JPH0140675B2 - - Google Patents
Info
- Publication number
- JPH0140675B2 JPH0140675B2 JP55015786A JP1578680A JPH0140675B2 JP H0140675 B2 JPH0140675 B2 JP H0140675B2 JP 55015786 A JP55015786 A JP 55015786A JP 1578680 A JP1578680 A JP 1578680A JP H0140675 B2 JPH0140675 B2 JP H0140675B2
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- wastewater
- calcium
- chelate resin
- compounds
- 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
- 239000011737 fluorine Substances 0.000 claims description 28
- 229910052731 fluorine Inorganic materials 0.000 claims description 28
- 239000002351 wastewater Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 10
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 10
- 239000013522 chelant Substances 0.000 claims description 10
- 150000002222 fluorine compounds Chemical class 0.000 claims description 10
- 229940043430 calcium compound Drugs 0.000 claims description 6
- 150000001674 calcium compounds Chemical class 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 3
- 238000004065 wastewater treatment Methods 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
Description
【発明の詳細な説明】
本発明は、フツ素化合物を含む廃水からフツ素
を除去する方法に関するものである。
リン酸肥料の製造工程、アルミニウム電解精練
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、例えばフツ素とホウ素が結
合し、BF- 4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。
本発明は、このように処理困難とされているフ
ツ素化合物を含む廃水からフツ素を効率よく除去
することを目的とするものである。
本発明は、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
よりフツ素を吸着除去することを特徴とし、この
廃水に遊離のフツ素も含まれているときにはあら
かじめカルシウム化合物により該フツ素をフツ化
カルシウムとして沈殿除去したのち、鉱酸にてPH
７以下とし、フツ化カルシウムの溶解分およびフ
ツ素化合物中のフツ素をキレート樹脂によつて吸
着除去するとよい。
さらに本発明の一実施態様を添付図を参照しな
がら説明すれば、第１図において、フツ素とフツ
素化合物を含む廃水１を反応槽２へ導き、ここで
塩化カルシウムや水酸化カルシウムなどのカルシ
ウム化合物３を添加して遊離のフツ素をフツ化カ
ルシウムとして析出させる。この場合のフツ化カ
ルシウム生成におけるPH領域としてはアルカリ域
が好ましい。フツ化カルシウム析出後廃水を沈殿
池４に導きここでフツ化カルシウムを沈殿分離す
るが、高分子凝集剤５を用いることによつて沈殿
効果が促進される。沈殿池４において分離された
上澄水は、ろ過器６を経て調整槽７に導かれる
が、原廃水１中に遊離のフツ素がほとんど含まれ
ない場合には上記反応槽２および沈殿池４を経由
せずに直接ろ過器６あるいは調整槽７に導くこと
ができる。調整槽７においては、塩酸、硫酸など
の鉱酸８によつてPH７以下に調整される。次いで
キレート樹脂塔９への通水となるが、廃水のPH領
域としては第２図に示したようにPH７以下でキレ
ート樹脂によるフツ素吸着効果がよく、PH７以上
では極めて吸着効果が悪い。したがつて廃水のPH
を７以下としてキレート樹脂塔９を通過させるこ
とによつて、フツ化カルシウムの溶解分やフツ素
化合物中のフツ素のほとんどが吸着除去される。
キレート樹脂塔９の流出水は、次に中和槽１０に
導かれて水酸化ナトリウム、水酸化カリウムなど
の苛性アルカリ１１によつてPH６〜８に中和され
最終処理水１２になる。
なお、キレート樹脂塔９におけるフツ素のブレ
ークによるキレート樹脂の再生は、水酸化ナトリ
ウムと塩酸で再生率90％以上にすることができ
る。
以上述べたように本発明によれば、極めて簡単
な操作によつて従来除去困難とされていたフツ素
化合物中のフツ素を効率よく除去することができ
るのである。
次に本発明の実施例を示す。
ホウ素と結合したフツ素を20、50、100、200
mg／含む４種類の廃水をHClにてPH３とし、各
廃水を通水速度SV＝20でキレート樹脂塔に通水
し、各処理水のフツ素濃度およびフツ素のブレー
クまでの各通水量を調べた。その結果は表−１お
よび第３図に示す通りであつて、処理水フツ素濃
度は、廃水フツ素濃度20、50、100、200mg／に
対して各々５、５、12.5、29mg／で、またフツ
素ブレーク時における各廃水の通水量は各々
1200、800、500、250／−Ｒであつた。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for removing fluorine from wastewater containing fluorine compounds. Fluorine-containing wastewater is discharged from processes such as the production of phosphate fertilizers, the electrolytic refining of aluminum, and the pickling of stainless steel. Conventionally,
Fluorine in such wastewater is composed of calcium chloride, calcium chloride,
Calcium compounds such as calcium hydroxide are used to make insoluble calcium fluoride, which is then removed by precipitation. However, in wastewater containing fluorine compounds, such as wastewater containing stable complex compounds such as BF - 4 in which fluorine and boron combine, it is possible to separate the fluorine by precipitation as calcium fluoride by adding a calcium compound. Can not. The object of the present invention is to efficiently remove fluorine from wastewater containing fluorine compounds, which are difficult to treat. The present invention uses mineral acid to treat wastewater containing fluorine compounds.
It is characterized by having a pH of 7 or less, and adsorbing and removing fluorine by contacting it with a chelating resin, and when this wastewater also contains free fluorine, the fluorine is precipitated and removed as calcium fluoride using a calcium compound. Later, PH with mineral acid
7 or less, and the dissolved content of calcium fluoride and fluorine in the fluorine compound are adsorbed and removed by a chelate resin. Further, one embodiment of the present invention will be described with reference to the attached drawings. In FIG. 1, wastewater 1 containing fluorine and fluorine compounds is led to a reaction tank 2, where calcium chloride, calcium hydroxide, etc. Calcium compound 3 is added to precipitate free fluorine as calcium fluoride. In this case, the pH range for calcium fluoride production is preferably an alkaline range. After calcium fluoride has been precipitated, the wastewater is led to a settling tank 4 where the calcium fluoride is separated by precipitation, and the use of a polymer flocculant 5 promotes the precipitation effect. The supernatant water separated in the sedimentation tank 4 is led to the adjustment tank 7 via the filter 6, but if the raw wastewater 1 contains almost no free fluorine, the reaction tank 2 and the settling tank 4 are The water can be directly led to the filter 6 or the adjustment tank 7 without passing through the water. In the adjustment tank 7, the pH is adjusted to 7 or less using a mineral acid 8 such as hydrochloric acid or sulfuric acid. Next, the water is passed to the chelate resin tower 9, but as shown in FIG. 2, the fluorine adsorption effect of the chelate resin is good at pH 7 or lower, and the adsorption effect is extremely poor at pH 7 or higher, as shown in FIG. Therefore, the pH of wastewater
By passing the resin through the chelate resin tower 9 with a value of 7 or less, most of the dissolved calcium fluoride and fluorine in the fluorine compound are adsorbed and removed.
The effluent water from the chelate resin tower 9 is then led to a neutralization tank 10, where it is neutralized to pH 6 to 8 with a caustic alkali 11 such as sodium hydroxide or potassium hydroxide, and becomes the final treated water 12. Note that the regeneration of the chelate resin by breaking fluorine in the chelate resin column 9 can be achieved at a regeneration rate of 90% or more using sodium hydroxide and hydrochloric acid. As described above, according to the present invention, fluorine in fluorine compounds, which was conventionally considered difficult to remove, can be efficiently removed by an extremely simple operation. Next, examples of the present invention will be shown. 20, 50, 100, 200 fluorine combined with boron
4 types of wastewater containing mg/mg were adjusted to PH3 with HCl, each wastewater was passed through a chelate resin tower at a water flow rate of SV = 20, and the fluorine concentration of each treated water and the amount of water passed until the fluorine broke were calculated. Examined. The results are shown in Table 1 and Figure 3, and the fluorine concentrations in the treated water were 5, 5, 12.5, and 29 mg/for the wastewater fluorine concentrations of 20, 50, 100, and 200 mg/, respectively. Also, the flow rate of each wastewater during fluorine break is different.
They were 1200, 800, 500, 250/-R. 【table】
第１図は本発明の一実施態様を示すフローシー
トで、第２図はキレート樹脂吸着における廃水の
PHとフツ素の吸着量を示す線図、第３図は各フツ
素濃度における通水実験結果を示す線図である。
１……廃水、２……反応槽、３……カルシウム
化合物、４……沈殿池、６……ろ過器、７……調
整槽、８……鉱酸、９……キレート樹脂塔、１０
……中和槽、１２……最終処理水。
Figure 1 is a flow sheet showing one embodiment of the present invention, and Figure 2 is a flow sheet showing an embodiment of the present invention.
A diagram showing PH and the amount of fluorine adsorbed, and FIG. 3 is a diagram showing the results of a water flow experiment at each fluorine concentration. 1... Wastewater, 2... Reaction tank, 3... Calcium compound, 4... Sedimentation tank, 6... Filter, 7... Adjustment tank, 8... Mineral acid, 9... Chelate resin tower, 10
...Neutralization tank, 12...Final treated water.
Claims (1)
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。[Scope of Claims] 1. Treatment of wastewater containing fluorine compounds, characterized in that the wastewater containing fluorine compounds is made to have a pH of 7 or lower with a mineral acid, and fluorine is adsorbed and removed by contacting the wastewater with a chelate resin. Method. 2. When free fluorine is contained in the wastewater, a calcium compound is added in advance to remove the fluorine as calcium fluoride. Wastewater treatment methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1578680A JPS56113391A (en) | 1980-02-12 | 1980-02-12 | Disposal of waste water containing fluorine compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1578680A JPS56113391A (en) | 1980-02-12 | 1980-02-12 | Disposal of waste water containing fluorine compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56113391A JPS56113391A (en) | 1981-09-07 |
| JPH0140675B2 true JPH0140675B2 (en) | 1989-08-30 |
Family
ID=11898506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1578680A Granted JPS56113391A (en) | 1980-02-12 | 1980-02-12 | Disposal of waste water containing fluorine compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56113391A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011007392A1 (en) * | 2011-04-14 | 2012-10-18 | Helmholtz-Zentrum Für Umweltforschung Gmbh - Ufz | Method and apparatus for solid phase extraction from a liquid |
| JP2014133188A (en) * | 2013-01-08 | 2014-07-24 | Toshiba Corp | Water treatment method and water treatment apparatus |
| JP2014151310A (en) * | 2013-02-13 | 2014-08-25 | Toshiba Corp | Water treatment method and water treatment equipment |
Citations (5)
| 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 |
| JPS5217000A (en) * | 1975-07-30 | 1977-02-08 | Nippon Denso Co Ltd | Bus sensibility device |
| JPS5238772A (en) * | 1975-09-19 | 1977-03-25 | Kurita Water Ind Ltd | Boron-containing fluorine waste water disposing method |
| JPS54144764A (en) * | 1978-05-02 | 1979-11-12 | Hitachi Plant Eng & Constr Co Ltd | Method of treating borofluoride in waste water |
-
1980
- 1980-02-12 JP JP1578680A patent/JPS56113391A/en active Granted
Patent Citations (5)
| 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 |
| JPS5217000A (en) * | 1975-07-30 | 1977-02-08 | Nippon Denso Co Ltd | Bus sensibility device |
| JPS5238772A (en) * | 1975-09-19 | 1977-03-25 | Kurita Water Ind Ltd | Boron-containing fluorine waste water disposing method |
| JPS54144764A (en) * | 1978-05-02 | 1979-11-12 | Hitachi Plant Eng & Constr Co Ltd | Method of treating borofluoride in waste water |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56113391A (en) | 1981-09-07 |
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