JPH039796B2 - - Google Patents
Info
- Publication number
- JPH039796B2 JPH039796B2 JP18039082A JP18039082A JPH039796B2 JP H039796 B2 JPH039796 B2 JP H039796B2 JP 18039082 A JP18039082 A JP 18039082A JP 18039082 A JP18039082 A JP 18039082A JP H039796 B2 JPH039796 B2 JP H039796B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- condensate
- treated water
- hydrazine
- collection device
- 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
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 61
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 57
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 238000011144 upstream manufacturing Methods 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000003957 anion exchange resin Substances 0.000 claims description 3
- 239000003729 cation exchange resin Substances 0.000 claims description 3
- 239000011347 resin Substances 0.000 description 17
- 229920005989 resin Polymers 0.000 description 17
- 150000001768 cations Chemical class 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- -1 iron ions Chemical class 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
Description
本発明は復水の処理方法に関し、詳しくは、発
電ボイラなどのアンモニアを含む復水を混床式イ
オン交換樹脂塔を用いて処理する方法に関する。
火力発電所などにおいては、ボイラ復水は復水
処理装置で脱塩処理を施した後、アンモニアでPH
値を所定値に調整し、再びボイラ給水として循環
使用されている。
復水処理装置は、通常、並列に配置された混床
塔（混床式イオン交換樹脂床塔）で構成され、混
床塔には水素形強酸性カチオン交換樹脂（以下、
Ｈ形カチオン樹脂という）と、遊離塩基形強塩基
性アニオン交換樹脂（以下、OH型アニオン樹脂
という）とを混合状態で充填して、復水中のイオ
ン除去に供されている。
復水中には、ナトリウムイオン、塩素イオン、
鉄イオンなどの不純物の他に、PH調整用のアンモ
ニウムイオンが多量（通常0.5〜10mg／）に含
まれているので、混床塔に復水を通水するとＨ形
カチオン樹脂は不純物の他に、このアンモニウム
イオンをも捕捉してしまい、飽和後は結局、混床
塔から水酸化アンモニウムがリークすることにな
る。この段階で復水の通水を停止して混床塔を再
生し、再度復水処理に用いる方法を通称Ｈ形運転
という。
復水中はアンモニウムイオンが多量に含まれる
ため、混床塔をＨ形運転すると再生を頻繁に行な
わなければならず、再生剤とアンモニアを浪費す
ることになる。そこで、混床塔内のＨ形カチオン
樹脂がアンモニウムイオンを捕捉して飽和した後
も復水の通水を継続し、復水中の不純物を水酸化
アンモニウムの形で置換することも行なわれてお
り、これを通称NH4形運転という。
火力発電所では、電力需要に合わせて深夜、週
末、盆・暮れ・正月などの時期には運転を停止す
ることがあり、停止中には、ボイラ缶内にヒドラ
ジンを多量（0.5〜500mg／）に添加して腐食を
防止している。また、脱酸素剤としてヒドラジン
を給水中に常時数＋μｇ／程度添加することも
ある。このヒドラジンはＨ形運転時に混床塔中に
捕捉されているが、Ｈ形運転から再生を行なわず
にNH4形運転に移行すると、その転移時にヒド
ラジンが多量にリークする。ヒドラジンが多量に
リークすると、節炭器入口の給水流量に対するヒ
ドラジンの濃度管理が困難になるため、従来の停
止−再起動を繰り返すボイラの復水処理では、Ｈ
形運転のみが採用され、Ｈ形運転にひきつづいて
NH4形運転ができなかつたという問題があつた。
本発明は、上記の問題点を解決するためになさ
れたもので、ヒドラジンの大量リークを防止し、
すみやかにＨ形運転からNH4形運転に切り換え
ることのできる復水処理方法を提供することを目
的とする。
すなわち、本発明の復水処理方法は、Ｈ形カチ
オン樹脂とOH形アニオン樹脂とを混合して充填
した混床塔にアンモニア含有復水を通水して復水
を処理する方法において、混床塔に集水装置を通
水方向の上流側および下流側に２段に設け、処理
水中にヒドラジンが漏出し始めるまで又は漏出す
る直前までは下流側の集水装置から処理水を取り
出し、その後は上流側の集水装置から処理水を取
り出すことを特徴とする。
以下、添付図面に沿つて本発明を詳細に説明す
る。第１図は本発明を実施するための装置につい
て示す概略図であり、復水は、ライン１から、イ
オン交換樹脂２（Ｈ形カチオン樹脂およびOH形
アニオン樹脂）を充填した混床塔３に下向流で供
給される。混床塔３の下部には上流側の集水装置
５および下流側の集水装置６が２段に設けられて
おり、ヒドラジンのリークが始まる前（Ｈ形運転
時）は下流側の集水装置６から処理水を取り出
し、リークが生じはじめたら上流側の集水装置５
から取り出す。なお従来の混床塔では、集水装置
は１つ設けそこから連続して集水されていた。
混床塔に復水を通過すると、復水中の不純物は
除去され、その不純物に見合う分のＨ形カチオン
樹脂およびOH形アニオン樹脂は形態を換え吸着
帯を構成する。第２−ａ図〜第２−ｃ図は混床塔
内のＨ形カチオン樹脂の吸着帯の状態についての
模式図であり、第２−ａ図はＨ形運転の初期を、
第２−ｂ図はＨ形運転の中期、第２−ｃ図はＨ形
運転からNH4形運転への過渡期を示したもので
ある。それぞれ縦方向は樹脂層の高さ方向の位置
を示し、上端は樹脂層表面を、下端は下流側の集
水装置の位置を示す。また、横方向は位置ではな
く、樹脂層の横断面に分布する樹脂の形態の割合
を示す。
ヒドラジンはＨ形樹脂には捕捉されるが、
NH4形樹脂には捕捉されない。そこで、ボイラ
にヒドラジンを添加して運転を停止した後ボイラ
を再起動し、復水の処理をＨ形運転で行なうと、
第２−ａ図に示すように、ヒドラジンの吸着帯が
形成され、処理を行なうにつれて、第２−ｂ図お
よび第２−ｃに示すように、ヒドラジンの吸着帯
はアンモニアの吸着帯に先立つてあるいはほぼ同
時に下降し、下部に到達する。そして、第２−ｃ
図以降も下流側の集水装置から処理水を取り出す
とヒドラジンが処理水中にリークする。そこで、
本発明では、ヒドラジンが下流側の集水装置から
リークし始めたら、第２−ｃ図に示すように、ヒ
ドラジンの吸収帯よりも通水方向の上流側の集水
装置から処理水を取り出すことにより、ヒドラジ
ンの大量リークを防止してNH4形運転に切り換
える。幸い、ヒドラジンの吸収帯の幅は短いの
で、混床塔の下部に２段に設ける集水装置の高さ
の差は200〜700mm程度でよい。また、ヒドラジン
が下流側の集水装置からリークする直前に切り換
えてもよく、要は、ヒドラジンの吸収帯ピークが
上流側の集水装置の位置を越え、下流側の集水装
置に到達する以前に処理水の取り出し位置を切り
換えればよい。なお、Ｈ形運転時に（たとえば、
第２−ｃ図の状態時に）、再度ボイラが停止され
てヒドラジンが添加され、ついでボイラが再起動
されて多量のヒドラジンを含む復水が混床塔に通
水された場合も、このヒドラジンはアンモニアの
吸収帯に先行する位置で捕捉されるので、ヒドラ
ジン吸収帯のピークが高くなるだけで、上記と同
様に処理水を取り出すことができる。
集水装置の切り換えは、処理水の電気電導度を
測定し、電気電導度が所定値に上昇したときに行
なつてもよいし、また、混床塔の全交換容量に対
応する復水処理総量のたとえば約８割程度の復水
を通水（これを定体積運転という）した後に行な
つてもよい。
本発明によれば、Ｈ形運転からNH4形運転へ
の移行の際、ヒドラジンの大量リークがなく、停
止−再起動を繰り返すボイラの復水処理であつて
もNH4形運転を行なうことができる。
実施例
Ｈ形に再生された強酸性カチオン交換樹脂（ダ
イヤイオンPK228；(株)三菱化成工業）の4000mlと
OH型に再生された強塩基性アニオン交換樹脂
（ダイヤイオンPA312；同）1900mlとを混合し、
内径80mmのカラムに充填して混床を形成し、カラ
ム頂部に復水入口、カラム底部に処理水第１出口
（Ｈ形運転時用）およびそれより300mm上部に処理
水第２出口（NH4形運転時用）を第１図のよう
に設けた。
この混床塔にボイラ復水を72ｍ／hrの流速で55
日間通水した。その間、６日目から８日目までの
３日間および19日目から20日目までの２日間の計
５日間ボイラの運転を停止し、缶水中に保缶剤と
してヒドラジンを添加した。処理水の電気伝導度
が0.07μS／cmから0.1μS／cmに上昇した第22日目
までは、処理水第１出口から処理水を取り出し、
その後は処理水第２出口に切り換えて採水を継続
したところ、その切換により処理水質は次のよう
に変化した。
The present invention relates to a method for treating condensate, and more particularly, to a method for treating condensate containing ammonia from a power generation boiler or the like using a mixed-bed ion exchange resin tower. In thermal power plants, etc., boiler condensate is desalted in a condensate treatment device and then PH-treated with ammonia.
The value is adjusted to a predetermined value and the water is recycled again as boiler feed water. Condensate treatment equipment usually consists of mixed bed towers (mixed bed type ion exchange resin bed towers) arranged in parallel, and the mixed bed towers contain hydrogen-form strongly acidic cation exchange resins (hereinafter referred to as
The reactor is filled with a mixture of a free base type strongly basic anion exchange resin (hereinafter referred to as an OH type anion resin) and used to remove ions from condensate. Condensate contains sodium ions, chloride ions,
In addition to impurities such as iron ions, it contains a large amount (usually 0.5 to 10 mg/) of ammonium ions for pH adjustment, so when condensate is passed through a mixed bed column, H-type cation resin contains not only impurities but also ammonium ions for pH adjustment. , this ammonium ion is also captured, and after saturation, ammonium hydroxide eventually leaks from the mixed bed column. At this stage, the flow of condensate is stopped, the mixed bed tower is regenerated, and the mixed bed tower is used again for condensate treatment, commonly known as H-type operation. Since the condensate contains a large amount of ammonium ions, if the mixed bed column is operated in the H type, regeneration must be performed frequently, resulting in waste of regenerant and ammonia. Therefore, even after the H-type cation resin in the mixed bed column captures ammonium ions and becomes saturated, condensate water continues to flow, and impurities in the condensate are replaced in the form of ammonium hydroxide. , this is commonly known as NH 4 type operation. Thermal power plants sometimes suspend operation at midnight, on weekends, during Obon, end of the year, and New Year's holidays to meet power demand.During shutdown periods, a large amount of hydrazine (0.5 to 500 mg/) is placed in the boiler can. It is added to prevent corrosion. Further, as an oxygen scavenger, hydrazine may be constantly added to the water supply in an amount of approximately several μg/kg. This hydrazine is captured in the mixed bed column during H-type operation, but if H-type operation is transferred to NH 4 type operation without regeneration, a large amount of hydrazine leaks during the transition. If a large amount of hydrazine leaks, it becomes difficult to control the concentration of hydrazine in relation to the water supply flow rate at the inlet of the economizer.
Only type operation was adopted, followed by H type operation.
There was a problem that the NH4 type could not be operated. The present invention was made to solve the above problems, and it prevents large amounts of hydrazine from leaking.
The purpose of the present invention is to provide a condensate treatment method that can quickly switch from H type operation to NH 4 type operation. That is, the condensate treatment method of the present invention is a method of treating condensate by passing ammonia-containing condensate through a mixed bed tower filled with a mixture of an H-type cation resin and an OH-type anion resin. Water collection devices are installed in the tower in two stages, one on the upstream side and one on the downstream side in the water flow direction, and the treated water is taken out from the downstream water collection device until hydrazine begins to leak into the treated water or just before it leaks, and then It is characterized by taking out treated water from a water collection device on the upstream side. Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. FIG. 1 is a schematic diagram showing an apparatus for carrying out the present invention, in which condensate is sent from line 1 to a mixed bed column 3 filled with ion exchange resin 2 (H type cation resin and OH type anion resin). Supplied with downward flow. At the bottom of the mixed bed tower 3, an upstream water collection device 5 and a downstream water collection device 6 are installed in two stages. Take out the treated water from the device 6, and if a leak starts to occur, remove the water from the upstream water collection device 5.
Take it out. Note that in conventional mixed bed towers, one water collection device was provided and water was collected continuously from there. When the condensate passes through the mixed bed column, impurities in the condensate are removed, and an amount of H-type cation resin and OH-type anion resin corresponding to the impurities changes form and forms an adsorption zone. Figures 2-a to 2-c are schematic diagrams of the state of the adsorption zone of H-type cation resin in the mixed bed tower, and Figure 2-a shows the initial stage of H-type operation.
Figure 2-b shows the middle stage of H-type operation, and Figure 2-c shows the transition period from H-type operation to NH 4 type operation. The vertical direction indicates the position in the height direction of the resin layer, the upper end indicates the surface of the resin layer, and the lower end indicates the position of the water collection device on the downstream side. Moreover, the horizontal direction does not indicate the position, but indicates the proportion of the resin form distributed in the cross section of the resin layer. Hydrazine is captured by H-type resin, but
Not captured by NH4 resin. Therefore, if hydrazine is added to the boiler, the operation is stopped, the boiler is restarted, and the condensate is treated in H-type operation.
As shown in Figure 2-a, a hydrazine adsorption zone is formed, and as the treatment progresses, the hydrazine adsorption zone precedes the ammonia adsorption zone, as shown in Figures 2-b and 2-c. Or they descend almost simultaneously and reach the bottom. And the second-c
Even after the figure, when treated water is taken out from the downstream water collection device, hydrazine leaks into the treated water. Therefore,
In the present invention, when hydrazine starts to leak from the water collection device on the downstream side, treated water is taken out from the water collection device on the upstream side in the water flow direction from the absorption band of hydrazine, as shown in Figure 2-c. This prevents large amounts of hydrazine from leaking and switches to NH 4 type operation. Fortunately, the width of the absorption band of hydrazine is short, so the difference in height between the two stages of water collection devices provided at the bottom of the mixed bed tower may be about 200 to 700 mm. Alternatively, the switch may be made just before hydrazine leaks from the downstream water collection device; in short, before the absorption band peak of hydrazine exceeds the position of the upstream water collection device and reaches the downstream water collection device. All you have to do is change the location where the treated water is taken out. Note that during H-type operation (for example,
2-c), the boiler is stopped again and hydrazine is added, and then the boiler is restarted and condensate containing a large amount of hydrazine is passed through the mixed bed tower. Since it is captured at a position preceding the ammonia absorption band, the treated water can be taken out in the same way as above, simply by increasing the peak of the hydrazine absorption band. The water collection device may be switched by measuring the electrical conductivity of the treated water and when the electrical conductivity rises to a predetermined value, or by switching the condensate treatment corresponding to the total exchange capacity of the mixed bed tower. This may be carried out after passing, for example, about 80% of the total amount of condensate (this is called constant volume operation). According to the present invention, when transitioning from H-type operation to NH 4- type operation, there is no large amount of hydrazine leakage, and NH 4- type operation can be performed even in the case of condensate treatment of a boiler that is repeatedly stopped and restarted. can. Example 4000 ml of strongly acidic cation exchange resin (Diaion PK228; Mitsubishi Chemical Industries, Ltd.) regenerated into H-form and
Mix with 1900ml of strongly basic anion exchange resin (Diaion PA312; same) that has been regenerated into OH type.
A column with an inner diameter of 80 mm is packed to form a mixed bed, with a condensate inlet at the top of the column, a first treated water outlet (for H-type operation) at the bottom of the column, and a second treated water outlet (NH 4 (for use during type operation) was installed as shown in Figure 1. Boiler condensate is fed into this mixed bed tower at a flow rate of 55 m/hr.
I ran water for days. During this period, the boiler operation was stopped for a total of 5 days, 3 days from the 6th day to the 8th day and 2 days from the 19th day to the 20th day, and hydrazine was added to the can water as a can preservation agent. Until the 22nd day when the electrical conductivity of the treated water increased from 0.07μS/cm to 0.1μS/cm, the treated water was taken out from the first outlet of the treated water.
Thereafter, the water sampling was continued by switching to the second outlet of the treated water, and the quality of the treated water changed as follows.
【表】
その後は、電気伝導度約5.5μS／cm、ヒドラジ
ン濃度2μｇ／以下と安定した処理水が得られ
た。
比較例
処理水第１出口から処理水第２出口への切換え
を行なわない他は実施例と同様にして復水を処理
したところ、第22日目に電気伝導度の上昇ととも
にヒドラジンがリークしはじめ、第25日目には最
大の950μｇ／となつた。第27日目には電気伝
導度約5.5μS／cm、ヒドラジン濃度2μｇ／以下
となつたが、Ｈ形運転からNH4形運転に変わる
４、５日間は、処理水が１mg／近いヒドラジン
を含んでいた。[Table] After that, stable treated water was obtained with an electrical conductivity of approximately 5.5 μS/cm and a hydrazine concentration of 2 μg/cm or less. Comparative Example When condensate was treated in the same manner as in the example except that the first outlet of the treated water was not switched to the second outlet of the treated water, hydrazine started leaking as the electrical conductivity increased on the 22nd day. On the 25th day, it reached a maximum of 950 μg/. On the 27th day, the electrical conductivity was approximately 5.5 μS/cm and the hydrazine concentration was less than 2 μg/cm, but for 4 or 5 days when the H-type operation was changed to NH4- type operation, the treated water contained nearly 1 mg/hydrazine. It was.
第１図は本発明を実施するための装置の一例を
示す概略図である。
第２−ａ図〜第２−ｃ図は混床塔内のＨ形カチ
オン樹脂の吸着帯の状態についての模式図であ
る。
２……イオン交換樹脂、３……混床塔、５……
上段の集水装置、６……下段の集水装置。
FIG. 1 is a schematic diagram showing an example of an apparatus for implementing the present invention. Figures 2-a to 2-c are schematic diagrams of the state of the adsorption zone of the H-type cation resin in the mixed bed tower. 2...Ion exchange resin, 3...Mixed bed tower, 5...
Upper water collection device, 6...lower water collection device.
Claims (1)
強塩基性アニオン交換樹脂とを混合して充填した
混床塔にアンモニア含有復水を通水して復水を処
理する方法において、混床塔に集水装置を通水方
向の上流側および下流側に２段に設け、処理水中
にヒドラジンが漏出し始めるまで又は漏出する直
前までは下流側の集水装置から処理水を取り出
し、その後は上流側の集水装置から処理水を取り
出すことを特徴とする復水処理方法。1 In a method of treating condensate by passing ammonia-containing condensate through a mixed bed tower filled with a mixture of a hydrogen-type strongly acidic cation exchange resin and a free base-type strongly basic anion exchange resin, Water collection devices are installed in two stages on the upstream and downstream sides in the water flow direction, and the treated water is taken out from the downstream water collection device until hydrazine starts leaking into the treated water or just before it leaks, and then the treated water is taken out from the downstream water collection device, and then the treated water is removed from the upstream side. A condensate treatment method characterized by taking out treated water from a water collection device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18039082A JPS5969187A (en) | 1982-10-14 | 1982-10-14 | Condensate treating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18039082A JPS5969187A (en) | 1982-10-14 | 1982-10-14 | Condensate treating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5969187A JPS5969187A (en) | 1984-04-19 |
| JPH039796B2 true JPH039796B2 (en) | 1991-02-12 |
Family
ID=16082393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18039082A Granted JPS5969187A (en) | 1982-10-14 | 1982-10-14 | Condensate treating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5969187A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2742976B2 (en) * | 1993-04-30 | 1998-04-22 | 整水工業株式会社 | Mixed bed type ion exchange apparatus and method for producing pure water and ultrapure water using the mixed bed type ion exchange apparatus |
| JP2019128091A (en) * | 2018-01-24 | 2019-08-01 | 三菱日立パワーシステムズ株式会社 | Power plant operation method and thermal power plant |
-
1982
- 1982-10-14 JP JP18039082A patent/JPS5969187A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5969187A (en) | 1984-04-19 |
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