JPH0140676B2 - - Google Patents
Info
- Publication number
- JPH0140676B2 JPH0140676B2 JP56038418A JP3841881A JPH0140676B2 JP H0140676 B2 JPH0140676 B2 JP H0140676B2 JP 56038418 A JP56038418 A JP 56038418A JP 3841881 A JP3841881 A JP 3841881A JP H0140676 B2 JPH0140676 B2 JP H0140676B2
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- wastewater
- calcium
- caustic soda
- hydrochloric acid
- 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
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
- Water Treatment By Sorption (AREA)
Description
本発明はフツ素化合物を吸着したキレート樹脂
の再生及び該再生廃液の処理方法に関するもので
ある。
アルミニウム電解精錬工程、リン酸肥料の製造
工程、ステンレス鋼などのピツクリング工程など
からは、フツ素を含む廃水が排出される。従来こ
のような廃水中のフツ素は塩化カルシウム、水酸
化カルシウム等のカルシウム化合物により不溶性
のフツ化カルシウムとし、これを沈殿分離するこ
とにより除去していた。しかしながらフツ素化合
物を含む廃水、たとえばフツ素とホウ素が結合し
BF4 -のような安定な錯化合物を含む廃水ではカ
ルシウム化合物の添加によりフツ素をフツ化カル
シウムとして沈殿分離することができない。
特願昭55−015786号においてこれらカルシウム
化合物の添加により沈殿分離できないフツ素化合
物の除去方法としてキレート樹脂による吸着除去
によつて述べた。
本発明は、特願昭55−015786号における処理方
法、すなわち、「１フツ素化合物を含む廃水を鉱
酸にてPH７以下とし、キレート樹脂と接触させる
ことによつてフツ素を吸着除去することを特徴と
するフツ素化合物を含む廃水の処理方法。
２ 廃水中に遊離のフツ素が含まれているとき
は、あらかじめカルシウム化合物を添加して該フ
ツ素をフツ化カルシウムとして除去するものであ
る特許請求の範囲第１項記載のフツ素化合物を含
む廃水の処理方法。」で得られるフツ素化合物を
吸着後のキレート樹脂を苛性ソーダと塩化ナトリ
ウムの混合溶液と塩酸、或いは苛性ソーダと塩酸
により再生し、ここで得られる再生廃水にカルシ
ウム化合物を添加することにより該廃液中のフツ
素をフツ化カルシウムとして固液分離するもので
ある。再生においては、再生剤として苛性ソーダ
と塩化ナトリウムの混合溶液と塩酸、或いは苛性
ソーダと塩酸が使用でき、いずれの場合にも吸着
されたフツ素量の90％以上が脱着可能である。又
脱着されたフツ素のうち70％以上がカルシウム化
合物の添加によりフツ化カルシウムとして固液分
離が可能である。
この作用機構としては、再生剤として使用した
酸やアルカリにより吸着されたBF4 -の一部が分
解し、フリーのF-が得られ、これがカルシウム
化合物の添加でCaF2となり析出するものと考え
られる。
従来、イオン交換、キレート樹脂等の再生廃液
処理としては、蒸発濃縮・乾燥固化回収が行われ
てきたが本発明によれば苛性ソーダと塩化ナトリ
ウム混合溶液と塩酸、或いは苛性ソーダと塩酸で
再生することにより再生廃液中のフツ素（脱着物
質）は沈殿物として回収することができ、ここで
の清澄分離水は原廃水に混合し循環処理できるも
のであり、蒸発濃縮、乾燥固化方式に比較しイニ
シヤル及びランニングコストとしてはかなりの低
減となる。
さらに本発明の一実施態様を添附図を参照しな
がら説明すれば、第１図においてフツ素化合物
（BF4 -）を吸着除去したキレート樹脂塔１に苛性
ソーダ或いは苛性ソーダと塩化ナトリウムの混合
液２、洗浄水３、塩酸４の順に通液しここで各廃
液５は反応槽６に導びかれ再生廃液となる。次に
反応槽６にカルシウム化合物７を添加し再生廃液
中の遊離のフツ素をフツ化カルシウムとして析出
させる。この反応におけるPH領域としてはアルカ
リ域が良く中和剤としては苛性アルカリ８を添加
すると良い。フツ化カルシウム析出後、廃水を沈
殿池９に導びきここでフツ化カルシウムを沈殿分
離するが沈殿反応を促進するため高分子凝集剤１
０を添加する必要がある。
次に沈殿池９において固液分離される。フツ化
カルシウム沈殿物は脱水機１４にて脱水され、ケ
ーキ１５として回収される。又脱水分離水１３は
沈殿池上澄水と共にあるいはいずれか一方でもよ
い（以下清澄分離水と称する）、原廃水１２に混
合され処理される。
この清澄分離水中には再生廃液処理で除去でき
ないフツ素（安定な錯化合物と考えられる。）が
残留しているのであるが（実施例では再生廃液の
フツ素濃度の21.8〜30％）、清澄分離水の液量が
原廃水に比べてわずかな量であることから適当な
水量比で原廃水に混合することにしたのである。
このような循環処理が可能なことは本願発明の特
徴の１つである。
即ち、原廃水中の安定な錯化合物としてのフツ
素をキレート樹脂で吸着および再生する過程で遊
離のフツ素に分解し、分解された遊離のフツ素を
カルシウム化合物の添加処理により容易にフツ化
カルシウムとして析出させ、ケーキとして回収す
ることができ、最終処理水中にフツ素が残留する
ことなく、完全な廃水の処理ができるのである。
以上述べたように本発明によればキレート樹脂
に吸着除去されたBF4 -は、苛性ソーダと塩酸、
或いは苛性ソーダと塩化ナトリウムの混合溶液と
塩酸による再性により90％以上の再生効率が得ら
れ、また、ここで生じる再生廃液にカルシウム化
合物を添加することにより再生で脱着されたフツ
素のうち70％以上がフツ化カルシウムとして析出
し、固液分離を行うことにより沈殿物として回収
されることになる。
次に本発明の実施例を示す。
フツ素濃度20、50、100mg／の３種類の廃水
をHCl＝３とし各廃水を通水速度SV＝20で各キ
レート樹脂塔に通水し、ブレーク後各キレート樹
脂を下記に示す条件で再生した結果表−１に示す
ごとくいずれも90％以上の再生率が得られた。
（再生条件）
１ ２％NaOH溶液、或いは２％NaOH＋５％
NaCl混合溶液の通水
通水量−４／−Ｒ
通水速度−SV＝２
２ 押出し
通水量−１／−Ｒ
通水速度−SV＝２
３ 2N−HClの通水
通水量−４／−Ｒ
通水速度−SV＝２
The present invention relates to a method for regenerating a chelate resin that has adsorbed a fluorine compound and for treating the regenerated waste liquid. Fluorine-containing wastewater is discharged from aluminum electrolytic refining processes, phosphate fertilizer manufacturing processes, and stainless steel pickling processes. Conventionally, fluorine in such wastewater has been removed by converting it into insoluble calcium fluoride using a calcium compound such as calcium chloride or calcium hydroxide, and then separating this by precipitation. However, wastewater containing fluorine compounds, such as fluorine and boron combined,
In wastewater containing stable complex compounds such as BF 4 - , fluorine cannot be precipitated and separated as calcium fluoride by adding calcium compounds. In Japanese Patent Application No. 55-015786, adsorption removal using a chelate resin was described as a method for removing fluorine compounds which cannot be separated by precipitation due to the addition of calcium compounds. The present invention is based on the treatment method disclosed in Japanese Patent Application No. 55-015786, that is, ``1 fluorine compound-containing wastewater is made to have a pH of 7 or lower with mineral acid, and fluorine is adsorbed and removed by contacting it with a chelate resin. A method for treating wastewater containing fluorine compounds, characterized by: 2. When free fluorine is contained in wastewater, a calcium compound is added in advance to remove the fluorine as calcium fluoride. A method for treating wastewater containing fluorine compounds according to claim 1. The chelate resin obtained by adsorbing fluorine compounds is regenerated with a mixed solution of caustic soda and sodium chloride and hydrochloric acid, or with caustic soda and hydrochloric acid. By adding a calcium compound to the recycled wastewater obtained here, fluorine in the wastewater is converted into calcium fluoride and subjected to solid-liquid separation. In regeneration, a mixed solution of caustic soda and sodium chloride and hydrochloric acid, or caustic soda and hydrochloric acid can be used as regenerants, and in either case, more than 90% of the adsorbed fluorine can be desorbed. Moreover, more than 70% of the desorbed fluorine can be separated into solid-liquid as calcium fluoride by adding a calcium compound. The mechanism of this action is that part of the BF 4 - adsorbed by the acid or alkali used as a regenerant is decomposed to obtain free F - , which becomes CaF 2 and precipitates when a calcium compound is added. It will be done. Conventionally, ion exchange, chelate resin, etc. regenerated waste liquid treatment has been carried out by evaporation concentration and dry solidification recovery, but according to the present invention, by regenerating with a mixed solution of caustic soda and sodium chloride and hydrochloric acid, or with caustic soda and hydrochloric acid. The fluorine (desorption substance) in the recycled waste liquid can be recovered as a precipitate, and the clarified separated water here can be mixed with the raw waste water and recycled, and the initial and This results in a considerable reduction in running costs. Further, one embodiment of the present invention will be described with reference to the accompanying drawings. In FIG . 1, caustic soda or a mixed solution of caustic soda and sodium chloride 2, Washing water 3 and hydrochloric acid 4 are passed in this order, and each waste liquid 5 is led to a reaction tank 6 and becomes a regenerated waste liquid. Next, a calcium compound 7 is added to the reaction tank 6 to precipitate free fluorine in the recycled waste liquid as calcium fluoride. The PH range for this reaction is preferably in the alkaline range, and caustic alkali 8 is preferably added as a neutralizing agent. After calcium fluoride is precipitated, the wastewater is led to a settling tank 9 where the calcium fluoride is separated by precipitation, but a polymer flocculant 1 is added to promote the precipitation reaction.
It is necessary to add 0. Next, solid-liquid separation is performed in a settling tank 9. The calcium fluoride precipitate is dehydrated in a dehydrator 14 and recovered as a cake 15. The dehydrated separated water 13 may be mixed with the raw wastewater 12 together with the sedimentation tank supernatant water (hereinafter referred to as clarified separated water) and treated. This clarified separated water contains residual fluorine (considered to be a stable complex compound) that cannot be removed by the recycled waste liquid treatment (21.8 to 30% of the fluorine concentration in the recycled waste liquid in the example). Since the amount of separated water is small compared to the raw wastewater, it was decided to mix it with the raw wastewater at an appropriate water ratio.
The ability to perform such cyclic processing is one of the features of the present invention. In other words, fluorine, which is a stable complex compound in raw wastewater, is decomposed into free fluorine during the adsorption and regeneration process with a chelate resin, and the decomposed free fluorine can be easily converted to fluorine by adding calcium compounds. It can be precipitated as calcium and recovered as a cake, allowing complete wastewater treatment without residual fluorine in the final treated water. As described above, according to the present invention, BF 4 - adsorbed and removed by the chelate resin is mixed with caustic soda and hydrochloric acid.
Alternatively, a regeneration efficiency of over 90% can be obtained by regeneration using a mixed solution of caustic soda and sodium chloride and hydrochloric acid, and by adding a calcium compound to the regeneration waste liquid generated here, 70% of the fluorine desorbed during regeneration can be obtained. The above precipitates as calcium fluoride, and is recovered as a precipitate by performing solid-liquid separation. Next, examples of the present invention will be shown. Three types of wastewater with fluorine concentrations of 20, 50, and 100mg/ were set to HCl = 3, and each wastewater was passed through each chelate resin tower at a water flow rate of SV = 20, and after breaking, each chelate resin was regenerated under the conditions shown below. As shown in Table 1, a regeneration rate of 90% or more was obtained in all cases. (Regeneration conditions) 1 2% NaOH solution or 2% NaOH + 5%
Water flow rate of NaCl mixed solution -4/-R Water flow rate -SV=2 2 Extrusion water flow rate -1/-R Water flow rate -SV=2 3 Water flow rate of 2N-HCl -4/-R Water flow rate - SV = 2
【表】
上記の再生により生じる再生廃液（表−１にお
ける実験No.１、２、３における再生操作で発生し
た廃液を全量混合したもの）（F-として2200mg／
含む）に対し塩化カルシウムを5000、7500、
10000、15000mg／まで段階的に添加し、その後
NaOHにてPH＝11として反応後、アニオンポリ
マー（0.2％）１〜２mg／添加して数分間撹拌
静置後、東洋ろ紙のNo.5Aにて濾過しここで得ら
れた濾過水についてＦ濃度を調べた。その結果は
表−２に示す通りであり処理水フツ素濃度は
CaCl25000、7500、10000、15000mg／の添加に
対して各々660、490、480、480mg／となり除去
率は70％以上を示した。[Table] Recycled waste liquid generated by the above regeneration (mixture of all waste liquids generated in the regeneration operations in Experiment Nos. 1, 2, and 3 in Table 1) (2200 mg/as F - )
Calcium chloride 5000, 7500,
Add in stages up to 10,000, 15,000mg/, then
After reaction with NaOH to pH=11, add 1-2 mg of anionic polymer (0.2%), stir and let stand for several minutes, filter with Toyo Roshi No. 5A, and the F concentration of the filtrated water obtained. I looked into it. The results are shown in Table 2, and the fluorine concentration in the treated water is
When CaCl 2 was added at 5000, 7500, 10000, and 15000 mg/, the removal rate was 660, 490, 480, and 480 mg/, respectively, and the removal rate was 70% or more.
第１図は本発明の一実施態様を示すフローシー
トである。
１……キレート樹脂塔、２……再生剤−１、３
……洗浄水、４……再生剤−２、５……再生廃
液、６……反応槽、７……カルシウム化合物、８
……苛性アルカリ、９……沈殿池、１０……高分
子凝集剤、１１……上澄水、１２……原廃水、１
３……脱水分離水、１４……脱水機、１５……ケ
ーキ、１６……最終処理水。
FIG. 1 is a flow sheet showing one embodiment of the present invention. 1...Chelate resin tower, 2...Regenerating agent-1, 3
... Washing water, 4 ... Regenerating agent-2, 5 ... Regeneration waste liquid, 6 ... Reaction tank, 7 ... Calcium compound, 8
... Caustic alkali, 9 ... Sedimentation tank, 10 ... Polymer flocculant, 11 ... Supernatant water, 12 ... Raw wastewater, 1
3... Dehydrated separated water, 14... Dehydrator, 15... Cake, 16... Final treated water.
Claims (1)
より、該廃水中のフツ素化合物を吸着したキレー
ト樹脂を苛性ソーダと塩化ナトリウムの混合溶液
と塩酸、又は苛性ソーダと塩酸により再生すると
共に、該再生工程で得られる再生液にカルシウム
化合物を添加してフツ化カルシウムを析出させた
後、高分子凝集剤を添加して固液分離することを
特徴するキレート樹脂の再生処理方法。 ２ 前記固液分離により得られた清澄分離水を前
記フツ素化合物を含む廃水に混合するものである
特許請求の範囲第１項記載の方法。[Claims] 1. By bringing wastewater containing fluorine compounds into contact with each other, the chelate resin that has adsorbed the fluorine compounds in the wastewater is regenerated with a mixed solution of caustic soda and sodium chloride and hydrochloric acid, or with caustic soda and hydrochloric acid, and A method for regenerating a chelate resin, which comprises adding a calcium compound to the regenerating solution obtained in the regenerating step to precipitate calcium fluoride, and then adding a polymer flocculant to perform solid-liquid separation. 2. The method according to claim 1, wherein the clear separated water obtained by the solid-liquid separation is mixed with the wastewater containing the fluorine compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3841881A JPS57153790A (en) | 1981-03-17 | 1981-03-17 | Regeneration of chelating resing having adsorbed fluorine compound in it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3841881A JPS57153790A (en) | 1981-03-17 | 1981-03-17 | Regeneration of chelating resing having adsorbed fluorine compound in it |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57153790A JPS57153790A (en) | 1982-09-22 |
| JPH0140676B2 true JPH0140676B2 (en) | 1989-08-30 |
Family
ID=12524757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3841881A Granted JPS57153790A (en) | 1981-03-17 | 1981-03-17 | Regeneration of chelating resing having adsorbed fluorine compound in it |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57153790A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6230596A (en) * | 1985-07-31 | 1987-02-09 | Mitsubishi Heavy Ind Ltd | Method for treating fluorine in waste water |
| US6998054B2 (en) * | 2003-12-31 | 2006-02-14 | The Boc Group, Inc. | Selective fluoride and ammonia removal by chromatographic separation of wastewater |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5044649A (en) * | 1973-08-27 | 1975-04-22 | ||
| JPS51115058A (en) * | 1975-04-02 | 1976-10-09 | Unitika Ltd | Method for treatment of fluorine-containing solution |
| JPS5310553A (en) * | 1976-07-15 | 1978-01-31 | Kurita Water Ind Ltd | Mehtod of treating waste water containing fluorine and boron |
| JPS5944920B2 (en) * | 1977-05-24 | 1984-11-01 | ミヨシ油脂株式会社 | How to remove heavy metals |
-
1981
- 1981-03-17 JP JP3841881A patent/JPS57153790A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57153790A (en) | 1982-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5403495A (en) | Fluoride removal system | |
| US2155318A (en) | Processes for the deacidification of liquids, especially water | |
| US5039428A (en) | Waste water treatment process using improved recycle of high density sludge | |
| CN113666561B (en) | A treatment process for high-salt sulfur-containing fluorine-containing wastewater | |
| JP4543481B2 (en) | Method for treating water containing boron and fluorine | |
| JP3334142B2 (en) | Treatment method for fluorine-containing water | |
| JP4543478B2 (en) | Method for treating boron-containing water | |
| JP3203745B2 (en) | Fluorine-containing water treatment method | |
| JPH0140676B2 (en) | ||
| JP2005324137A (en) | Fluorine ion removal method in waste water | |
| JPS5924876B2 (en) | How to treat boron-containing water | |
| JPS5815193B2 (en) | How to treat boron-containing water | |
| JPH0975925A (en) | Treatment of flue gas desulfurization wastewater | |
| KR100201179B1 (en) | Process for valorizing a liquid acid effluent containing heavy metals | |
| JP3252521B2 (en) | Rinse wastewater treatment method | |
| US2471213A (en) | Treatment of aqueous liquids | |
| RU2815146C1 (en) | Method for treating terephthalic acid production wastewater from cobalt, manganese and bromine ions | |
| JPH10314797A (en) | Method for treating water containing fluoride ions and COD components | |
| JPH0368757B2 (en) | ||
| CN86108737A (en) | The preparation method of sodium chloride aqueous solution and the production method of sodium bicarbonate | |
| KR19990029232A (en) | Treatment of flue gas desulfurization drainage | |
| EP0369831B1 (en) | Process for the chemical treatment of regeneration effluents of ion exchange resins from sugar decoloration solutions, and their regenerative use | |
| JP2751875B2 (en) | Treatment method for wastewater containing fluorine | |
| JPH05269472A (en) | Method for treating water containing ammonia and fluorine ions | |
| JP4665279B2 (en) | Method for treating boron-containing water |