material Z01 in which the content was 1.0%. Table 2 shows the test results. In the table, ◎ indicates that the elution amount is less than 0.010%, ○ indicates that the elution amount is 0.010 to 0.200%, and x indicates that the elution amount is 0.200% or more. From Table 2, the test material Z0 containing zirconia as a main raw material was obtained.
It can be seen that 1, Z03, Z04, Z05, and Z06 all have good alkali resistance. When the content of zirconia exceeds 97%, good acid resistance is obtained (Z01, Z03). When the content of zirconia is less than 94%, acid resistance is reduced (Z04, Z05, Z0
6) Further, it can be seen that the test material Z01 using zirconia as a main material is superior in both alkali resistance and acid resistance as compared with the test material A01 using alumina as a main material.
【０００９】[0009]
【表２】 [Table 2]
【００１０】（溶出試験２）ジルコニアを主原料とする
供試材の耐食性と、アルミナを主原料とする供試材の耐
食性と、チタニアを主原料とする供試材の耐食性とを比
較すべく、ジルコニアの含有量が多い供試材Ｚ０１、Ｚ
０２と、アルミナの含有量が多い供試材Ａ０１と、チタ
ニアの含有量が多いＴ０１、Ｔ０２とを、60℃の1.0 ％
NaOH 水溶液、または60℃の1.0 ％ HNO3 水溶液、また
は90℃の熱水中に所定時間静置した後、供試材の重量減
少を計測した。試験結果を表３に示す。表中、◎は重量
減少量が0.010 ％未満であることを示し、○は重量減少
量が0.010 〜 0.200％であることを示し、×は重量減少
量が 0.200％以上であることを示している。表３から、
ジルコニアを主原料とする供試材Ｚ０１、Ｚ０２は、ア
ルミナを主原料とする供試材Ａ０１、チタニアを主原料
とする供試材Ｔ０１、Ｔ０２に比べて耐食性が優れてい
ることが分かる。(Dissolution test 2) To compare the corrosion resistance of a test material using zirconia as a main material, the corrosion resistance of a test material using alumina as a main material, and the corrosion resistance of a test material using titania as a main material. Materials Z01, Z with high zirconia content
02, the test material A01 having a high alumina content, and T01 and T02 having a high titania content were combined with 1.0% of 60 ° C.
After standing in a NaOH aqueous solution, a 1.0% HNO 3 aqueous solution at 60 ° C., or hot water at 90 ° C. for a predetermined time, the weight loss of the test material was measured. Table 3 shows the test results. In the table, ◎ indicates that the weight loss is less than 0.010%, ○ indicates that the weight loss is 0.010 to 0.200%, and X indicates that the weight loss is 0.200% or more. . From Table 3,
It can be seen that the test materials Z01 and Z02 using zirconia as a main raw material have better corrosion resistance than the test materials A01 and T02 using alumina as a main raw material and the test materials T01 and T02 using titania as a main raw material.
【００１１】[0011]
【表３】 [Table 3]
【００１２】（溶出試験３）ジルコニアを主原料とする
供試材の耐食性と、アルミナを主原料とする供試材の耐
食性と、チタニアを主原料とする供試材の耐食性とを比
較すべく、ジルコニアの含有量が多い供試材Ｚ０１、Ｚ
０２と、アルミナの含有量が多い供試材Ａ０１と、チタ
ニアの含有量が多い供試材Ｔ０１、Ｔ０２とを、60℃の
1.0 ％ NaOH水溶液、または60℃の1.0 ％ HNO3 水溶
液、または90℃の熱水中に所定時間静置した後、ＩＣＰ
発光分析により、不純物をも含む酸化物の溶出量を測定
した。試験結果を表４に示す。表中、◎は溶出量が0.01
0 ％未満であることを示し、○は溶出量が0.010 〜 0.2
00％であることを示し、×は溶出量が 0.200％以上であ
ることを示している。表４から、ジルコニアを主原料と
する供試材Ｚ０１、Ｚ０２は、アルミナを主原料とする
供試材Ａ０１、チタニアを主原料とする供試材Ｔ０１、
Ｔ０２に比べて耐食性が優れていることが分かる。(Dissolution test 3) In order to compare the corrosion resistance of a test material using zirconia as a main material, the corrosion resistance of a test material using alumina as a main material, and the corrosion resistance of a test material using titania as a main material. Materials Z01, Z with high zirconia content
02, a test material A01 having a large content of alumina, and test materials T01 and T02 having a large content of titania at 60 ° C.
After leaving it in a 1.0% NaOH aqueous solution, a 1.0% HNO 3 aqueous solution at 60 ° C., or hot water at 90 ° C. for a predetermined time, the ICP
The amount of the oxide including impurities was eluted by emission analysis. Table 4 shows the test results. In the table, ◎ means the elution amount is 0.01
0 means less than 0%.
X indicates that the elution amount is 0.200% or more. From Table 4, the test materials Z01 and Z02 using zirconia as the main raw material are the test materials A01 using alumina as the main material, the test materials T01 using titania as the main material,
It turns out that corrosion resistance is excellent compared with T02.
【００１３】[0013]
【表４】 [Table 4]
【００１４】以上の実施例から、97.0重量％以上のジル
コニアを含むセラミック多孔質膜をセラミック多孔質支
持体の表面に形成することにより、耐食性に優れたセラ
ミック分離膜が得られることが分かる。The above examples show that a ceramic separation membrane having excellent corrosion resistance can be obtained by forming a ceramic porous membrane containing 97.0% by weight or more of zirconia on the surface of a ceramic porous support.
【００１５】[0015]
【効果】以上説明したごとく、本発明に係るセラミック
分離膜は、セラミック多孔質膜が97.0重量％以上のジル
コニアを含むので、耐食性に優れている。セラミック多
孔質膜の平均細孔径を0.06μm 以上0.2 μm 以下とする
ことにより、耐食性にすぐれ、且つ実用的な透過流束値
を有する無菌濾過膜が得られる。As described above, the ceramic separation membrane according to the present invention is excellent in corrosion resistance because the ceramic porous membrane contains 97.0% by weight or more of zirconia. By setting the average pore diameter of the ceramic porous membrane to 0.06 μm or more and 0.2 μm or less, a sterile filtration membrane having excellent corrosion resistance and having a practical permeation flux value can be obtained.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平３−124435（ＪＰ，Ａ) 特開 平３−155776（ＪＰ，Ａ) 特開 平２−126924（ＪＰ，Ａ) 特開 平４−26572（ＪＰ，Ａ) 特開 平４−314851（ＪＰ，Ａ) 特開 平２−111669（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01D 71/02 C04B 35/48 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-124435 (JP, A) JP-A-3-155776 (JP, A) JP-A-2-126924 (JP, A) JP-A-4-124 26572 (JP, A) JP-A-4-314851 (JP, A) JP-A-2-111669 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B01D 71/02 C04B 35 / 48
Claims (2)
の表面に、支持体の平均細孔径より小さい平均細孔径を
有するセラミック多孔質膜が形成され、セラミック多孔
質膜は、97.0重量％以上のジルコニアを含むことを特徴
とするセラミック分離膜。1. A ceramic porous membrane having an average pore diameter smaller than the average pore diameter of a support is formed on the surface of one or more layers of a ceramic porous support, and the ceramic porous membrane is 97.0% by weight or more. A ceramic separation membrane characterized by containing zirconia.
μm 以上0.2 μm 以下であることを特徴とする請求項１
に記載のセラミック分離膜。2. The ceramic porous membrane has an average pore diameter of 0.06.
2. The method according to claim 1, wherein the thickness is not less than μm and not more than 0.2 μm.
3. The ceramic separation membrane according to 1.).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20017893A JP3304526B2 (en) | 1993-07-21 | 1993-07-21 | Ceramic separation membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20017893A JP3304526B2 (en) | 1993-07-21 | 1993-07-21 | Ceramic separation membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0739732A JPH0739732A (en) | 1995-02-10 |
| JP3304526B2 true JP3304526B2 (en) | 2002-07-22 |
Family
ID=16420096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20017893A Expired - Fee Related JP3304526B2 (en) | 1993-07-21 | 1993-07-21 | Ceramic separation membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3304526B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4759664B2 (en) * | 2005-06-17 | 2011-08-31 | 独立行政法人産業技術総合研究所 | Hydrogen separation membrane and hydrogen separation method |
| JP2007254222A (en) * | 2006-03-24 | 2007-10-04 | Ngk Insulators Ltd | Porous ceramic film, ceramic filter and its manufacturing method |
| CN112044285A (en) * | 2020-08-21 | 2020-12-08 | 华南理工大学 | High-flux ceramic filtering membrane and preparation method thereof |
-
1993
- 1993-07-21 JP JP20017893A patent/JP3304526B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0739732A (en) | 1995-02-10 |
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