JP4338705B2 - Method for treating waste liquid containing borofluoride ions - Google Patents
Method for treating waste liquid containing borofluoride ions Download PDFInfo
- Publication number
- JP4338705B2 JP4338705B2 JP2006021868A JP2006021868A JP4338705B2 JP 4338705 B2 JP4338705 B2 JP 4338705B2 JP 2006021868 A JP2006021868 A JP 2006021868A JP 2006021868 A JP2006021868 A JP 2006021868A JP 4338705 B2 JP4338705 B2 JP 4338705B2
- Authority
- JP
- Japan
- Prior art keywords
- ions
- boron
- waste liquid
- fluorine
- borofluoride
- 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 - Fee Related
Links
- 150000002500 ions Chemical class 0.000 title claims description 43
- 239000007788 liquid Substances 0.000 title claims description 31
- 239000002699 waste material Substances 0.000 title claims description 30
- 238000000034 method Methods 0.000 title claims description 27
- -1 boron ions Chemical class 0.000 claims description 78
- 229910052796 boron Inorganic materials 0.000 claims description 51
- 239000011737 fluorine Substances 0.000 claims description 38
- 229910052731 fluorine Inorganic materials 0.000 claims description 38
- 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 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 14
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 13
- 239000000920 calcium hydroxide Substances 0.000 claims description 13
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 13
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 6
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 5
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 3
- 229910001432 tin ion Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 23
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000033228 biological regulation Effects 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- ZOXJGFHDIHLPTG-BJUDXGSMSA-N Boron-10 Chemical compound [10B] ZOXJGFHDIHLPTG-BJUDXGSMSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229940043430 calcium compound Drugs 0.000 description 2
- 150000001674 calcium compounds Chemical class 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Images
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Removal Of Specific Substances (AREA)
Description
本発明は、メッキ廃液やガラスの表面処理等から発生するホウフッ化物イオンを含む廃液を、簡単な工程でホウ素およびフッ素を公共水域放流規制値（ホウ素１０ｐｐｍ、フッ素８ｐｐｍ）を満足させる濃度まで除去する方法に関する。
The present invention removes waste liquid containing borofluoride ions generated from plating waste liquid and glass surface treatment, etc. to a concentration satisfying the public water body discharge regulation values (
廃液中のホウ素イオンは多価金属イオンやホウ素吸着樹脂による吸着で除去され、フッ素イオンはカルシウムイオンによるフッ化カルシウムの凝集沈殿で除去される処理が一般的に行われているが、ホウ素イオンとフッ素イオンが同一廃液に混在する場合に酸性にするとホウフッ化物イオンが生成し、ホウ素イオンやフッ素イオンの従来の処理方法では除去が完全にできず、ホウフッ化化合物が残存する。従って、ホウフッ化物イオンをホウ素イオンとフッ素イオンに分解して処理する必要がある。 Boron ions in the waste liquid are removed by adsorption with polyvalent metal ions or boron adsorption resin, and fluorine ions are generally removed by agglomeration and precipitation of calcium fluoride with calcium ions. When fluorine ions are mixed in the same waste liquid, borofluoride ions are produced when acidified, and cannot be completely removed by conventional treatment methods for boron ions and fluorine ions, and borofluoride compounds remain. Therefore, it is necessary to decompose borofluoride ions into boron ions and fluorine ions for treatment.
特許文献１には、ホウフッ化物イオンを分解処理する方法として、ホウフッ化物イオンを含む廃液にアルミニウムまたは鉄の可溶性塩を加えた後、アルカリ性カルシウム塩で凝集沈殿処理を行うことにより、フッ素濃度８〜１４．４ｍｇ／ｌ程度まで処理できることが記載されている。しかしながら、ホウ素の処理結果については何ら記載がない。 In Patent Document 1, as a method for decomposing borofluoride ions, after adding a soluble salt of aluminum or iron to a waste liquid containing borofluoride ions, a coagulation precipitation treatment with an alkaline calcium salt is performed, thereby obtaining a fluorine concentration of 8 to 8. It is described that it can be processed up to about 14.4 mg / l. However, there is no description about the treatment result of boron.
特許文献２には、ホウ酸が混入したホウフッ化物の除去処理は極めて困難であることが記載され、そのための方法としてホウフッ化物含有廃液にアルミニウム化合物、塩化第二鉄、および鉄粉を加えて反応させ、該反応物にカルシウム化合物を添加して中和する方法が提案されている。しかしながら、この文献もフッ素の処理結果は記載されているが、ホウ素の処理結果については何ら記載がない。 Patent Document 2 describes that it is extremely difficult to remove borofluoride mixed with boric acid, and as a method therefor, an aluminum compound, ferric chloride, and iron powder are added to a borofluoride-containing waste liquid to react. And a method of neutralizing the reaction product by adding a calcium compound has been proposed. However, this document also describes the treatment result of fluorine, but does not describe any treatment result of boron.
ホウ素イオンを含む廃液のホウ素の固定化として、ホウ素イオンを含む廃液にアルミニウム化合物（硫酸アルミニウム）およびカルシウム化合物（消石灰）を加えてｐＨ９以上の条件下で不溶性沈殿物を生成させ、固液分離する方法が、特許文献３に記載があるように公知である。この方法はホウ素に対する硫酸アルミニウムの使用量が多く、沈殿物が多量に発生し、国内における廃棄物の最終処分場が減少していることからも、処理による沈殿物いわゆる二次廃棄物の削減が強く望まれている。 For immobilization of boron in waste liquid containing boron ions, an aluminum compound (aluminum sulfate) and calcium compound (slaked lime) are added to the waste liquid containing boron ions to form an insoluble precipitate under conditions of pH 9 or higher, and solid-liquid separation is performed. Methods are known as described in US Pat. This method uses a large amount of aluminum sulfate with respect to boron, generates a large amount of precipitates, and reduces the number of final waste disposal sites in Japan. It is strongly desired.
上述した公知の方法は、ホウ素に対する硫酸アルミニウムの使用量が多く、沈殿物が多量に発生するため、特許文献４では、硫酸アルミニウムおよび水酸化カルシウムの添加前に硫酸カルシウムを存在させておくことにより、硫酸アルミニウムおよび水酸化カルシウムの使用量を削減させる方法が提案されているが、他の薬剤が必要で、処理工程が複雑でコストが高くなる問題がある。 In the known method described above, the amount of aluminum sulfate used with respect to boron is large, and a large amount of precipitates are generated. Therefore, in Patent Document 4, calcium sulfate is present before addition of aluminum sulfate and calcium hydroxide. Although a method for reducing the amount of aluminum sulfate and calcium hydroxide used has been proposed, there is a problem that other chemicals are required, the treatment process is complicated, and the cost is increased.
以上のように、過去の検討においては、ホウフッ化物イオンの分解、フッ素イオンの処理、およびホウ素イオンの処理が別々に検討されてきたため、簡単な工程で廃液中のホウ素およびフッ素の両方を公共水域放流規制値以下の濃度に低減させる方法が提案されてこなかった。
本発明は、かかる従来技術の現状に鑑み創案されたものであり、その目的は、ホウフッ化物イオンを含む廃液を、簡単な工程でホウ素およびフッ素濃度を公共水域放流規制値（ホウ素１０ｐｐｍ、フッ素８ｐｐｍ）以下まで除去する処理方法を提供することにある。
The present invention was devised in view of the current state of the prior art. The purpose of the present invention is to reduce the waste liquid containing borofluoride ions, the boron and fluorine concentrations in a simple process, and the release values for public water bodies (
本発明者らは、かかる目的を達成するために、ホウフッ化物イオンの分解、フッ素イオンおよびホウ素イオンの処理について鋭意検討した結果、本発明の完成に至った。 In order to achieve such an object, the present inventors diligently studied the decomposition of borofluoride ions and the treatment of fluorine ions and boron ions, and as a result, the present invention was completed.
即ち、本発明は、ホウフッ化物イオン、さらに所望によりホウ素イオンおよび／またはフッ素イオンを含む廃液の処理方法であって、前記廃液にｐＨ３以下、好ましくはｐＨ２以下で多価金属イオンを添加し３５℃以上、好ましくは４０℃以上に加熱してホウフッ化物イオンをホウ素イオンとフッ素イオンに分解した後、消石灰を添加してｐＨ１０以上でフッ素イオンをフッ化カルシウムにして不溶化し、３５℃以下に冷却してから凝集剤として硫酸アルミニウムを添加し、生じた凝集物を濾過除去する工程を含むことを特徴とする方法である。
That is, the present invention is a method for treating a waste liquid containing borofluoride ions, and further optionally boron ions and / or fluorine ions, and a polyvalent metal ion is added to the waste liquid at a pH of 3 or less, preferably 2 or less. Above, preferably after heating to 40 ° C. or higher to decompose borofluoride ions into boron ions and fluorine ions, adding slaked lime to insoluble fluoride ions into calcium fluoride at
本発明の方法の好ましい実施態様では、多価金属イオンが三価の鉄イオン（二価の鉄イオンを廃液に添加した後に酸化されて生成されるものであってもよい）、三価のアルミニウムイオン、および四価の錫イオンからなる群から選択される少なくとも一種のイオンである。 In a preferred embodiment of the method of the present invention, the polyvalent metal ion is a trivalent iron ion (which may be formed by oxidation after adding a divalent iron ion to a waste liquid), trivalent aluminum It is at least one ion selected from the group consisting of ions and tetravalent tin ions.
本発明の廃液の処理方法は、基本的に、ホウフッ化物イオンをホウ素イオンおよびフッ素イオンに分解する工程、フッ素イオンを処理する工程、およびホウ素イオンを処理する工程からなることを特徴とする。本発明の処理対象となる廃液は、ホウフッ化物イオンを含むものであり、さらにホウ素イオンおよび／またはフッ素イオンを含むことができる。 The waste liquid treatment method of the present invention basically comprises a step of decomposing borofluoride ions into boron ions and fluorine ions, a step of treating fluorine ions, and a step of treating boron ions. The waste liquid to be treated in the present invention contains borofluoride ions, and can further contain boron ions and / or fluorine ions.
本発明の方法においてホウフッ化物イオンをホウ素イオンおよびフッ素イオンに分解する工程は、廃液にｐＨ３以下、好ましくはｐＨ２以下で多価金属イオンを添加し、３５℃以上、好ましくは４０℃以上に加熱し、撹拌することによって行う。この工程によってホウフッ化物イオンは多価金属イオンと反応してフッ素イオンとホウ素イオンに分解される。 In the method of the present invention, the step of decomposing borofluoride ions into boron ions and fluorine ions is performed by adding polyvalent metal ions to the waste liquid at pH 3 or lower, preferably pH 2 or lower, and heating to 35 ° C. or higher, preferably 40 ° C. or higher. , By stirring. By this step, the borofluoride ions react with the polyvalent metal ions to be decomposed into fluorine ions and boron ions.
この工程で使用される多価金属イオンとしては、三価の鉄イオン、三価のアルミニウムイオン、または四価の錫イオンなどが挙げられるが、ホウフッ化物イオンをホウ素イオンとフッ素イオンに分解する能力を有するイオンであれば特に限定されない。三価の鉄イオンを使用する場合はホウフッ化物イオンの重量に対して鉄イオン５倍以上の重量を添加し、三価のアルミニウムイオンを使用する場合はホウフッ化物イオンの重量に対してアルミニウムイオン換算０．６倍以上の重量を添加することが好ましい。なお、三価の鉄イオンに関しては、二価の鉄イオンを廃液に添加した後に酸化剤又は空気で酸化されて生成されるものを利用してもよい。 Examples of the polyvalent metal ions used in this step include trivalent iron ions, trivalent aluminum ions, and tetravalent tin ions. The ability to decompose borofluoride ions into boron ions and fluorine ions If it is an ion which has, it will not specifically limit. When using trivalent iron ions, add more than 5 times the weight of iron ions to the weight of borofluoride ions. When using trivalent aluminum ions, convert the aluminum ions to the weight of borofluoride ions. It is preferable to add a weight of 0.6 times or more. As for the trivalent iron ions, those produced by adding divalent iron ions to the waste liquid and then being oxidized with an oxidizing agent or air may be used.
多価金属イオンの供給源となる化合物としては、塩化第二鉄、塩化アルミニウム、水酸化アルミニウム、硫酸アルミニウム、または塩化第二錫等が挙げられるが、このうち塩化化合物は他の化合物のように塩酸等を加えて酸性にせずとも、それ自体の添加でｐＨ３以下になるため、有利である。 Examples of compounds that supply polyvalent metal ions include ferric chloride, aluminum chloride, aluminum hydroxide, aluminum sulfate, and stannic chloride. Of these, chloride compounds are like other compounds. Even if hydrochloric acid or the like is not added to make it acidic, it is advantageous because it becomes pH 3 or less by adding itself.
後述する参考例３において、ホウフッ化物イオンの分解温度とｐＨの関係を図１および図２に示すとおり、廃液のｐＨが１の時、温度が３５℃で、ホウフッ化物イオンのホウ素イオンとフッ素イオンへの平衡移動が促進され、ホウフッ化物イオンが減少しフッ素イオンが増加することがわかった。この分解開始温度は、廃液のｐＨが２の時が５０℃であり、ｐＨ３の時が６０℃であった。このことから、ホウフッ化物イオンの分解する温度は、３５℃以上、好ましくは４０℃以上であればよい。また、ｐＨは３以下、好ましくは２以下が望ましいことがわかった。 In Reference Example 3 to be described later, the relationship between the decomposition temperature and pH of borofluoride ions is as shown in FIGS. 1 and 2, when the pH of the waste liquid is 1, the temperature is 35 ° C., and boron ions and fluoride ions of borofluoride ions It was found that the equilibrium transfer to is promoted, borofluoride ions decrease, and fluorine ions increase. The decomposition start temperature was 50 ° C. when the pH of the waste liquid was 2, and 60 ° C. when the pH was 3. From this, the temperature at which borofluoride ions decompose is 35 ° C. or higher, preferably 40 ° C. or higher. It was also found that the pH is desirably 3 or less, preferably 2 or less.
次に、本発明の方法においてフッ素化物イオンを処理する工程は、廃液に消石灰を添加してｐＨ１０以上でフッ素イオンをフッ化カルシウムにして不溶化することによって行う。フッ素イオンの不溶化を完結させるためにはｐＨは１０以上でなければならず、より好ましくは１１以上であることが好ましい。
Next, the step of treating fluoride ions in the method of the present invention is performed by adding slaked lime to the waste liquid and insolubilizing the fluoride ions to calcium fluoride at
前述のフッ素イオンの処理工程で生成したフッ化カルシウムの凝集剤として、硫酸アルミニウムを添加すると、硫酸アルミニウムは過剰のカルシウムイオンと反応してアルミン酸カルシウムとなり、ホウ素イオンを吸着する。この時の温度によってホウ素イオンを吸着する能力が大きく変化する。本発明では、後述する実験の結果、吸着時の温度は、３５℃以下、好ましくは３０℃以下が好適であることがわかった。 When aluminum sulfate is added as an aggregating agent for calcium fluoride produced in the above-described fluorine ion treatment step, aluminum sulfate reacts with excess calcium ions to form calcium aluminate and adsorbs boron ions. The ability to adsorb boron ions greatly varies depending on the temperature at this time. In the present invention, as a result of experiments to be described later, it has been found that the temperature during adsorption is 35 ° C. or lower, preferably 30 ° C. or lower.
こうして廃液中のフッ素イオンおよびホウ素イオンの処理が終わった後、生じた凝集物を濾過除去することによってフッ素およびホウ素の濃度を公共水域放流規制値（ホウ素１０ｐｐｍ、フッ素８ｐｐｍ）以下の値に低減することができる。
After the treatment of fluorine ions and boron ions in the waste liquid is finished in this way, the concentration of fluorine and boron is reduced to a value below the public water body discharge regulation value (
実施例１
ホウフッ化物イオン１ｇ／ｌを含む溶液２００ｍｌを５０℃まで加熱し、鉄イオン１ｇ相当量の塩化第二鉄を添加して、必要であれば塩酸を添加してｐＨ２以下にし、分解時間として６０分間撹拌した後、２０重量％の消石灰懸濁液でｐＨ１１．２として３０分間撹拌した。その後２５℃まで冷却し、酸化アルミ換算８重量％の硫酸アルミニウム水溶液を３ｍｌ添加し、Ｎｏ．２の濾紙で沈殿物を除去した濾過液を分析した結果、ホウ素濃度は３．３ｐｐｍ、フッ素濃度は４．５ｐｐｍであった。いずれの値も公共水域放流規制値以下であった。
Example 1
200 ml of a solution containing 1 g / l of borofluoride ions is heated to 50 ° C., ferric chloride equivalent to 1 g of iron ions is added, and if necessary, hydrochloric acid is added to pH 2 or less, and the decomposition time is 60 minutes. After stirring, the mixture was stirred for 30 minutes with a 20% by weight slaked lime suspension at pH 11.2. After cooling to 25 ° C., 3 ml of an aluminum sulfate aqueous solution of 8% by weight in terms of aluminum oxide was added. As a result of analyzing the filtrate from which the precipitate was removed with the filter paper of No. 2, the boron concentration was 3.3 ppm and the fluorine concentration was 4.5 ppm. All values were below the public water discharge limit.
実施例２
ホウフッ化物イオン１ｇ／ｌを含む溶液２００ｍｌを６０℃まで加熱し、アルミニウムイオン１１８ｍｇ相当量の塩化アルミニウムを添加してｐＨ３以下にし、分解時間として６０分間撹拌した後、２０重量％の消石灰懸濁液でｐＨ１１．０として３０分間撹拌した。その後２５℃まで冷却し、酸化アルミ換算８重量％の硫酸アルミニウム水溶液を５ｍｌ添加し、Ｎｏ．２の濾紙で沈殿物を除去した濾過液を分析した結果、ホウ素濃度は４．２ｐｐｍ、フッ素濃度は６．４ｐｐｍであった。いずれの値も公共水域放流規制値以下であった。
Example 2
200 ml of a solution containing 1 g / l of borofluoride ions is heated to 60 ° C., aluminum chloride equivalent to 118 mg of aluminum ions is added to a pH of 3 or less, stirred for 60 minutes as the decomposition time, and then 20% by weight of slaked lime suspension At pH 11.0 and stirred for 30 minutes. Thereafter, it was cooled to 25 ° C., 5 ml of an aluminum sulfate aqueous solution of 8% by weight in terms of aluminum oxide was added. As a result of analyzing the filtrate from which the precipitate was removed with filter paper No. 2, the boron concentration was 4.2 ppm and the fluorine concentration was 6.4 ppm. All values were below the public water discharge limit.
実施例３
ホウフッ化物イオン１ｇ／ｌを含む溶液２００ｍｌを４５℃まで加熱し、アルミニウムイオン１５０ｍｇ相当量の水酸化アルミニウムを添加し、塩酸でｐＨ２にして、分解時間として６０分間撹拌した後、２０重量％の消石灰懸濁液でｐＨ１１．５として３０分間撹拌した。その後３０℃まで冷却し、酸化アルミ換算８重量％の硫酸アルミニウム水溶液を５ｍｌ添加し、Ｎｏ．２の濾紙で沈殿物を除去した濾過液を分析した結果、ホウ素濃度は６．２ｐｐｍ、フッ素濃度は６．８ｐｐｍであった。いずれの値も公共水域放流規制値以下であった。
Example 3
200 ml of a solution containing 1 g / l of borofluoride ions is heated to 45 ° C., aluminum hydroxide equivalent to 150 mg of aluminum ions is added, the pH is adjusted to 2 with hydrochloric acid, the mixture is stirred for 60 minutes, and then 20% by weight of slaked lime The suspension was adjusted to pH 11.5 and stirred for 30 minutes. Thereafter, the mixture was cooled to 30 ° C., 5 ml of an aluminum sulfate aqueous solution of 8% by weight in terms of aluminum oxide was added. As a result of analyzing the filtrate from which the precipitate was removed with the filter paper of No. 2, the boron concentration was 6.2 ppm and the fluorine concentration was 6.8 ppm. All values were below the public water discharge limit.
実施例４
フッ素イオン１ｇ／ｌおよびホウフッ化物イオン１ｇ／ｌを含む廃液２００ｍｌを塩酸でｐＨ０．５とし、アルミニウム換算２００ｍｇの塩化アルミニウムを添加し、４０℃で６０分間攪拌した。その後、２５℃まで冷却し、酸化アルミ換算８重量％の硫酸アルミニウム水溶液を５ｍｌ添加し、Ｎｏ．２の濾紙で沈殿物を除去した濾過液を分析した結果、ホウ素濃度は８．１ｐｐｍ、フッ素濃度は６．４ｐｐｍであった。いずれの値も公共水域放流規制値以下であった。
Example 4
200 ml of waste liquid containing 1 g / l of fluoride ions and 1 g / l of borofluoride ions was adjusted to pH 0.5 with hydrochloric acid, 200 mg of aluminum chloride in terms of aluminum was added, and the mixture was stirred at 40 ° C. for 60 minutes. Thereafter, the mixture was cooled to 25 ° C., 5 ml of an aluminum sulfate aqueous solution of 8% by weight in terms of aluminum oxide was added. As a result of analyzing the filtrate from which the precipitate was removed with filter paper No. 2, the boron concentration was 8.1 ppm and the fluorine concentration was 6.4 ppm. All values were below the public water discharge limit.
実施例５
ホウ素イオン０．５ｇ／ｌ、ホウフッ化物イオン１ｇ／ｌを含む廃液２００ｍｌを５５℃まで加熱し、鉄イオン１ｇ相当の塩化第二鉄を添加し、塩酸でｐＨ０．８にして、６０分間攪拌した。その後２０重量％消石灰懸濁液でｐＨ１１．２として３０分間攪拌した。その後、２５℃まで冷却し、酸化アルミ換算８重量％の硫酸アルミニウム水溶液を３．５ｍｌ添加し、Ｎｏ．２の濾紙で沈殿物を除去した濾過液を分析した結果、ホウ素濃度は６．８ｐｐｍ、フッ素濃度は４．８ｐｐｍであった。いずれの値も公共水域放流規制値以下であった。
Example 5
200 ml of waste liquid containing 0.5 g / l boron ion and 1 g / l borofluoride ion was heated to 55 ° C., ferric chloride equivalent to 1 g iron ion was added, the pH was adjusted to 0.8 with hydrochloric acid, and the mixture was stirred for 60 minutes. . Thereafter, the mixture was adjusted to pH 11.2 with a 20 wt% slaked lime suspension and stirred for 30 minutes. Thereafter, it was cooled to 25 ° C., and 3.5 ml of an aluminum sulfate aqueous solution of 8% by weight in terms of aluminum oxide was added. As a result of analyzing the filtrate from which the precipitate was removed with the filter paper of No. 2, the boron concentration was 6.8 ppm and the fluorine concentration was 4.8 ppm. All values were below the public water discharge limit.
実施例６
ホウフッ化物イオン１ｇ／ｌを含む溶液２００ｍｌを５０℃まで加熱し、鉄イオン１ｇ相当量の塩化第一鉄を添加し、塩酸でｐＨ１にして、６０分間空気をバブリングする。その後２０重量％の消石灰懸濁液でｐＨ１１．２として３０分間撹拌した。その後２５℃まで冷却し、酸化アルミ換算８重量％の硫酸アルミニウム水溶液を３ｍｌ添加し、Ｎｏ．２の濾紙で沈殿物を除去した濾過液を分析した結果、ホウ素濃度は７．５ｐｐｍ、フッ素濃度は６．８ｐｐｍであった。いずれの値も公共水域放流規制値以下であった。
Example 6
200 ml of a solution containing 1 g / l of borofluoride ions is heated to 50 ° C., ferrous chloride equivalent to 1 g of iron ions is added, the pH is adjusted to 1 with hydrochloric acid, and air is bubbled for 60 minutes. Thereafter, the mixture was adjusted to pH 11.2 with 20% by weight of slaked lime suspension and stirred for 30 minutes. After cooling to 25 ° C., 3 ml of an aluminum sulfate aqueous solution of 8% by weight in terms of aluminum oxide was added. As a result of analyzing the filtrate from which the precipitate was removed with the filter paper of No. 2, the boron concentration was 7.5 ppm and the fluorine concentration was 6.8 ppm. All values were below the public water discharge limit.
参考例１
実施例１の冷却工程で冷却せずに実施例１と同様の処理を行い、濾過液を分析したところ、ホウ素濃度は９５ｐｐｍ、フッ素濃度は４．５ｐｐｍであり、ホウ素濃度が公共水域放流規制値を満足しなかった。
Reference example 1
The same treatment as in Example 1 was performed without cooling in the cooling step of Example 1, and the filtrate was analyzed. As a result, the boron concentration was 95 ppm, the fluorine concentration was 4.5 ppm, and the boron concentration was a public water discharge limit value. I was not satisfied.
参考例２
ホウフッ化物イオン１ｇ／ｌを含む溶液１００ｍｌを５０℃まで加熱し、塩化第二鉄または塩化アルミニウムの各量を変化させて添加し、塩酸でｐＨ１とした後３０分間または６０分間撹拌して反応させたときのホウフッ化物イオンの残存量を測定した。その結果を表１、表２に示す。なお、ホウフッ化物イオンが分解されていれば（即ち、残存していなければ）、分解後の処理は実施例１と同様に行うことにより、ホウ素濃度およびフッ素濃度はともに公共水域放流規制値を満足した。
100 ml of a solution containing 1 g / l of borofluoride ions is heated to 50 ° C., added in various amounts of ferric chloride or aluminum chloride, adjusted to pH 1 with hydrochloric acid, and stirred for 30 or 60 minutes to react. The residual amount of borofluoride ions was measured. The results are shown in Tables 1 and 2. If borofluoride ions are decomposed (that is, if they do not remain), the post-decomposition treatment is carried out in the same manner as in Example 1, so that both the boron concentration and the fluorine concentration satisfy the public water discharge regulations. did.
参考例３
５００mlビーカにホウフッ化物イオン１００ｐｐｍの溶液４００ｍｌを仕込み、塩酸で所定のｐＨに調整後、各温度で１０分間攪拌し、ホウフッ化物イオンとフッ素イオン濃度を測定した結果を図１および図２に示す。ｐＨ１の場合、３５℃以上でホウフッ化物イオンのホウ素イオンおよびフッ素イオンへの平衡移動が促進されることがわかる。
Reference example 3
FIG. 1 and FIG. 2 show the results of charging 400 ml of a solution of 100 ppm borofluoride ions into a 500 ml beaker, adjusting the pH to a predetermined value with hydrochloric acid, stirring for 10 minutes at each temperature, and measuring the concentration of borofluoride ions and fluoride ions. It can be seen that at pH 1 the equilibrium transfer of borofluoride ions to boron ions and fluorine ions is promoted at 35 ° C. or higher.
参考例４
ホウ素イオン５１６ｐｐｍの溶液２００ｍｌを２０重量％消石灰懸濁液でｐＨ１１．０として３０分間撹拌し、その後アルミニウムイオン０．５６ｇ相当量の硫酸アルミニウムを添加し、様々な温度で、固液分離した溶液部分のホウ素濃度を測定した。測定したホウ素濃度の消石灰懸濁液添加による希釈量を補正した結果を図３に示す。図３からホウ素濃度を公共水域放流規制値まで低下させるには３５℃以下、好ましくは３０℃以下にしなければならないことがわかる。
Reference example 4
200 ml of a boron ion 516 ppm solution was stirred for 30 minutes at a pH of 11.0 with a 20% by weight slaked lime suspension, and then aluminum sulfate equivalent to 0.56 g of aluminum ions was added, followed by solid-liquid separation at various temperatures. The boron concentration of was measured. FIG. 3 shows the result of correcting the dilution amount due to the addition of the slaked lime suspension having the measured boron concentration. It can be seen from FIG. 3 that the boron concentration must be 35 ° C. or lower, preferably 30 ° C. or lower, in order to reduce the boron concentration to the public water body discharge regulation value.
本発明の方法によれば、ホウフッ化物イオン、さらにホウ素イオンおよびフッ素イオンを含む廃液を簡単な方法で公共水域放流規制値を満足するフッ素およびホウ素濃度まで低減する処理が可能であり、産業上極めて有用である。 According to the method of the present invention, it is possible to treat waste liquid containing borofluoride ions, and further boron ions and fluorine ions to a fluorine and boron concentration that satisfies the public water area discharge regulation value by a simple method, which is extremely industrially Useful.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006021868A JP4338705B2 (en) | 2006-01-31 | 2006-01-31 | Method for treating waste liquid containing borofluoride ions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006021868A JP4338705B2 (en) | 2006-01-31 | 2006-01-31 | Method for treating waste liquid containing borofluoride ions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007203135A JP2007203135A (en) | 2007-08-16 |
| JP4338705B2 true JP4338705B2 (en) | 2009-10-07 |
Family
ID=38483073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006021868A Expired - Fee Related JP4338705B2 (en) | 2006-01-31 | 2006-01-31 | Method for treating waste liquid containing borofluoride ions |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4338705B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014200743A (en) * | 2013-04-05 | 2014-10-27 | オルガノ株式会社 | Method of treating waste liquid containing boron fluoride ion and apparatus of treating waste liquid containing boron fluoride ion |
| KR20150120971A (en) | 2013-02-28 | 2015-10-28 | 쿠리타 고교 가부시키가이샤 | Method and apparatus for treating borofluoride-containing water |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4863302B2 (en) * | 2007-10-19 | 2012-01-25 | Ｎｅｃファシリティーズ株式会社 | Method and apparatus for treating wastewater containing boron |
| CN106145440B (en) * | 2016-07-18 | 2019-03-29 | 中石化石油工程技术服务有限公司 | Solid-liquid separation method for waste water-based drilling fluid in oil and gas fields |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60117B2 (en) * | 1981-03-03 | 1985-01-05 | 栗田工業株式会社 | How to treat fluoride-containing water |
| JPS62227496A (en) * | 1986-03-31 | 1987-10-06 | Nippon Furitsuto Kk | Method for treating waste water containing borofluoride and salts of fluorine |
| JPH09131592A (en) * | 1995-11-09 | 1997-05-20 | Babcock Hitachi Kk | Treatment of wet stack gas desulfurization waste water and device therefor |
| JP4315567B2 (en) * | 2000-03-30 | 2009-08-19 | オルガノ株式会社 | Method for treating wastewater containing fluorine and boron |
| JP2004314009A (en) * | 2003-04-18 | 2004-11-11 | Japan Organo Co Ltd | Fluorine crystallization treatment method for fluorine-containing waste water |
| JP2005193167A (en) * | 2004-01-08 | 2005-07-21 | Sophia Co Ltd | Wastewater purification method and purification method |
| JP4546764B2 (en) * | 2004-05-21 | 2010-09-15 | パナソニック株式会社 | Calcium fluoride manufacturing method and manufacturing apparatus |
-
2006
- 2006-01-31 JP JP2006021868A patent/JP4338705B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150120971A (en) | 2013-02-28 | 2015-10-28 | 쿠리타 고교 가부시키가이샤 | Method and apparatus for treating borofluoride-containing water |
| JP2014200743A (en) * | 2013-04-05 | 2014-10-27 | オルガノ株式会社 | Method of treating waste liquid containing boron fluoride ion and apparatus of treating waste liquid containing boron fluoride ion |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007203135A (en) | 2007-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100221556B1 (en) | Treatment method of flue gas desulfurization drainage | |
| JP7372691B2 (en) | How to obtain scorodite with a high arsenic content from an acidic solution with a high sulfuric acid content | |
| CN105060431B (en) | A kind of method for handling high arsenic acid water | |
| CN110240122B (en) | A kind of method for one-step detoxification of arsenic sulfide residue and recovery of sulfur | |
| CN108483690B (en) | A kind of method for treating high arsenic wastewater | |
| JP5257469B2 (en) | Remover of harmful substances in waste water and removal method using the same | |
| JP6269651B2 (en) | Method and apparatus for treating borofluoride-containing water | |
| JP4338705B2 (en) | Method for treating waste liquid containing borofluoride ions | |
| JP4306422B2 (en) | Cement kiln extraction dust processing method | |
| JPWO2005100253A1 (en) | Method for treating strongly acidic wastewater containing hazardous substances | |
| TWI263623B (en) | Effluent water treatment method | |
| JP2010234306A (en) | Method for insolubilizing selenium | |
| JP4558633B2 (en) | Wastewater treatment method containing fluoride ions | |
| JP5848119B2 (en) | Treatment method for fluorine-containing wastewater | |
| JP4604203B2 (en) | Treatment method for waste liquid containing heavy metals | |
| JP2005138017A (en) | Cement kiln extraction dust processing method | |
| JPS59199097A (en) | Disposal of waste cement slurry | |
| JP4407236B2 (en) | Treatment method of wastewater containing antimony | |
| JP5850294B2 (en) | Waste disposal method | |
| JP2009262109A (en) | Treating agent of chromium and arsenic, and treatment method using the same | |
| JP2003136070A (en) | Treatment method and treatment agent for lead-containing wastewater | |
| JP2007203239A (en) | Arsenic wastewater treatment method | |
| JP2000246229A (en) | Detoxification method for arsenic-contaminated soil | |
| JP6413772B2 (en) | Chromium-containing water treatment method | |
| JP7448129B2 (en) | How to treat wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090417 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090609 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090630 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4338705 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120710 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120710 Year of fee payment: 3 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120710 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130710 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130710 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |