JPH0476334B2 - - Google Patents
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- Publication number
- JPH0476334B2 JPH0476334B2 JP29357088A JP29357088A JPH0476334B2 JP H0476334 B2 JPH0476334 B2 JP H0476334B2 JP 29357088 A JP29357088 A JP 29357088A JP 29357088 A JP29357088 A JP 29357088A JP H0476334 B2 JPH0476334 B2 JP H0476334B2
- Authority
- JP
- Japan
- Prior art keywords
- zirconium
- fine particles
- aqueous solution
- concentration
- mol
- 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
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 7
- 229910052726 zirconium Inorganic materials 0.000 claims 7
- 239000007864 aqueous solution Substances 0.000 claims 6
- 239000010419 fine particle Substances 0.000 claims 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000002245 particle Substances 0.000 claims 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims 2
- 150000003754 zirconium Chemical class 0.000 claims 2
- 230000032683 aging Effects 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 238000010992 reflux Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
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つたジルコニウム
微粒子の製法と、当該ジルコニウム微粒子を用い
たダイナミツ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(株)広信社「表面」にVol.25No.３（1987）に
も記載されるように一般的な手法として知られて
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 a general method as described in Koshinsha Co., Ltd. "Surface" Vol. 25 No. 3 (1987). It is known as a method.
一方、限外濾過膜或いは逆浸透膜として使用す
るダイナミツク膜の製法として、セラミツクス製
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。 On the other hand, as a method for producing a dynamic membrane used as an ultrafiltration membrane or a reverse osmosis membrane, a solution of zirconium oxychloride (ZrOCl 2 ) is refluxed under pressure on a porous support made of ceramics, and zirconium oxychloride is coated on the surface of the support. A method of depositing it as a colloid layer is known.
上述した従来法によつて得たダイナミツク膜の
コロイド層は物理的及び化学的に不安定で、再現
性良くダイナミツク膜を形成できず、また連続し
た使用もできない。ダイナミツク膜としての性能
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つ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調
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, and it is not possible to form a dynamic film with good reproducibility, nor can it be used continuously. In order to improve the performance of a dynamic film, it is necessary to deposit zirconium fine particles in a close-packed state, and this requires that the particle diameters be small and uniform. However, the methods for preparing inorganic colloid particles do not give satisfactory results.
上記課題を解決すべく第１発明にあつては、ジ
ルコニウム濃度が10-4mol／〜10-2mol／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発明にあつては第１発
明によつ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 problems, in the first invention, a dilute zirconium salt aqueous solution having a zirconium concentration of 10 -4 mol/~10 -2 mol/ is prepared, and this aqueous solution has a concentration ratio of 1:0.5 to zirconium.
Sulfate ions are added so that the ratio is ~1:100, and then the above aqueous solution is aged under predetermined conditions to precipitate zirconium fine particles. A colloidal solution in which the zirconium fine particles obtained by the method were dispersed was refluxed under pressure through a porous support to form a layer of zirconium oxide fine 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／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／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
のとなり好ましくはない。好ましくはジルコニウ
ム濃度５×10-3mol／〜１×10-2mol／の範
囲で用いる。 In the present invention, any water-soluble zirconium salt can be used, such as chlorides and oxychlorides. When the zirconium concentration in the zirconium salt aqueous solution is less than 10 -4 mol/, zirconium fine particles are not formed;
If the concentration exceeds 10 -2 mol/, zirconium fine particles will not be formed, or even if they are formed, the particle size distribution of the fine particles will be extremely large, which is not preferred. Preferably, the zirconium concentration is used within the range of 5×10 −3 mol/ to 1×10 −2 mol/.
次に、硫酸イオンを与える化合物としては
H2SO4，（NH4）2SO4，K2SO4，Na2SO4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。 Next, as a compound that gives sulfate ions,
Examples include H 2 SO 4 , (NH 4 ) 2 SO 4 , K 2 SO 4 , Na 2 SO 4 , and among these, when H 2 SO 4 is used, the particle size of the 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。
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
20〜75℃にて１時間以上、通常は50℃で１〜２時
間行えばよい。 The concentration ratio with zirconium sulfate ion should be within the above range. Outside this range, the desired zirconium particles will not be formed.
Preferably, the concentration ratio is in the range of 1:0.5 to 1:10. Note that the aging for forming the particles is performed at a temperature
It may be carried out at 20 to 75°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0.3μｍ（300nm）以下、通常は0.1μｍ
（100nm）以下であり、しかも粒径が揃つている。 The zirconium fine particles obtained by the above method have a particle size of 0.3 μm (300 nm) or less, usually 0.1 μm.
(100nm) or less, and the particle size is uniform.
次に、ジルコニウム微粒子を用いてダイナミツ
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図はダイナミツ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によつて構成されている。 FIG. 1 is a schematic diagram of a dynamic film forming apparatus, which is composed of a pump 1, a tank 2, a flow meter 3, a pressure gauge 4, a porous support 5, and piping 6 connecting these. There is.
多孔質支持体５はAl2O3質のセラミツク製筒体
とし、その寸法は例えば外径（D1）10mm、内径
（D2）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
ダイナミツク膜を形成するには、タンク２内に前
記方法によつ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0.05〜2.0MPa、好ましく
は0.1〜1.0MPa、温度０〜90℃、好ましくは15〜
35℃、速度0.1〜10m／sec.，好ましくは１〜
3msec.が適当である。 The porous support 5 is a cylinder made of Al 2 O 3 ceramic, and its dimensions are, for example, an outer diameter (D 1 ) of 10 mm, an inner diameter (D 2 ) of 8 mm, a length (L) of 550 mm, and a pore diameter of about 0.5 μm. Use a homogeneous one. To form a dynamic film on the surface of this porous support, a colloidal solution in which fine zirconium particles obtained by the above method are dispersed is placed in a tank 2, and is passed through the porous support 5 under pressure using a pump 1. The solution is refluxed to deposit zirconium oxide in a layer on the surface of the porous support. The conditions for refluxing the colloidal solution include a pressure of 0.05 to 2.0 MPa, preferably 0.1 to 1.0 MPa, and a temperature of 0 to 90°C, preferably 15 to 1.0 MPa.
35℃, speed 0.1~10m/sec., preferably 1~
3msec. is appropriate.
次に、本発明を実施例により詳しく説明する。 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（ZrOCl2）水溶液に対してジルコニウム
と硫酸イオン（SO2 4 -）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℃で２時間エージングを行
つた後、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H2SO4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（20000倍）であ
り、第３図はジルコニウム濃度を10-3mol／、
濃度比を１：0.7とし、第４図はジルコニウム濃
度を10-3mol／、濃度比を１：１とし、第５図
はジルコニウム濃度を10-3mol／、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、H2SO4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30nm〜0.2μｍの
範囲で変化することが分かつた。Example 1 The concentration ratio of zirconium and sulfate ions (SO 2 4 - ) to an aqueous solution of zirconium oxychloride (ZrOCl 2 ) having a predetermined amount of zirconium is 1:0.1 to 1:
H 2 SO 4 (special grade reagent or higher) to be in the range of 100
After adding a predetermined amount of zirconium and aging at 50° C. for 2 hours, the presence or absence of formation of zirconium fine particles was examined. The results are shown in Figure 2. Also, Figures 3 to 5
The figure is an electron micrograph (20,000x) showing the structure of zirconium fine particles when H 2 SO 4 is added. Figure 3 shows the zirconium concentration at 10 -3 mol/,
The concentration ratio is 1:0.7, and in Figure 4, the zirconium concentration is 10 -3 mol/, and the concentration ratio is 1:1, and in Figure 5, the zirconium concentration is 10 -3 mol/, and the concentration ratio is 1:5. Indicate the case. As is clear from these figures, when H 2 SO 4 is used, the particle size of the zirconium fine particles formed changes in the range of approximately 30 nm to 0.2 μm in proportion to the concentration ratio of zirconium and sulfate ions. I found out.
実施例 ２
実施例１においてH2SO4の代りに（NH4）2SO4
を用いたこと以外は実施例１と同様に行つた。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であつた。Example 2 In Example 1, instead of H 2 SO 4 (NH 4 ) 2 SO 4
The same procedure as in Example 1 was carried out except that . The results are shown in Figure 6. As shown in Figure 7, the particle size of the formed zirconium particles is 0.1 regardless of the ratio of zirconium concentration to sulfate ion concentration.
It was ~0.2 μm.
実施例 ３
実施例１においてH2SO4の代りにK2SO4を用い
たこと以外は実施例１と同様に行つた。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の場合と同じであつた。Example 3 The same procedure as in Example 1 was carried out except that K 2 SO 4 was used instead of H 2 SO 4 in Example 1. 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H2SO4の代りにNa2SO4を用
いたこと以外は実施例１と同様に行つた。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の場合と同じであつた。Example 4 The same procedure as in Example 1 was conducted except that Na 2 SO 4 was used instead of H 2 SO 4 in Example 1. The results are shown in Figure 9. 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ツ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D1：10mm，D2：８mm，
Ｌ：550mmのAl2O3質セラミツクス製筒体を用い、
ポンプ１により下記の条件でコロイド溶液を該多
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
A colloid solution containing 30-50 mm) was added.
In addition, as a porous support, D 1 : 10 mm, D 2 : 8 mm,
L: Using a 550mm Al 2 O 3 quality ceramic cylinder,
The colloidal solution was refluxed through the porous support using pump 1 under the following conditions.
圧力：0.5MPa
温度：25℃
速度：１ｍ／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。 Pressure: 0.5 MPa Temperature: 25°C Speed: 1 m/sec. As a result, the permeation flow rate reached a steady state in about 2 hours, and as shown in FIG. uniformly formed.
このダイナミツ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５〜６万であつた。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, this membrane
The point of 90% inhibition was at a molecular weight of 50,000 to 60,000. In addition,
α-Cyclodextrin and various dextran 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と同様に行つた。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 The same procedure as in Example 5 was carried out except that zirconium fine particles having a particle size of 0.2 to 0.3 μm were used. As a result, the thickness is 200μm
A film was uniformly formed on the surface of the support.
このダイナミツ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
つた。 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
つ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、上記によつ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ツク膜を形成することが
できる。
According to the present invention, it is possible to obtain zirconium fine particles having an extremely small diameter and a uniform particle size. In particular, if H 2 SO 4 is added to add sulfate ions, the particle size can be controlled. You can also do it. By adhering the fine particles obtained as described above to the surface of a porous support, a dynamic film that is both physically and chemically stable 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SO2 4 -の濃度比をとつたグラフ、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図はダイナミツク膜の阻止性能を
示すグラフである。
なお、第１図中１はポンプ、２はタンク、５は
多孔質支持体、７は含水酸化ジルコニウムの膜で
ある。
Figure 1 is a schematic diagram of the film forming apparatus, Figure 2, Figure 6.
Figures 8 and 9 are graphs showing the Zr concentration on the vertical axis and the concentration ratio of Zr and SO 2 4 - on the horizontal axis, and Figures 3 to 5 and 7 show the zirconium particle structure. A micrograph, FIG. 10 is an enlarged sectional view of the porous support, and FIG. 11 is a graph showing the blocking performance of the dynamic membrane. In FIG. 1, 1 is a pump, 2 is a tank, 5 is a porous support, and 7 is a hydrous zirconium oxide membrane.
Claims (1)
10-2mol／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（SO2 4 -）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。 ２ ジルコニウム（Zr）濃度が10-4mol／〜
10-2mol／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（SO2 4 -）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
ダイナミツク膜の製法。[Claims] 1. Zirconium (Zr) concentration is 10 -4 mol/~
Prepare a 10 -2 mol/zirconium salt aqueous solution,
The concentration ratio of this aqueous solution to zirconium is 1:
A method for producing zirconium fine particles by adding sulfate ions (SO 2 4 - ) in a ratio of 0.5 to 1:100, and then aging the aqueous solution to precipitate zirconium fine particles. 2 Zirconium (Zr) concentration is 10 -4 mol/~
Prepare a 10 -2 mol/zirconium salt aqueous solution,
The concentration ratio of this aqueous solution to zirconium is 1:
Sulfate ions (SO 2 4 - ) are added in a ratio of 0.5 to 1:100, 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 transferred to a porous support under pressure. A method for producing a dynamic membrane using fine zirconium particles, characterized in that the fine particles of zirconium oxide are deposited in a layer on the surface of the porous support by refluxing the particles through a porous support.
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 JPH02141424A (en) | 1990-05-30 |
| JPH0476334B2 true 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) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3713294B2 (en) * | 1994-03-31 | 2005-11-09 | オリンパス株式会社 | Endoscopic treatment tool |
| JP4815809B2 (en) * | 2005-01-24 | 2011-11-16 | 東ソー株式会社 | Novel structure containing sulfated zirconia and method for producing the same |
-
1988
- 1988-11-22 JP JP29357088A patent/JPH02141424A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02141424A (en) | 1990-05-30 |
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