JPH02141424A - Production of fine particle of zirconium and production of dynamic film utilizing the fine zirconium particle - Google Patents
Production of fine particle of zirconium and production of dynamic film utilizing the fine zirconium particleInfo
- Publication number
- JPH02141424A JPH02141424A JP29357088A JP29357088A JPH02141424A JP H02141424 A JPH02141424 A JP H02141424A JP 29357088 A JP29357088 A JP 29357088A JP 29357088 A JP29357088 A JP 29357088A JP H02141424 A JPH02141424 A JP H02141424A
- Authority
- JP
- Japan
- Prior art keywords
- zirconium
- fine
- particles
- fine particles
- particle size
- 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.)
- Granted
Links
- 239000002245 particle Substances 0.000 title claims abstract description 30
- 239000010419 fine particle Substances 0.000 title claims abstract description 28
- 229910052726 zirconium Inorganic materials 0.000 title claims description 40
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000012528 membrane Substances 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- 150000003754 zirconium Chemical class 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims 2
- 239000000919 ceramic Substances 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- 150000002500 ions Chemical class 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 229910007928 ZrCl2 Inorganic materials 0.000 abstract 1
- -1 ZrCl2 Chemical class 0.000 abstract 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 abstract 1
- 230000003204 osmotic effect Effects 0.000 abstract 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 description 1
- 241000473391 Archosargus rhomboidalis Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 1
- 229940043377 alpha-cyclodextrin Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は小径で且つ粒径が揃ったジルコニウム微粒子の
製法と、当該ジルコニウム微粒子を用いたダイナミック
膜の製法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing zirconium fine particles having a small diameter and uniform particle size, and a method for producing a dynamic membrane using the zirconium fine particles.
０．０１μｍ〜１０μｍの無機コロイド粒子を調製する
方法として、塩溶液に酸又はアルカリを添加する方法が
■広信社「表面」にＶｏｌ、 ２５ Ｎ０． ３（１９
８７）にも記載されるように一般的な手法イナミック膜
の製法として、セラミックス製の多孔質支持体にオキシ
塩化ジルコニウム（ＺｒＯＣｌ２）の溶液を加圧下で還
流せしめ、支持体表面にオキシ塩化ジルコニウムをコロ
イド層として付着させる方法が知られている。As a method for preparing inorganic colloidal particles of 0.01 μm to 10 μm, a method of adding acid or alkali to a salt solution is described in ■ Koshinsha "Surface" Vol. 25 No. 0. 3 (19
As described in 87), as a general method for producing dynamic membranes, a solution of zirconium oxychloride (ZrOCl2) is refluxed under pressure on a porous ceramic support, and zirconium oxychloride is deposited on the surface of the support. A method of depositing it as a colloidal layer is known.
上述した従来法によって得たダイナミック膜のコロイド
層は物理的及び化学的に不安定で、再現性良くダイナミ
ック膜を形成できず、また連続した使用もできない。ダ
イナミック膜としての性能を高めるには、ジルコニウム
微粒子を最密充填に近く堆積させることが必要であり、
このためには、粒子径が小さく且つ揃っていることが条
件となるが、上述した一般的な無機コロイド粒子の鯛製
法では満足な結果が得られない。The colloidal layer of the dynamic film obtained by the above-mentioned conventional method is physically and chemically unstable, making it impossible to form a dynamic film with good reproducibility and also making it impossible to use it continuously. In order to improve the performance as a dynamic membrane, it is necessary to deposit zirconium particles close to close-packed.
For this purpose, the particle diameter must be small and uniform, but the above-mentioned general method for producing sea bream using inorganic colloid particles does not give satisfactory results.
上記課題を解決すべく第１発明にあっては、ジルコニウ
ム濃度が１０−’ｍｏｆｆｉ／ ｊ！〜１０−”ｍｏｊ
２／ １である希薄なジルコニウム塩水溶液を調製し、
この水溶液にジルコニウムに対する濃度比が１：０．５
〜１ ： １００となるように硫酸イオンを添加し、こ
の後上記の水溶液を所定の条件で熟成（エージング）す
るぼことによりジルコニウム微粒子を沈澱せしめるよう
にし、また第２発明にあっては第１発明によって得たジ
ルコニウム微粒子を分散したコロイド溶液を用いて加圧
下で多孔質支持体を通して還流させ、該多孔質支持体表
面に酸化ジルコニウム微粒子の層を形成するようにした
。In order to solve the above problem, in the first invention, the zirconium concentration is 10-'moffi/j! ~10-”moj
Prepare a dilute zirconium salt aqueous solution with a ratio of 2/1,
The concentration ratio of zirconium to this aqueous solution is 1:0.5.
1:100, and then the above aqueous solution is aged under predetermined conditions to precipitate zirconium fine particles. A colloidal solution in which fine zirconium particles obtained according to the invention were dispersed was refluxed under pressure through a porous support to form a layer of fine zirconium oxide particles on the surface of the porous support.
本発明においてジルコニウム塩としては水溶性のもので
あれば任意に使用でき、たとえば塩化物オキシ塩化物な
どがある。ジルコニウム塩水溶液中のジルコニウム濃度
が１０−４ｍｏｌ ／ Ｉ！未満であると、ジルコニウ
ム微粒子が形成されず、一方１０−２ｍｏｌ／ｌを越え
る濃度で用いると、ジルコニウム微粒子が形成されない
か、もしくは形成されたとしても該微粒子の粒径分布が
著しく大きいものとなり好ましくない。好ましくはジル
コニウム濃度５ Ｘ １０−３ｍｏＩ！、／Ｉ！、〜Ｉ
Ｘ １０−”ｍｏｆｆｉ／ｆｆの範囲で用いる。In the present invention, any water-soluble zirconium salt can be used, such as chloride and oxychloride. The zirconium concentration in the zirconium salt aqueous solution is 10-4 mol/I! If the concentration is less than 10-2 mol/l, zirconium fine particles will not be formed, and if it is used at a concentration exceeding 10-2 mol/l, zirconium fine particles will not be formed, or even if they are formed, the particle size distribution of the fine particles will be significantly large, which is preferable. do not have. Preferably the zirconium concentration is 5 x 10-3 moI! ,/I! ,~I
It is used in the range of X 10-”moffi/ff.
次に、硫酸イオンを与える化合物としてはＨｚＳＯｎ。Next, HzSOn is a compound that provides sulfate ions.
（ＮＨ４）ＪＬ ＳＯＳ、、 ＫｇＳＯ４，ＮａｚＳＯ
ａなどがあるが、これらのうちＨ２ＳＯ４を用いると、
ジルコニウム微粒子の粒径をコントロールすることがで
きる。(NH4) JL SOS, KgSO4, NazSO
Among these, when H2SO4 is used,
The particle size of zirconium fine particles can be controlled.
ジルコニウム硫酸イオンとの濃度比は上記した範囲内と
すべきである。この範囲を外れると、目的とするジルコ
ニウム粒子の形成がなされない。The concentration ratio with zirconium sulfate ion should be within the above range. Outside this range, the desired zirconium particles will not be formed.
好ましくは濃度比が１：０．５〜１：１０の範囲で用い
る。なお、該粒子形成を行うための熟成は温度２０〜７
５°Ｃにて１時間以上、通常は５０°Ｃで１〜２時間行
えばよい。Preferably, the concentration ratio is in the range of 1:0.5 to 1:10. In addition, the aging for forming the particles is carried out at a temperature of 20 to 7
It may be carried out at 5°C for 1 hour or more, usually at 50°C for 1 to 2 hours.
上記方法により得られるジルコニウム微粒子は粒径が０
．３ｔｔｍ （３００ｎｍ）以下、通常は０．１μｍ（
１００ｎｍ）以下であり、しかも粒径が揃っている。The zirconium fine particles obtained by the above method have a particle size of 0.
．． 3ttm (300nm) or less, usually 0.1μm (
100 nm) or less, and the particle sizes are uniform.
次に、ジルコニウム微粒子を用いてダイナミック膜を形
成する方法について説明する。Next, a method for forming a dynamic film using zirconium fine particles will be explained.
第１図はダイナミック膜形成装置の概略図であり、膜形
成装置はポンプ１．タンク２．流量計３゜圧力計４．多
孔質支持体５およびこれらを接続する配管６によって構
成されている。FIG. 1 is a schematic diagram of a dynamic film forming apparatus, and the film forming apparatus includes a pump 1. Tank 2. Flow meter 3゜Pressure gauge 4. It is composed of a porous support 5 and piping 6 connecting these.
多孔質支持体５はＡ ｌ ｚＯｓ質のセラミックス製筒
体とし、その寸法は例えば外径（Ｄ＋）１０ｍｍ、内径
（Ｄｚ）８ｍｍ、長さ（Ｌ）５５０ｍｍで、孔径が約０
．５μｍの均質なものを使用する。この多孔質支持体の
表面にダイナミック膜を形成するには、タンク２内に前
記方法によって得たジルコニウム微粒子を分散させたコ
ロイド溶液を入れ、ポンプ１により加圧下に多孔質支持
体５を通して該溶液を還流させ、酸化ジルコニウムを多
孔質支持体の表面に層状に沈着せしめる。なお、コロイ
ド溶液を還流させる際の条件としては、圧力０．０５〜
２．ＯＭＰａ 、好ましくは０．１〜１．０ ＭＰａ
、温度０〜９０°Ｃ１好ましくは１５〜３５°Ｃ１速度
０．１〜１０ ｍ／ｓｅｃ、、好ましくは１〜３ ｍ／
ｓｅｃ、 が適当である。The porous support 5 is a cylindrical body made of AlzOs ceramics, and its dimensions are, for example, an outer diameter (D+) of 10 mm, an inner diameter (Dz) of 8 mm, a length (L) of 550 mm, and a pore diameter of about 0.
．． Use a homogeneous material with a diameter of 5 μm. To form a dynamic membrane on the surface of this porous support, a colloidal solution in which the zirconium fine particles obtained by the above method are dispersed is placed in a tank 2, and the solution is passed through the porous support 5 under pressure using a pump 1. is refluxed to deposit zirconium oxide in a layer on the surface of the porous support. Note that the conditions for refluxing the colloidal solution include a pressure of 0.05~
2. OMPa, preferably 0.1-1.0 MPa
, temperature 0-90°C, preferably 15-35°C, speed 0.1-10 m/sec, preferably 1-3 m/sec.
sec, is appropriate.
〔実施例〕 次に、本発明を実施例により詳しく説明する。〔Example〕 Next, the present invention will be explained in detail with reference to examples.
実施例１
ジルコニウム濃度が所定量のオキシ塩化ジルコニウム（
ＺｒＯＣＩ！、２）水溶液に対してジルコニウムと硫酸
イオン（ＳＱＬ−）の濃度比が１：０．１〜１：１００
の範囲となるようにＨ２ＳＯ４（特級試薬以上）の所定
量を添加し、５０″Ｃで２時間エージングを行った後、
ジルコニウム微粒子の形成の有無を調べた。結果を第２
図に示す。また、第３図乃至第５図は１１□Ｓ０４を添
加した場合のジルコニウム微粒子の構造を示す電子顕微
鏡写真（２０，０００倍）であり、第３図はジルコニウ
ム濃度を１０−３ｍｏｆｆ／ｌ、濃度比を１：０．７と
し、第４図はジルコニウム濃度を１０−３ｍｏｌ／１、
濃度比を１：１とし、第５図はジルコニウム濃度を１０
−３ｍｏｊ２ ／ ｊ２、濃度比を１＝５とした場合を
示す。これらの図から明らかなよう、１１゜ＳＯ４を用
いた場合には、ジルコニウムと硫酸イオンとの濃度比に
比例して形成されるジルコニウム微粒子の粒径が約３０
ｎｍ〜０．２μｍの範囲で変化することが分かった。Example 1 Zirconium oxychloride with a predetermined zirconium concentration (
ZrOCI! , 2) The concentration ratio of zirconium and sulfate ions (SQL-) to the aqueous solution is 1:0.1 to 1:100.
After adding a predetermined amount of H2SO4 (special grade reagent or higher) to the range of , and aging at 50"C for 2 hours,
The presence or absence of zirconium fine particle formation was investigated. Second result
As shown in the figure. In addition, Fig. 3 to Fig. 5 are electron micrographs (20,000 times magnification) showing the structure of zirconium fine particles when 11□S04 is added. The ratio is 1:0.7, and in Figure 4, the zirconium concentration is 10-3 mol/1,
The concentration ratio is 1:1, and the zirconium concentration in Figure 5 is 10.
-3moj2/j2, the case where the concentration ratio is 1=5 is shown. As is clear from these figures, when 11° SO4 is used, the particle size of the zirconium fine particles formed is approximately 30° in proportion to the concentration ratio of zirconium and sulfate ions.
It was found that it varies in the range of nm to 0.2 μm.
実施例２
実施例１においてＨｇＳＯ４の代りに（ＮＨ４１１ｚ
Ｓ０４を用いたこと以外は実施例１と同様に行った。結
果を第６図に示す。なお、形成されたジルコニウム微粒
子の粒径は、第７図に示した如く、ジルコニウム濃度と
硫酸イオン濃度の比に関係なく０．１〜０．２μｍであ
った。Example 2 In Example 1, instead of HgSO4 (NH411z
The same procedure as in Example 1 was carried out except that S04 was used. The results are shown in Figure 6. As shown in FIG. 7, the particle size of the formed zirconium fine particles was 0.1 to 0.2 μm regardless of the ratio of zirconium concentration to sulfate ion concentration.
実施例３
実施例１においてＨ２ＳＯ４の代りにに、ＳＯ４を用い
たこと以外は実施例１と同様に行った。結果を第８図に
示す。なお、形成されたジルコニウム微粒子の粒径は実
施例２の場合と同じであった。Example 3 The same procedure as in Example 1 was conducted except that SO4 was used instead of H2SO4. The results are shown in FIG. Note that the particle size of the formed zirconium fine particles was the same as in Example 2.
実施例４
実施例１において１１２５Ｏ４の代りにＮａｚＳＯ，を
用いたこと以外は実施例１と同様に行った。結果を第９
図に示す。なお、形成されたジルコニウム微粒子の粒径
は実施例２の場合と同じであった。Example 4 The same procedure as in Example 1 was conducted except that NazSO was used instead of 1125O4. 9th result
As shown in the figure. Note that the particle size of the formed zirconium fine particles was the same as in Example 2.
実施例５
第１図に示したダイナミック膜形成装置のタンク２に実
施例１で得たジルコニウム微粒子（粒径３０〜５０ｍｍ
）を分散させたコロイド溶液を入れた。また、多孔質支
持体としてり、 ： １０ｍｍ、 Ｄ、 ：溶液を該多
孔質支持体を通して還流せしめた。Example 5 The zirconium fine particles obtained in Example 1 (particle size 30 to 50 mm) were placed in tank 2 of the dynamic film forming apparatus shown in FIG.
) was added to the colloid solution. In addition, a porous support was used, and the solution was refluxed through the porous support.
圧力 ： ０．５ ＭＰａ 温度 ： ２５°Ｃ 速度 ： ｌ ｍ／ｓｅｃ。Pressure: 0.5 MPa Temperature: 25°C Speed: lm/sec.
その結果、約２時間で定常透過流速となり、第１０図に
示した如く、厚さ２０μｍの酸化ジルコニウムの膜７が
支持体５の表面に均一に形成された。As a result, the permeation flow rate reached a steady state in about 2 hours, and a 20 μm thick zirconium oxide film 7 was uniformly formed on the surface of the support 5, as shown in FIG.
このダイナミック膜の阻止性能の実験結果を第１１図に
示す。図から明らかなように、この膜の９０％阻止の点
が分子量５〜６万であった。なお、実験にはα−サイク
ロデキストリンおよび各種デキストランを使用した。The experimental results of the blocking performance of this dynamic membrane are shown in FIG. As is clear from the figure, the point at which this membrane achieved 90% inhibition was at a molecular weight of 50,000 to 60,000. Note that α-cyclodextrin and various dextrans were used in the experiment.
実施例６
実施例５において、ジルコニウム微粒子として粒径０．
２〜０．３μｍのものを使用したこと以外は実施例５と
同様に行った。その結果、厚さ２００μｍの膜が支持体
表面に均一に形成された。Example 6 In Example 5, the zirconium fine particles had a particle size of 0.
The same procedure as in Example 5 was carried out except that one having a diameter of 2 to 0.3 μm was used. As a result, a film with a thickness of 200 μm was uniformly formed on the surface of the support.
このダイナミック膜の阻止性能を実施例５と同様にして
測定したところ、第１１図に示した如く、９０％阻止の
点が分子量２００万であることが分った。The blocking performance of this dynamic membrane was measured in the same manner as in Example 5, and as shown in FIG. 11, it was found that the point of 90% blocking was at a molecular weight of 2 million.
本発明によれば、極めて小径で、且つ粒径が揃ったジル
コニウム微粒子を得ることができ、特に硫酸イオンを添
加するためにＨ２ＳＯ４を添加するようにすれば、粒径
をコントロールすることもできる。そして、上記によっ
て得た微粒子を多孔質支持体表面に付着させることで、
物理的にも化学的にも安定したダイナミック膜を形成す
ることができる。According to the present invention, zirconium fine particles having an extremely small diameter and uniform particle size can be obtained, and the particle size can also be controlled, especially if H2SO4 is added to add sulfate ions. Then, by attaching the fine particles obtained above to the surface of the porous support,
A physically and chemically stable dynamic film can be formed.
第１図は膜形成装置の概略図、第２図、第６図。
第８図および第９図は縦軸にＺｒ濃度を横軸にＺｒとＳ
Ｏエニー濃度比をとったグラフ、第３図乃至第５図およ
び第７図はジルコニウム微粒子構造を示す顕微鏡写真、
第１０図は多孔質支持体の拡大断面図、第１１図はダイ
ナミック膜の阻止性能を示すグラ（７／ｌ０ＬＬ＋ ）
」Ｚ
× ００
Ｘ Ｏ■
（γ／１０ＩＪＪ）」ＺFIG. 1 is a schematic diagram of a film forming apparatus, FIG. 2, and FIG. 6. Figures 8 and 9 show Zr concentration on the vertical axis and Zr and S on the horizontal axis.
Graphs showing the O-any concentration ratio, Figures 3 to 5, and 7 are micrographs showing the structure of zirconium fine particles;
Figure 10 is an enlarged cross-sectional view of the porous support, and Figure 11 is a graph showing the blocking performance of the dynamic membrane (7/l0LL+).
"Z × 00 X O■ (γ/10IJJ)"Z
Claims (2)
／ｌ〜１０＾−＾２ｍｏｌ／ｌのジルコニウム塩水溶液
を調製し、この水溶液にジルコニウムに対する濃度比が
１：０．５〜１：１００の範囲で硫酸イオン（ＳＯ＿４
＾２＾−）を添加し、次いで上記水溶液を熟成してジル
コニウム微粒子を沈澱させるようにしたジルコニウム微
粒子の製法。(1) Zirconium (Zr) concentration is 10^-^4 mol
/l ~ 10^-^2 mol/l of zirconium salt aqueous solution is prepared, and sulfate ion (SO_4
A method for producing zirconium fine particles by adding ^2^-) and then aging the above aqueous solution to precipitate zirconium fine particles.
／ｌ〜１０＾−＾２ｍｏｌ／ｌのジルコニウム塩水溶液
を調製し、この水溶液にジルコニウムに対する濃度比が
１：０．５〜１：１００の範囲で硫酸イオン（ＳＯ＿４
＾２＾−）を添加し、次いで上記水溶液を熟成してジル
コニウム微粒子を形成せしめ、このジルコニウム微粒子
を分散させたコロイド溶液を加圧下で多孔質支持体を通
して還流させ、該多孔質支持体表面に酸化ジルコニウム
微粒子を層状に沈着せしめるようにしたことを特徴とす
るジルコニウム微粒子を用いたダイナミック膜の製法。(2) Zirconium (Zr) concentration is 10^-^4 mol
/l ~ 10^-^2 mol/l of zirconium salt aqueous solution is prepared, and sulfate ion (SO_4
^2^-) is added, and then the above aqueous solution is aged to form zirconium fine particles, and the colloidal solution in which the zirconium fine particles are dispersed is refluxed under pressure through a porous support, so that it is coated on the surface of the porous support. A method for producing a dynamic membrane using fine zirconium particles, characterized in that fine particles of zirconium oxide are deposited in a layered manner.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29357088A JPH02141424A (en) | 1988-11-22 | 1988-11-22 | Production of fine particle of zirconium and production of dynamic film utilizing the fine zirconium particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29357088A JPH02141424A (en) | 1988-11-22 | 1988-11-22 | Production of fine particle of zirconium and production of dynamic film utilizing the fine zirconium particle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02141424A true JPH02141424A (en) | 1990-05-30 |
| JPH0476334B2 JPH0476334B2 (en) | 1992-12-03 |
Family
ID=17796451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29357088A Granted JPH02141424A (en) | 1988-11-22 | 1988-11-22 | Production of fine particle of zirconium and production of dynamic film utilizing the fine zirconium particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02141424A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5681348A (en) * | 1994-03-31 | 1997-10-28 | Olympus Optical Co., Ltd. | Endoscope-specific therapeutic instrument |
| JP2006199560A (en) * | 2005-01-24 | 2006-08-03 | Tosoh Corp | New structure containing sulfated zirconia and its manufacturing method |
-
1988
- 1988-11-22 JP JP29357088A patent/JPH02141424A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5681348A (en) * | 1994-03-31 | 1997-10-28 | Olympus Optical Co., Ltd. | Endoscope-specific therapeutic instrument |
| JP2006199560A (en) * | 2005-01-24 | 2006-08-03 | Tosoh Corp | New structure containing sulfated zirconia and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0476334B2 (en) | 1992-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5342431A (en) | Metal oxide membranes for gas separation | |
| US5269926A (en) | Supported microporous ceramic membranes | |
| Marcinkowsky et al. | Hyperfiltration studies. IV. Salt rejection by dynamically formed hydrous oxide membranes1 | |
| US5342521A (en) | Reverse osmosis or nanofiltration membrane and its production process | |
| EP0692303B1 (en) | Process for the production of an inorganic porous composite membrane | |
| CA1264994A (en) | Process for the production of porous, permeable mineral membranes | |
| JP3625682B2 (en) | Method for producing filter using ceramic porous membrane as separation membrane | |
| JPS61192306A (en) | Permeable porous inorganic membrane | |
| Guo et al. | Modifications of polyethersulfone membrane by doping sulfated-TiO 2 nanoparticles for improving anti-fouling property in wastewater treatment | |
| JPH02140239A (en) | Porous polytetrafluoroethylene membrane and production thereof | |
| US6613384B1 (en) | Method for manufacturing a membrane | |
| EP1024886A1 (en) | A manufacturing method of composite membrane having hydrophilic coating layer on hydrophobic support membrane | |
| JP2520214B2 (en) | Microporous alumina ceramic membrane | |
| JPH04227825A (en) | Porous inorganic composite semi-permeable membrane and manufacture thereof | |
| CN103041716A (en) | Preparation method of silicon dioxide film with quasi-symmetric film structure | |
| JPH02141424A (en) | Production of fine particle of zirconium and production of dynamic film utilizing the fine zirconium particle | |
| Yazawa et al. | Preparation of water and alkali durable porous glass membrane coated on porous alumina tubing by sol-gel method | |
| JP2000288325A (en) | Production of filter having ceramic porous membrane as separation membrane | |
| JPH0321330A (en) | Preparation of upper layer of two dimensional membrane | |
| JP3108709B2 (en) | Method for producing inorganic ultra-thin film with controlled thickness | |
| US4880544A (en) | Crystal growth process for preparing inorganic dynamic membranes | |
| JPH0457373B2 (en) | ||
| JPH0571548B2 (en) | ||
| JPH0582249B2 (en) | ||
| JPH0243928A (en) | Inorganic porous membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 19930608 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |