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JPH02233503A - Purification of hydrochloric acid - Google Patents

Purification of hydrochloric acid

Info

Publication number
JPH02233503A
JPH02233503A JP5444689A JP5444689A JPH02233503A JP H02233503 A JPH02233503 A JP H02233503A JP 5444689 A JP5444689 A JP 5444689A JP 5444689 A JP5444689 A JP 5444689A JP H02233503 A JPH02233503 A JP H02233503A
Authority
JP
Japan
Prior art keywords
hydrochloric acid
activated carbon
reducing agent
anion exchange
free
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
Application number
JP5444689A
Other languages
Japanese (ja)
Other versions
JPH0569761B2 (en
Inventor
Hiroshi Takatomi
廣志 高富
Shinji Yamauchi
信次 山内
Koji Ogawa
浩二 小川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Osaka Soda Co Ltd
Original Assignee
Daiso Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Daiso Co Ltd filed Critical Daiso Co Ltd
Priority to JP5444689A priority Critical patent/JPH02233503A/en
Publication of JPH02233503A publication Critical patent/JPH02233503A/en
Publication of JPH0569761B2 publication Critical patent/JPH0569761B2/ja
Granted legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00Halogens; Halogen acids
    • C01B7/01Chlorine; Hydrogen chloride
    • C01B7/07Purification ; Separation
    • C01B7/0706Purification ; Separation of hydrogen chloride
    • C01B7/0718Purification ; Separation of hydrogen chloride by adsorption
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00Halogens; Halogen acids
    • C01B7/01Chlorine; Hydrogen chloride
    • C01B7/07Purification ; Separation
    • C01B7/0706Purification ; Separation of hydrogen chloride
    • C01B7/0718Purification ; Separation of hydrogen chloride by adsorption
    • C01B7/0725Purification ; Separation of hydrogen chloride by adsorption by active carbon

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

PURPOSE:To improve purification efficiency by dechlorinating a hydrochloric acid containing free Cl and Fe component with a specific reducing agent and/or a lowly activated carbon and contacting the dechlorinated acid with a strongly basic anion exchange resin. CONSTITUTION:Free Cl of a hydrochloric acid containing free Cl and Fe component is removed by mixing the hydrochloric acid with stoichiometric amount or less than stoichiometric amount (based on the free Cl) of a reducing agent (e.g. hydrazine, hydroxylamine hydrochloride or urea) or mixing the acid with a lowly activated carbon having a specific surface area of <=500m<2>/g and filtering the mixture. When the free C1 concentration in the hydrochloric acid exceeds 10ppm, it is decreased to about 10ppm with the reducing agent and then further decreased to <=1ppm with the lowly activated carbon. When the concentration of the obtained hydrochloric acid is >=15wt.%, Fe component existing as FeCl ion is effectively adsorbed and removed by contacting with a strongly basic anion exchange resin.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は遊離塩素及び鉄分を含何する塩酸の精製方法に
関するものである。
DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for purifying hydrochloric acid containing free chlorine and iron.

[従来の技術とその課題] 金属の洗浄液に使用ざれた塩酸廃液は大部分塩化第一鉄
として鉄分を含有している。このような塩鼠を精製する
場合、まず塩素ガスで第一鉄塩を第二鉄塩に酸化する。
[Prior art and its problems] Hydrochloric acid waste used as a metal cleaning solution contains iron mostly as ferrous chloride. When refining such salt rats, first ferrous salts are oxidized to ferric salts using chlorine gas.

また有機化合物製造時に副生ずる塩酸中にも遊離塩素及
び第二鉄塩を含む場合が多い。第二銖塩でおれば強塩基
性陰イオン交換樹脂例えばα型陰イオン交換樹脂で除去
できるので、陰イオン交換樹脂保護のために、活性炭で
′t1離塩素を除去した後に樹脂塔に送る方法が行われ
ている。すなわち活性炭による遊離塩素除去の目的は、
陰イオン交換樹脂が遊離塩素により酸化され交換容量が
低下するのを防ぐことや塩酸の着色を防ぐことであるが
、このような活性炭による脱塩素処理を行った塩酸は鉄
分が十分除去できないという問題点がめった。
Furthermore, hydrochloric acid produced as a by-product during the production of organic compounds often contains free chlorine and ferric salts. If it is a secondary salt, it can be removed with a strongly basic anion exchange resin, such as an α-type anion exchange resin, so in order to protect the anion exchange resin, 't1 free chlorine is removed with activated carbon and then sent to the resin column. is being carried out. In other words, the purpose of free chlorine removal using activated carbon is
The aim is to prevent the anion exchange resin from being oxidized by free chlorine and reduce its exchange capacity, and to prevent the coloring of hydrochloric acid, but the problem is that iron cannot be removed sufficiently from hydrochloric acid that has been dechlorinated using activated carbon. I scored very few points.

(課題を解決するための手段〕 本発明者らは以上の問題点を解決するため、鋭意検討を
行った結果、濃度15重母%以上の塩酸に含まれる鉄分
は第二鉄であればFe(Ja″″イオンとして存在する
ので強塩基性陰イオン交換樹脂に吸着するが、通常の活
性炭と接触すると活性炭の還元力で一部が第一鉄となり
、陰イオン交換樹脂で鉄分を完全に除去できなくなるこ
とが判明した。
(Means for Solving the Problems) In order to solve the above problems, the present inventors conducted intensive studies and found that if the iron contained in hydrochloric acid with a concentration of 15% or more is ferric iron, Fe (Since it exists as Ja″″ ions, it is adsorbed by the strongly basic anion exchange resin, but when it comes into contact with ordinary activated carbon, some of it becomes ferrous iron due to the reducing power of the activated carbon, and the iron content is completely removed by the anion exchange resin. It turned out that it would not be possible.

本発明は以上の知見に基いて完成ざれたものであってす
なわち、遊離塩素及び鉄分を含有する塩敢に、還元剤を
添加するか又は比表面積500尻/Q以下の低賦活活性
炭を接触させて脱塩素処理を行った後、強塩基性陰イオ
ン交換樹脂と接触させることを特徴とする塩薗の精製方
法である。また還元剤を添加後、上記低試活活性炭を接
触させてもよい。
The present invention has been completed based on the above findings, namely, by adding a reducing agent or contacting low-activation activated carbon with a specific surface area of 500 sides/Q or less to a salt containing free chlorine and iron. This is a method for purifying shiokon, which is characterized by carrying out dechlorination treatment using chlorine and then contacting it with a strongly basic anion exchange resin. Further, after adding the reducing agent, the low test activated carbon may be brought into contact with the reducing agent.

本発明において用いられる活性炭は比表面積SOOボ/
g以下2好ましくは300尻/g以下の低斌活活性炭で
あり、通常の平均約1000TIi/gの比表面積を有
する活性炭とは異なるものである。このような低賦活活
性炭は炭化温度500〜600℃,水蒸気による賦活温
度850〜1000℃にて通常の活性炭より例えば賦活
時間を短縮する等の方法により比表面積の増加を加減し
て製造することができる。また水蒸気賦活法に特に限定
ざれず例えば亜鉛を使用する方法等他の斌活法によって
も製造し得る。
The activated carbon used in the present invention has a specific surface area of SOO/
The activated carbon has a low density of less than 2 g, preferably less than 300 TIi/g, and is different from ordinary activated carbon having a specific surface area of about 1000 TIi/g on average. Such low-activation activated carbon can be produced at a carbonization temperature of 500 to 600°C and an activation temperature of 850 to 1000°C with steam, by adjusting the increase in specific surface area by, for example, shortening the activation time compared to ordinary activated carbon. can. Further, it is not particularly limited to the steam activation method, and can also be produced by other activation methods such as a method using zinc.

この低賦活活性炭と塩酸との接触方法は特に限定される
ことなく、例えば低賦活活性炭の充填層に塩酸を通過さ
せてもよく、塩酸と低賦活活性炭とを十分混合した後枦
過してもよい。通常、塩酸中の遊離塩素が約10ppm
程度であれば、このような低賦活活性炭により1 pp
m以下にまで脱塩素することができ、強塩基性陰イオン
交換樹脂を損傷することがない。
The method of contacting the low-activation activated carbon with hydrochloric acid is not particularly limited; for example, the hydrochloric acid may be passed through a packed bed of low-activation activated carbon, or the hydrochloric acid and the low-activation activated carbon may be sufficiently mixed and then passed through. good. Usually, free chlorine in hydrochloric acid is about 10 ppm
If the level of
It can be dechlorinated to less than m and does not damage the strongly basic anion exchange resin.

また塩酸中の鉄分は第一鉄塩にまで遠元されず第二鉄塩
の形態を保っているので強塩基性陰イオン交換樹脂によ
り効率のよい脱鉄を行うことができる。
Furthermore, since the iron content in hydrochloric acid is not dissipated into ferrous salt and remains in the form of ferric salt, it is possible to efficiently remove iron using a strongly basic anion exchange resin.

本発明において使用ざれる還元剤はヒドラジン、塩酸ヒ
ドロキシルアミン,尿素,過酸化水素の少なくとも1種
が好ましく、このような還元剤を用いることにより塩酸
中への不純物の混入を避けることができる。還元剤の添
加母は遊離塩素に対し化学量論的量もしくはそれ以下で
よく、還元剤が過剰にならないよう注意する。還元剤の
添加母は遊離塩素自動分析計で測定しながら調節すれば
よい。
The reducing agent used in the present invention is preferably at least one of hydrazine, hydroxylamine hydrochloride, urea, and hydrogen peroxide, and by using such a reducing agent, it is possible to avoid contamination of the hydrochloric acid with impurities. The reducing agent may be added in a stoichiometric amount or less relative to free chlorine, and care must be taken not to add too much reducing agent. The amount of reducing agent added may be adjusted while measuring with an automatic free chlorine analyzer.

脱塩lA処理は還元剤の添加又は低賦活活性炭のみによ
って行うことも可能であるが、被精製塩酸中の遊m塩素
濃度が10ppmを越える場合は、必らかじめ還元剤を
添加して10ppm程度にまで遊離塩素を除去した後、
ざらに低賦活活性炭により脱塩素処理を行う方法が工業
的に好ましい。このように還元剤の添加により大部分の
遊離塩素を還元し、残存する少量の遊離塩素を低賦活活
性炭により除去すれば、活性炭の負荷を小にしその寿命
を長くすることができる。
Desalination 1A treatment can be carried out by adding a reducing agent or by using only low activated carbon, but if the free m chlorine concentration in the hydrochloric acid to be purified exceeds 10 ppm, be sure to add a reducing agent in advance to reduce the concentration to 10 ppm. After removing free chlorine to a certain extent,
A method in which dechlorination is carried out using low-activation activated carbon is industrially preferred. In this way, by reducing most of the free chlorine by adding a reducing agent and removing the small amount of remaining free chlorine using low activation activated carbon, it is possible to reduce the load on the activated carbon and extend its life.

実施例1 直径25mm,高さ500mmのガラムカラムに、あら
かじめ塩酸で洗浄した低賦活活性炭(ヤシ殻炭を水蒸気
試活,比表面積130M/(J .粒度12〜40メッ
シュ》を150威充填したく第1塔)。また同形のカラ
ムに強塩基性陰イオン交換樹脂(商品名アンバーライト
I RA−400 ,ロームアンドハース社製>  1
50dを充填した(第2塔)。遊離塩素32ppm,鉄
分42ppmを含む濃度27%の塩酸を28℃にて第1
塔,第2塔の順にそれぞれ空間速度( S V )  
8hrlで下向流で通過させたところ、第2塔出口の塩
酸中の遊離塩素0. 3ppm,鉄分は0.2ppmで
あった。
Example 1 A gallium column with a diameter of 25 mm and a height of 500 mm was filled with 150 pieces of low activation activated carbon (coconut shell charcoal, steam tested, specific surface area: 130 M/(J. particle size: 12 to 40 mesh)) which had been washed with hydrochloric acid in advance. 1 column).In addition, a strongly basic anion exchange resin (trade name Amberlite I RA-400, manufactured by Rohm and Haas Co., Ltd.> 1 column) was used in the same column.
50d (second column). Hydrochloric acid with a concentration of 27% containing 32 ppm of free chlorine and 42 ppm of iron was first added at 28°C.
space velocity (SV) in the order of the column and the second column, respectively.
When it was passed in a downward flow at 8 hrl, free chlorine in the hydrochloric acid at the outlet of the second column was 0. The iron content was 3 ppm, and the iron content was 0.2 ppm.

比較例1 実施例1の低賦活活性炭の代りに、あらかじめ塩酸で洗
浄した粒状ヤシ殻活性炭(商品名 白鷺W:武田薬品工
業(株)!!!)を使用し他は同様にして、同じ塩酸の
精製を行ったところ、第2塔出口の塩酸中の遊離塩素0
. 2pI)m,鉄分4.5ppmであった。この活性
炭の比表面積を自動ボロシメーターオートポア9200
 ( (株)島津製作所製)にて測定したところ110
0TIi/fjであった。
Comparative Example 1 In place of the low activation activated carbon of Example 1, granular coconut shell activated carbon (trade name: Shirasagi W: Takeda Pharmaceutical Company Ltd.!!!) which had been washed with hydrochloric acid in advance was used, and the other conditions were the same, and the same hydrochloric acid was used. When purified, 0 free chlorine was found in the hydrochloric acid at the outlet of the second column.
.. The iron content was 2pI)m, and the iron content was 4.5ppm. The specific surface area of this activated carbon was measured using an automatic borosimeter Autopore 9200.
(Manufactured by Shimadzu Corporation): 110
It was 0TIi/fj.

実施例2 遊離塩素85ppm,鉄分36ppmを含む濃度32%
の塩酸1gに15℃の室温にて濃度1%のヒドラジン水
溶液6dを添加し同温度にて10分間放置した。
Example 2 Concentration 32% including free chlorine 85 ppm and iron 36 ppm
To 1 g of hydrochloric acid was added 6 d of a 1% aqueous hydrazine solution at a room temperature of 15° C., and the mixture was left at the same temperature for 10 minutes.

この塩酸の遊離塩素濃度は0. 8ppmでおった。次
いでこの塩酸を実施例1と同様の強塩基性陰イオン交換
樹脂充填力ラムに空間速度(SV)10hr″″1で下
向流で通過させたところ樹脂筒出口の塩酸中の遊離塩素
0. li)pm,鉄分0. 81)pmテあった。
The free chlorine concentration of this hydrochloric acid is 0. It was 8 ppm. Next, this hydrochloric acid was passed through a strongly basic anion exchange resin packing force ram similar to that in Example 1 in a downward flow at a space velocity (SV) of 10 hr''1, and free chlorine in the hydrochloric acid at the outlet of the resin cylinder was 0.0. li) pm, iron content 0. 81) There was a pm te.

実施例3 遊!Ii塩素1oappm.鉄分30ppmを含む濃度
35%の塩酸りに、15℃にて濃度1%の尿素水溶液5
dを添加し同温度にて15分間放置した。この塩酸中の
遊離塩素は13ppmとなった。次いであらかじめ塩薗
で洗浄した低賦活活性炭(比表面積270m/0,粒度
12X40メッシュ)150威を充填した第1塔,及び
実施例1と同じ第2塔を空間速度(SV)7hr″″1
で下向流で通過させたところ、第2塔出口の塩酸中の遊
離塩素0.1ppln,鉄分0.5ppmでおった。
Example 3 Play! Ii Chlorine 1oappm. Add a 1% aqueous urea solution 5 to 35% hydrochloric acid containing 30 ppm iron at 15°C.
d was added and left at the same temperature for 15 minutes. Free chlorine in this hydrochloric acid was 13 ppm. Next, the first column filled with 150 liters of low-activation activated carbon (specific surface area 270 m/0, particle size 12 x 40 mesh) which had been washed with salt in advance, and the second column which was the same as in Example 1, were heated at a space velocity (SV) of 7 hr''1.
When the hydrochloric acid was passed through in a downward flow, the free chlorine and iron content in the hydrochloric acid at the outlet of the second column were 0.1 ppln and 0.5 ppm, respectively.

[発明の効果] 本発明方法によれば、塩酸中の遊離塩素及び鉄分を除去
する際、従来の活性炭にかえて、還元剤又は低試活活性
炭を使用し又はこれらを併用して脱塩素処理を行うこと
により、塩酸中の鉄分を第一鉄塩にまで還元することな
く強塩基性陰イオン交換樹脂による効率のよい脱鉄を行
うことができるので工業的に有用である。
[Effects of the Invention] According to the method of the present invention, when removing free chlorine and iron from hydrochloric acid, dechlorination treatment is carried out by using a reducing agent or low-test activated carbon, or in combination with these, in place of conventional activated carbon. By carrying out this process, iron removal can be carried out efficiently using a strongly basic anion exchange resin without reducing the iron content in hydrochloric acid to ferrous salt, which is industrially useful.

Claims (3)

【特許請求の範囲】[Claims] (1)遊離塩素及び鉄分を含有する塩酸に、還元剤を添
加するか又は比表面積500m^2/g以下の低賦活活
性炭を接触させて脱塩素処理を行つた後、強塩基性陰イ
オン交換樹脂と接触させることを特徴とする塩酸の精製
方法。
(1) Hydrochloric acid containing free chlorine and iron is dechlorinated by adding a reducing agent or brought into contact with low activation activated carbon with a specific surface area of 500 m^2/g or less, followed by strong basic anion exchange. A method for purifying hydrochloric acid, which comprises bringing it into contact with a resin.
(2)遊離塩素及び鉄分を含有する塩酸に還元剤を添加
後、比表面積500m^2/g以下の低賦活活性炭と接
触させて脱塩素処理を行った後、強塩基性陰イオン交換
樹脂と接触させることを特徴とする塩酸の精製方法。
(2) After adding a reducing agent to hydrochloric acid containing free chlorine and iron, it is brought into contact with low activation activated carbon with a specific surface area of 500 m^2/g or less for dechlorination treatment, and then treated with a strong basic anion exchange resin. A method for purifying hydrochloric acid, which comprises bringing it into contact.
(3)還元剤がヒドラジン、塩酸ヒドロキシルアミン、
尿素、過酸化水素より選ばれた少なくとも1種である請
求項1もしくは請求項2に記載の塩酸の精製方法。
(3) The reducing agent is hydrazine, hydroxylamine hydrochloride,
The method for purifying hydrochloric acid according to claim 1 or 2, wherein at least one selected from urea and hydrogen peroxide is used.
JP5444689A 1989-03-06 1989-03-06 Purification of hydrochloric acid Granted JPH02233503A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP5444689A JPH02233503A (en) 1989-03-06 1989-03-06 Purification of hydrochloric acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP5444689A JPH02233503A (en) 1989-03-06 1989-03-06 Purification of hydrochloric acid

Publications (2)

Publication Number Publication Date
JPH02233503A true JPH02233503A (en) 1990-09-17
JPH0569761B2 JPH0569761B2 (en) 1993-10-01

Family

ID=12970929

Family Applications (1)

Application Number Title Priority Date Filing Date
JP5444689A Granted JPH02233503A (en) 1989-03-06 1989-03-06 Purification of hydrochloric acid

Country Status (1)

Country Link
JP (1) JPH02233503A (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5330735A (en) * 1993-01-21 1994-07-19 Dow Corning Corporation Purification of hydrochloric acid
EP0618170A1 (en) * 1993-03-31 1994-10-05 Basf Corporation Process for producing reagent grade hydrochloric acid from the manufacture of organic isocyanates
US5426944A (en) * 1993-08-31 1995-06-27 American Air Liquide, Inc. Chemical purification for semiconductor processing by partial condensation
US6290927B1 (en) * 1994-06-03 2001-09-18 Norsk Hydro A/S Method for the removal of unwanted color from hydrochloric acid
CN109553070A (en) * 2018-12-17 2019-04-02 江苏诺斯特拉环保科技有限公司 Waste hydrochloric acid recycles method of disposal
CN110436416A (en) * 2019-08-19 2019-11-12 四川金山制药有限公司 A kind of technique preparing electronic grade hydrochloric acid except free chlorine
CN110562922A (en) * 2019-08-19 2019-12-13 四川金山制药有限公司 Process for producing atomic fluorescent grade hydrochloric acid by gasification method
CN111960384A (en) * 2020-08-26 2020-11-20 浙江凯圣氟化学有限公司 Method for removing free chlorine in hydrochloric acid
CN114180525A (en) * 2021-12-30 2022-03-15 南通醋酸化工股份有限公司 Separation method of hydrogen chloride/dichloromethane in synthesis of 4-chloroacetoacetic acid ethyl ester

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5330735A (en) * 1993-01-21 1994-07-19 Dow Corning Corporation Purification of hydrochloric acid
EP0618170A1 (en) * 1993-03-31 1994-10-05 Basf Corporation Process for producing reagent grade hydrochloric acid from the manufacture of organic isocyanates
US5426944A (en) * 1993-08-31 1995-06-27 American Air Liquide, Inc. Chemical purification for semiconductor processing by partial condensation
US6290927B1 (en) * 1994-06-03 2001-09-18 Norsk Hydro A/S Method for the removal of unwanted color from hydrochloric acid
CN109553070A (en) * 2018-12-17 2019-04-02 江苏诺斯特拉环保科技有限公司 Waste hydrochloric acid recycles method of disposal
CN110436416A (en) * 2019-08-19 2019-11-12 四川金山制药有限公司 A kind of technique preparing electronic grade hydrochloric acid except free chlorine
CN110562922A (en) * 2019-08-19 2019-12-13 四川金山制药有限公司 Process for producing atomic fluorescent grade hydrochloric acid by gasification method
CN111960384A (en) * 2020-08-26 2020-11-20 浙江凯圣氟化学有限公司 Method for removing free chlorine in hydrochloric acid
CN111960384B (en) * 2020-08-26 2022-04-12 浙江凯圣氟化学有限公司 Method for removing free chlorine in hydrochloric acid
CN114180525A (en) * 2021-12-30 2022-03-15 南通醋酸化工股份有限公司 Separation method of hydrogen chloride/dichloromethane in synthesis of 4-chloroacetoacetic acid ethyl ester

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