JPH03188930A - Separation membrane - Google Patents
Separation membraneInfo
- Publication number
- JPH03188930A JPH03188930A JP32892789A JP32892789A JPH03188930A JP H03188930 A JPH03188930 A JP H03188930A JP 32892789 A JP32892789 A JP 32892789A JP 32892789 A JP32892789 A JP 32892789A JP H03188930 A JPH03188930 A JP H03188930A
- Authority
- JP
- Japan
- Prior art keywords
- sodium
- separation membrane
- purify
- oxide
- 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.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 21
- 238000000926 separation method Methods 0.000 title claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims description 31
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 26
- 229910052708 sodium Inorganic materials 0.000 claims description 25
- HGBJDVIOLUMVIS-UHFFFAOYSA-N [Co]=O.[Na] Chemical compound [Co]=O.[Na] HGBJDVIOLUMVIS-UHFFFAOYSA-N 0.000 claims description 10
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 2
- 239000007858 starting material Substances 0.000 abstract 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 102000005393 Sodium-Potassium-Exchanging ATPase Human genes 0.000 description 1
- 108010006431 Sodium-Potassium-Exchanging ATPase Proteins 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 glassy substances Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011533 mixed conductor Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、ナトリウムの分離・精製効率の高い分離膜に
関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a separation membrane with high efficiency in separating and purifying sodium.
［従来の技術とその課題］
ナトリウム蒸気を分離・精製する場合、従来技術では、
その分離膜としてβ−ＡＩ２２０３（ベタ・アルミナ）
等のイオン伝導体を用いていた。[Conventional technology and its issues] When separating and refining sodium vapor, conventional technology requires
β-AI2203 (solid alumina) is used as the separation membrane.
They used ionic conductors such as
しかし、これらのイオン伝導体では電子伝導性が乏しい
ため、系外に電子伝導用回路を設け、非分離側の一次側
と、分離精製された減圧側に面した二次側を導通する必
要があった。ナトリウムの沸点は８７７℃であり、室温
での蒸気圧は低いため、ナトリウムを蒸気にして分離精
製する場合は、温度を少なくとも２５０℃以上にしなけ
ればならない。そういう高温度で、電子伝導性が低い分
離膜両面を電子伝導体で導通するには大変な技術を要し
、またコストも高いため、あまり活用されていない。However, these ionic conductors have poor electron conductivity, so it is necessary to provide an electron conduction circuit outside the system to establish continuity between the primary side on the non-separated side and the secondary side facing the separated and purified reduced pressure side. there were. The boiling point of sodium is 877°C and its vapor pressure at room temperature is low, so if sodium is to be separated and purified as vapor, the temperature must be at least 250°C or higher. At such high temperatures, creating electrical conduction between both sides of a separation membrane with low electron conductivity using an electron conductor requires a very difficult technology and is also expensive, so it is not widely used.
［課題を解決するための手段］
本発明者は、ナトリウムイオン伝導性が高く、かつ電子
伝導性が高い物質を種々探索したところ、ナトリウム・
コバルト酸化物が適することをつきとめ、本発明を完成
するに至った。[Means for Solving the Problems] The present inventor searched for various substances with high sodium ion conductivity and high electron conductivity, and found that sodium
They found that cobalt oxide was suitable and completed the present invention.
ナトリウム・コバルト酸化物はナトリウムとコバルトの
原子比により結晶構造が異なり、α型、β型、γ型等が
あることが知られている。本発明に於ては、いかなる結
晶構造のナトリウム・コバルト酸化物を用いても良い。It is known that the crystal structure of sodium-cobalt oxide differs depending on the atomic ratio of sodium and cobalt, and there are α-type, β-type, γ-type, etc. In the present invention, sodium cobalt oxide having any crystal structure may be used.
しかし、イオン伝導性が高く、電子伝導性が高く、かつ
、温度変化に対しても強度があるのはγ型ナトリウム・
コバルト酸化物である。However, γ-type sodium has high ionic conductivity, high electronic conductivity, and is strong against temperature changes.
It is cobalt oxide.
よって、特に好ましい結晶形態としてγ型を推奨できる
。その中でもナトリウムとコバルトの原子比は０．６：
１〜１：１の間がよい。Therefore, the γ type can be recommended as a particularly preferable crystal form. Among them, the atomic ratio of sodium and cobalt is 0.6:
A ratio between 1 and 1:1 is preferable.
ナトリウム・コバルト酸化物を分離膜にするには膜状に
固める必要があるが、その方法としてはナトリウム・コ
バルト酸化物を合成する際に、膜状に原料を適当な形に
成型してから焼結することにより分離膜を作ることもで
きるし、また焼結体を膜状に切断して分離膜にすること
もできるし、合成したナトリウム・コバルト酸化物を再
焼成することで、分離膜を作ることもできる。また、他
の無機質バインダーや金属、例えば、ガラス状物質や三
酸化ビスマスや鉛またはカドミウム等をナトリウム・コ
バルト酸化物に添加し成型して分離膜を作ることもでき
る。In order to make sodium/cobalt oxide into a separation membrane, it is necessary to solidify it into a membrane, but the method for this is to mold raw materials into an appropriate membrane shape and then sinter it when synthesizing sodium/cobalt oxide. Separation membranes can be made by sintering, or separation membranes can be made by cutting the sintered body into membranes, and separation membranes can be made by re-firing the synthesized sodium cobalt oxide. You can also make one. Furthermore, a separation membrane can also be made by adding other inorganic binders or metals, such as glassy substances, bismuth trioxide, lead, or cadmium, to the sodium cobalt oxide and molding the mixture.
また有機質バインダーを添加し、求める形状に成型して
から焼成処理して分離膜を作ることもできる。Alternatively, a separation membrane can be made by adding an organic binder, molding it into a desired shape, and then firing it.
ナトリウム蒸気の精製分離の原理は、ナトリウムイオン
及び電子混合伝導体であるナトリウム・コバルト酸化物
を隔壁として二基を区切り、一方を他の物質を含んだナ
トリウム蒸気にさらし、他方を吸引するとナトリウム濃
淡電池が形成されるが、隔壁内の電子伝導により両極が
短絡される。The principle of purification and separation of sodium vapor is to separate two groups using sodium cobalt oxide, which is a mixed conductor of sodium ions and electrons, as a partition wall, expose one side to sodium vapor containing other substances, and draw out the other substance to determine the concentration of sodium. A cell is formed, but electron conduction within the partitions shorts the poles.
即ち、ナトリウム蒸気室界面（正極）でＮａ→Ｎａ”＋
ｅ−なる式でイオン化したＮａ＋がナトリウム・コバル
ト酸化物に入り、減圧室界面（負極）でＮａ”＋ｅ−→
Ｎａなる反応が起こりナトリウムが減圧室内に放出され
純ナトリウムに精製される。That is, at the sodium vapor chamber interface (positive electrode), Na→Na”+
Ionized Na+ enters the sodium cobalt oxide according to the formula e-, and at the decompression chamber interface (negative electrode) Na"+e-→
A reaction called Na occurs and sodium is released into the vacuum chamber and purified to pure sodium.
一方、上記式中での電子は、ナトリウム・コバルト酸化
物自身に電子伝導性（正孔伝導性）があるため、電極も
外部回路も不要となり、圧力差だけでナトリウムが選択
的に透過するのである。On the other hand, the electrons in the above formula have electron conductivity (hole conductivity) in the sodium cobalt oxide itself, so there is no need for electrodes or external circuits, and sodium selectively permeates just by the pressure difference. be.
［実施例］ 次に本発明の実施例を述べる。[Example] Next, examples of the present invention will be described.
炭酸ナトリウム（Ｎａ２ＣＯ３１と酸化コバルト［ＣＯ
３０４１を等モルずつ秤量し、乳鉢を用いよく粉砕しな
がら混合した。次いで、この混合物を厚み２ｍｍ、直径
２０ｍｍの円板状にプレス成型した。この板を酸素雰囲
気炉に入れ徐々に昇温し、８００℃で１５時間焼成した
後、自然冷却した。でき上がったものは元の形状を全く
維持したままγ型のナトリウム・コバルト酸化物になっ
ていることをＸ線回折により確認した。次いでこの円板
を内径２０ｍｍの高純度アルミナ製円筒管の内側にアル
ミナ製接着剤で固定し、円筒管内を２室に分けた。円筒
管の一方をナトリウム製造用小型溶融塩電解槽の出口付
近に接続し、円筒管の他方を高耐食性吸引ポンプの吸入
口側に接続した。円筒管−次側と二次側の一部を外部加
熱法で６００℃４こ加熱し、吸引ポンプで吸引するとナ
トリウム蒸気はγ型ナトリウム・コバルト酸化物からな
る隔壁を通して、二次側に放出され、さらに二次側室出
口附近をナトリウムの液化温度以下（この実施例では２
００℃）に冷却することによりナトリウムを液化し、分
岐させてナトリウムを採取した。このナトリウムの純度
は９９．９９９％以上であった。Sodium carbonate (Na2CO31 and cobalt oxide [CO
Equimolar amounts of 3041 were weighed out and mixed while thoroughly grinding using a mortar. Next, this mixture was press-molded into a disk shape with a thickness of 2 mm and a diameter of 20 mm. This plate was placed in an oxygen atmosphere furnace and the temperature was gradually raised, and after firing at 800° C. for 15 hours, it was naturally cooled. It was confirmed by X-ray diffraction that the resulting product had become a γ-type sodium cobalt oxide while maintaining its original shape. Next, this disk was fixed to the inside of a high-purity alumina cylindrical tube with an inner diameter of 20 mm using an alumina adhesive, and the inside of the cylindrical tube was divided into two chambers. One end of the cylindrical tube was connected to the vicinity of the outlet of a small molten salt electrolytic cell for producing sodium, and the other end of the cylindrical tube was connected to the suction side of a highly corrosion-resistant suction pump. When the inlet and secondary sides of the cylindrical tube are heated to 600°C four times using an external heating method and suctioned with a suction pump, sodium vapor is released to the secondary side through the partition wall made of γ-type sodium cobalt oxide. , furthermore, the area near the outlet of the secondary side chamber is below the liquefaction temperature of sodium (in this example, 2
Sodium was liquefied by cooling to 00° C.) and branched to collect sodium. The purity of this sodium was 99.999% or more.
［発明の効果］
以上述べたように、本発明の分離膜は、電解還元したナ
トリウムの精製用にも用いることができるし、熱媒とし
て用いているナトリウムを分離精製することにも用いる
ことができ産業上極めて有効である。[Effects of the Invention] As described above, the separation membrane of the present invention can be used to purify electrolytically reduced sodium, and can also be used to separate and purify sodium used as a heating medium. It is extremely effective industrially.
Claims (2)
リウム蒸気の分離膜。(1) Separation membrane for sodium vapor whose main components are sodium and cobalt oxides.
ルトの原子比が０．６：１乃至１：１の範囲内であり、
γ型結晶構造を有する請求項（１）記載の分離膜。(2) The atomic ratio of sodium and cobalt in the sodium-cobalt oxide is within the range of 0.6:1 to 1:1,
The separation membrane according to claim 1, which has a γ-type crystal structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32892789A JPH03188930A (en) | 1989-12-19 | 1989-12-19 | Separation membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32892789A JPH03188930A (en) | 1989-12-19 | 1989-12-19 | Separation membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03188930A true JPH03188930A (en) | 1991-08-16 |
Family
ID=18215650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32892789A Pending JPH03188930A (en) | 1989-12-19 | 1989-12-19 | Separation membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03188930A (en) |
-
1989
- 1989-12-19 JP JP32892789A patent/JPH03188930A/en active Pending
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