JPS6339694A - Method for treating waste water containing fluorine - Google Patents
Method for treating waste water containing fluorineInfo
- Publication number
- JPS6339694A JPS6339694A JP18002786A JP18002786A JPS6339694A JP S6339694 A JPS6339694 A JP S6339694A JP 18002786 A JP18002786 A JP 18002786A JP 18002786 A JP18002786 A JP 18002786A JP S6339694 A JPS6339694 A JP S6339694A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- waste water
- wastewater
- concentration
- boron
- 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
Links
- 239000002351 wastewater Substances 0.000 title claims abstract description 39
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 38
- 239000011737 fluorine Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 14
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 37
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 24
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052796 boron Inorganic materials 0.000 claims abstract description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 6
- 239000003546 flue gas Substances 0.000 claims description 6
- 238000002485 combustion reaction Methods 0.000 claims description 5
- 238000006477 desulfuration reaction Methods 0.000 claims description 5
- 230000023556 desulfurization Effects 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 5
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract 1
- 238000004220 aggregation Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 7
- -1 chlorine ions Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 238000004065 wastewater treatment Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052602 gypsum Inorganic materials 0.000 description 4
- 239000010440 gypsum Substances 0.000 description 4
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229940043430 calcium compound Drugs 0.000 description 2
- 150000001674 calcium compounds Chemical class 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はフッ素含有排水の処理方法に関し、訂しくはフ
ッ素を高濃度で含み、かつホウ素が共存する排水の処理
方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for treating fluorine-containing wastewater, and more particularly to a method for treating wastewater that contains a high concentration of fluorine and coexists with boron.
［従来の技術］
フッ素含有排水としては、たとえば石炭燃焼排ガスをカ
ルシウム化合物などを含む吸収液で処理する排煙脱硫袋
δから排出される排水等がある。[Prior Art] Fluorine-containing wastewater includes, for example, wastewater discharged from a flue gas desulfurization bag δ that treats coal combustion flue gas with an absorption liquid containing calcium compounds and the like.
通常、排水中においてフッ素は溶解度が小さく、カルシ
ウムと反応させてフッ化カルシウムを生成させることに
よって除去することができる。Generally, fluorine has a low solubility in wastewater and can be removed by reacting with calcium to produce calcium fluoride.
しかしながら、排水中にホウ素も含まれていると、フッ
素と反応してフルオロホウ酸等のポウフッ化物が生成す
るため、通常の方法では除去することが困難である。However, if boron is also contained in the wastewater, it will react with fluorine to produce fluoroboric acid and other fluoroborates, which is difficult to remove using normal methods.
そこで、フッ素含有排水の処理にあたり、アルミニウム
化合物を添加する方法が提案されている（Ｇｙｐｓｕｍ
＆ Ｌｉｍｅ 、 Ｎｏ、１３３．１９７４年）、こ
こで。Therefore, a method of adding aluminum compounds to treat fluorine-containing wastewater has been proposed (Gypsum
& Lime, No. 133.1974), here.
アルミニウム化合物としては硫酸アルミニウム（硫酸パ
ン上）やポリ塩化アルミニウム（ＰＡＣ）が使用されて
いる。通常のフッ素含有排水はフッ素濃度３００ＰＰ−
以下であり、ホウ素濃度も１５ｐｐｍ以下であるため、
これらアルミニウム化合物を用いる排水処理法によって
・応の成果を挙げている。As aluminum compounds, aluminum sulfate (on sulfuric acid pan) and polyaluminum chloride (PAC) are used. Normal fluorine-containing wastewater has a fluorine concentration of 300PP-
or less, and the boron concentration is also less than 15 ppm,
Wastewater treatment methods using these aluminum compounds have achieved significant results.
［発明が解決しようとする問題点］
しかしながら、本発明者らの研究により、排水中のフッ
素およびホウ素のいずれか−・方の濃度が通常の値より
も高い場合、特にホウ素濃度が高くなると、フッ素の除
去が困難となり、硫酸パンＬやＰＡＣの添加量の大巾な
増加を必要とし、フッ素やホウ素の濃度がさらに高くな
ると、これらアルミニウム化合物を使用しても安定した
処理を行うことが出来なくなることを知見した。[Problems to be Solved by the Invention] However, research by the present inventors has revealed that when the concentration of either fluorine or boron in wastewater is higher than the normal value, especially when the boron concentration is high, It becomes difficult to remove fluorine, necessitating a large increase in the amount of pansulfate L and PAC added, and when the concentration of fluorine and boron becomes even higher, stable processing cannot be performed even with these aluminum compounds. I found out that it disappears.
排水処理のために用いる硫酸パン上やＰＡＣの添加量が
増加することは、単に処理コストを高くするだけでなく
、下流側でのＮａＯＨ等の使用量増加につながり、さら
にはスラッジ賃が増加することになり、新たな公害聞届
の発生が避けられない、また、硫酸パン上使用量の増加
は処理水中の硫酸イオン濃度の増加をもたらし、石膏ス
ケーリングの発生という問題点がある。さらに、硫酸パ
ン−ＬやＰＡＣの使用は凝集剤であることから水酸化ア
ルミニウム等の沈看やスケーリングの発生を伴うため、
安定した排水処理を行えないという毛大な欠点がある。An increase in the amount of sulfuric acid pan and PAC used for wastewater treatment not only increases treatment costs, but also leads to an increase in the amount of NaOH, etc. used downstream, and further increases sludge fees. As a result, new pollution reports are unavoidable, and an increase in the amount of sulfuric acid pan used increases the concentration of sulfate ions in the treated water, resulting in the problem of gypsum scaling. Furthermore, since the use of Pan-L sulfate and PAC are flocculants, they are accompanied by precipitation and scaling of aluminum hydroxide, etc.
The major drawback is that stable wastewater treatment cannot be performed.
一般に、排水量はフッ素やホウ素のｅ度によって決めら
れるものではなく、液中の塩素イオン濃度やシール水量
、洗浄水量等の排煙脱硫装置系の水バランスにより決め
られるものである。Generally, the amount of drainage is not determined by the degree of e of fluorine or boron, but by the water balance of the flue gas desulfurization system, such as the concentration of chlorine ions in the liquid, the amount of sealing water, and the amount of cleaning water.
しかし、排水規制の強化、工業用水の使用制限の強化等
の実情から、排水量の底減が強く望まれている。そのた
め、処理水中の塩素イオン濃度についての対策や洗浄方
法の改良等が行われており、排水量を低減するための試
みがなされつつある。However, due to the current situation of stricter wastewater regulations and stricter restrictions on the use of industrial water, there is a strong desire to reduce the amount of wastewater. Therefore, measures are being taken to reduce the chlorine ion concentration in treated water, improvements are being made to cleaning methods, and attempts are being made to reduce the amount of waste water.
燃料である石炭は、その産地等により組成が変化するた
め、石炭燃焼排ガスを処理したときに排出される排水中
のフッ素やホウ素の濃度も様々に変化する。排水中にお
けるこれら成分の濃度変化、特に通常よりも高濃度とな
った場合、前記した従来技術で対応することは技術的に
困難であるばかりでなく、経済的にも不利である。Since the composition of coal, which is a fuel, changes depending on its production area, the concentration of fluorine and boron in waste water discharged when coal combustion exhaust gas is treated also varies. It is not only technically difficult to respond to changes in the concentration of these components in wastewater, especially when the concentration becomes higher than usual, using the above-mentioned conventional techniques, but also economically disadvantageous.
なお、フッ素を高濃度に含有する排水の処理を容易にす
るために、稀釈して排水量を増加することは、前記した
排水規制の立場から実現性が困難である。In addition, it is difficult to realize increasing the amount of waste water by diluting it in order to facilitate the treatment of waste water containing a high concentration of fluorine due to the above-mentioned waste water regulations.
［問題点を解決するための手段］
本発明は上記のような背景のもとに完成されたものであ
る。[Means for Solving the Problems] The present invention was completed against the above background.
すなわち本発明は、フッ素濃度が５００ｐｐ腸以−ヒで
あり、かつホウ素を含有する排水に塩化アルミニウムを
添加することを特徴とするフッ素含有排水の処理方法を
提供するものである。That is, the present invention provides a method for treating fluorine-containing wastewater, which is characterized by adding aluminum chloride to wastewater containing boron and having a fluorine concentration of 500 pp or more.
本発明の対象となる排水は、Ｌ記の如くフッ素を高濃度
に含み、かつホウ素を含有するものである。このような
排水として、たとえば石炭燃焼排ガスを適当な吸収剤、
たとえばカルシウム化合物を含有する吸収液で処理する
排煙脱硫装置から排出される排水などを挙げることがで
きる。The wastewater that is the object of the present invention contains a high concentration of fluorine as shown in L, and also contains boron. As such wastewater, for example, coal combustion exhaust gas is treated with an appropriate absorbent,
For example, wastewater discharged from a flue gas desulfurization device that is treated with an absorption liquid containing a calcium compound can be cited.
本発明の方法は、フッ素濃度５００ｐｐｍｌＪ Ｊｌ、
通常は５００〜３０００ｐｐｍ程度であり、かつ４０ｐ
ｐ鳳以し、通常は４０〜３００ｐｐｍ程度のホウ素を含
有する排水に対して好適に適用することができる。The method of the present invention includes a fluorine concentration of 500 ppmlJJl,
Usually about 500-3000ppm, and 40p
It can be suitably applied to wastewater that normally contains about 40 to 300 ppm of boron.
塩化アルミニウムの使用量は、Ｌ記排水中のフッ素を除
去しうる驕でよく、その形態は粉状。The amount of aluminum chloride used may be as large as it can remove fluorine from the waste water, and its form is powder.
液状など任意であるが、水溶液が取扱土岐も好ましい。Although it can be used in any form such as a liquid, it is also preferable to use an aqueous solution.
塩化アルミニウムを添加すると、排水中のフッ素、たと
えばホウ素と結合してフルオロホウ酸などのホウフッ化
物として存在するフッ素は分解し、ざらに共沈凝集効果
により糸外に除去することができる。排水中のホウフッ
化物の分解には、アルミニウムイオンの存在が必要であ
る。硫酸パン土やＰＡＣは凝集剤としての作用が強く発
現するため、液中にアルミニウムイオンとして溶解し難
いが、塩化アルミニウムは容易に解離してアルミニウム
イオンを形成する。さらに、１１！素イオンの増加から
溶解カルシウム濃度が増加するため、溶解度積からフッ
素除去効果のあるフッ化カルシウムの生成が促進され、
フッ素の除去率が向ヒする。そのため、少ない添加量で
効率よくフッ素を除去することができる。When aluminum chloride is added, fluorine in the wastewater, for example, fluorine that is present in the form of fluoroboric acid such as fluoroboric acid when combined with boron, is decomposed and can be removed from the fibers through the co-precipitation and flocculation effect. Decomposition of fluoroborides in wastewater requires the presence of aluminum ions. Since sulfuric acid clay and PAC strongly act as flocculants, they are difficult to dissolve in the liquid as aluminum ions, but aluminum chloride easily dissociates to form aluminum ions. Furthermore, 11! Since the concentration of dissolved calcium increases due to the increase in elementary ions, the production of calcium fluoride, which has a fluoride removal effect, is promoted from the solubility product.
Fluorine removal rate is improved. Therefore, fluorine can be efficiently removed with a small amount of addition.
［発明の効果］
本発明によれば、ホウ素と共に高濃度のフッ素を含有す
る排水を効率よく処理することができる。特に、排水量
の低減という要請を満足しつつ排水中のフッ素処理を行
うことができる。しかも、塩化アルミニウムを選択、使
用したことにより、従来の硫酸イオンに起因する石膏ス
ケールの発生がなく、石膏スラッジの生成がなく、安定
した状態で排水処理を行うことが可能となった。また、
塩化アルミニウムは凝集剤として作用が小さいため、配
管、タンク類への沈着やスケーリングの進行発生が極め
て小さい。[Effects of the Invention] According to the present invention, wastewater containing high concentration of fluorine as well as boron can be efficiently treated. In particular, fluorine treatment in waste water can be performed while satisfying the requirement of reducing the amount of waste water. Moreover, by selecting and using aluminum chloride, there is no generation of gypsum scale caused by conventional sulfate ions, no generation of gypsum sludge, and it is now possible to perform wastewater treatment in a stable state. Also,
Since aluminum chloride has a small effect as a flocculant, it is extremely unlikely to deposit on piping or tanks or cause scaling.
［実施例］ 次に、本発明を実施例により説明する。[Example] Next, the present invention will be explained by examples.
実施例および比較例
石炭燃焼排ガスを処理する排煙脱硫装置からの排水（フ
ッ素濃度１４００ＰＰＭ＋、ホウ素濃度１５Ｏｐｐ層、
アルミニウム濃度５０ｐｐｍ）を３■３／ｈｒで流し、
第１図に示すフッ素処理工程において添加アルミニウム
剤としてＰＡＧ 、硫酸パン上または塩化アルミニウ
ムを用いてフッ素の除去性能と失アルミニウムフロック
の付着やスケーリング状況について評価した。結果を第
２図に示す。Examples and Comparative Examples Drainage from a flue gas desulfurization equipment that processes coal combustion exhaust gas (fluorine concentration 1400 PPM+, boron concentration 15 Opp layer,
Aluminum concentration 50 ppm) was flowed at a rate of 3×3/hr.
In the fluorine treatment step shown in FIG. 1, PAG, sulfuric acid pan, or aluminum chloride was used as the additive aluminum agent to evaluate the fluorine removal performance and the adhesion and scaling of lost aluminum flocs. The results are shown in Figure 2.
図から明らかなように、フッ素除去効率は塩化アルミニ
ウムを用いた場合が最も高く、スケーリング等の発生量
は塩化アルミニウムの場合が最も少なかった。As is clear from the figure, the fluorine removal efficiency was highest when aluminum chloride was used, and the amount of scaling etc. generated was the lowest when aluminum chloride was used.
第１図は排水のフッ未処理■程の１例を示す説明図、第
２図は各種アルミニウム剤の使用による排水処理の結果
を示すグラフである。FIG. 1 is an explanatory diagram showing an example of untreated wastewater, and FIG. 2 is a graph showing the results of wastewater treatment using various aluminum agents.
Claims (3)
素を含有する排水に塩化アルミニウムを添加することを
特徴とするフッ素含有排水の処理方法。(1) A method for treating fluorine-containing wastewater, which comprises adding aluminum chloride to wastewater having a fluorine concentration of 500 ppm or more and containing boron.
から排出されるものである特許請求の範囲第１項記載の
方法。(2) The method according to claim 1, wherein the waste water is discharged from a flue gas desulfurization device that processes coal combustion exhaust gas.
つホウ素濃度４０ｐｐｍ以上のものである特許請求の範
囲第１項記載の方法。(3) The method according to claim 1, wherein the waste water has a fluorine concentration of 500 ppm or more and a boron concentration of 40 ppm or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61180027A JPH0790228B2 (en) | 1986-08-01 | 1986-08-01 | Treatment method for fluorine-containing wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61180027A JPH0790228B2 (en) | 1986-08-01 | 1986-08-01 | Treatment method for fluorine-containing wastewater |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7016390A Division JP2596908B2 (en) | 1995-01-09 | 1995-01-09 | Treatment method for fluorine-containing wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6339694A true JPS6339694A (en) | 1988-02-20 |
| JPH0790228B2 JPH0790228B2 (en) | 1995-10-04 |
Family
ID=16076187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61180027A Expired - Lifetime JPH0790228B2 (en) | 1986-08-01 | 1986-08-01 | Treatment method for fluorine-containing wastewater |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0790228B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011118808A1 (en) | 2010-03-26 | 2011-09-29 | 千代田化工建設株式会社 | Treatment method of wastewater containing persistent substances |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5310553A (en) * | 1976-07-15 | 1978-01-31 | Kurita Water Ind Ltd | Mehtod of treating waste water containing fluorine and boron |
-
1986
- 1986-08-01 JP JP61180027A patent/JPH0790228B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5310553A (en) * | 1976-07-15 | 1978-01-31 | Kurita Water Ind Ltd | Mehtod of treating waste water containing fluorine and boron |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011118808A1 (en) | 2010-03-26 | 2011-09-29 | 千代田化工建設株式会社 | Treatment method of wastewater containing persistent substances |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0790228B2 (en) | 1995-10-04 |
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