JPS6365991A - Treatment of waste water containing fluorine - Google Patents
Treatment of waste water containing fluorineInfo
- Publication number
- JPS6365991A JPS6365991A JP21043986A JP21043986A JPS6365991A JP S6365991 A JPS6365991 A JP S6365991A JP 21043986 A JP21043986 A JP 21043986A JP 21043986 A JP21043986 A JP 21043986A JP S6365991 A JPS6365991 A JP S6365991A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- waste water
- wastewater
- aluminum
- treatment
- 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.)
- Pending
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 31
- 239000011737 fluorine Substances 0.000 title claims abstract description 31
- 239000002351 wastewater Substances 0.000 title claims abstract description 29
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title abstract 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract description 3
- 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 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910002007 uranyl nitrate Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- KWMLJOLKUYYJFJ-UHFFFAOYSA-N 2,3,4,5,6,7-Hexahydroxyheptanoic acid Chemical compound OCC(O)C(O)C(O)C(O)C(O)C(O)=O KWMLJOLKUYYJFJ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000005289 uranyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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廃水の処理方法に関し、特に核燃料
を取扱う工程から出るフッ素含有廃水の処理に好適の方
法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for treating fluorine-containing wastewater, and particularly to a method suitable for treating fluorine-containing wastewater discharged from a process that handles nuclear fuel.
ＵＦ’ からＵＯに再転換する方法の一つに、ＵＦ６
ガス？Ａｌ（Ｎｏ３） ３水溶液に吹さ込んで硝酸ウラ
ニル（ＵＯ２（Ｎｏ３） ２） Ｙ生成せしめ、次いで
この溶液からＵＯ２（ＮＯ３）２のみｆｍ媒抽出し、重
ウラン酸アンモニウム、ＵＯを経由してＵＯとする方法
がある。One of the ways to reconvert from UF' to UO is to use UF6.
gas? Uranyl nitrate (UO2(No3)2)Y is produced by blowing into an aqueous solution of Al(No3)3, and then only UO2(NO3)2 is extracted with fm medium from this solution, and UO is extracted via ammonium deuterate and UO. There is a way to do this.
＋−引戸に４＋ 仙ＩＪＪ イｔハ 肉体ｌ→ Ａ
ＩＭ ＩＪ）Ｊｌ”ｌ −Δ／ ｒｌＪｎ
）のほかにｆｆ＆ ｆｆｉのＵを含んでいるが、この
廃液に７ツ酸を添加して廃液中のＴ！ｌｋｌ比を幾分高
めるとフッ素の大部分がＡＩＦ として析出回収され
る。+-Sliding door 4+ Sen IJJ Itha body l → A
IM IJ) Jl”l −Δ/ rlJn
) and U of ff&ffi, but by adding heptonic acid to this waste liquid, the T! When the lkl ratio is increased somewhat, most of the fluorine is precipitated and recovered as AIF.
フッ素濃度が低下したＨＮＯｅ主成分とする濾液はＵＦ
６を処理するＡｌ （Ｎｏ３）３水溶液の製造用に繰り
返し使用され、一方Ｕを殆んど含まない回収ＡＩＦ
はアルミニウム製錬用の融剤などに用いられ、かくして
上記抽出廃液はほぼ完全に処理される。The filtrate containing HNOe as the main component with a reduced fluorine concentration is UF.
The recovered AIF was repeatedly used for the production of Al (No. 3) aqueous solution for treating 6, while containing almost no U.
is used as a flux for aluminum smelting, etc., and the above-mentioned extraction waste liquid is almost completely treated in this way.
しかしながらこのＡＩＦ 回収工程においても多少洗
浄水等の廃水が発生し、この廃水はｋｌＦ を溶解し
ている。このようなフッ素を含有する廃水からフッ素を
除去するため、従来は水酸化カルシウム、炭酸カルシウ
ムご添加してフッ素ＦＳｌｉｌｉ溶性のＯａＦ とし
て回収する方法が採られている。このＯａＦ 沈殿法
により達成でさるフッ素濃度はＣａＦ２の溶解度から、
１８Ｃで約ｓ ｐｐｍと計算されるが、実際上は１５
ｐｐｍ程度が限度である。しかも回収されたＣａＦ
Ｇま殆んど利用価値がなく、堆積しておく以外に処分の
方法がない。However, even in this AIF recovery process, some wastewater such as washing water is generated, and this wastewater dissolves klF. In order to remove fluorine from such fluorine-containing wastewater, a conventional method has been adopted in which calcium hydroxide and calcium carbonate are added to recover the fluorine as FSlili-soluble OaF. The fluorine concentration achieved by this OaF precipitation method is based on the solubility of CaF2.
It is calculated to be about s ppm at 18C, but in reality it is 15
The limit is around ppm. Moreover, the recovered CaF
G has almost no usable value, and there is no other way to dispose of it other than to let it accumulate.
本発明の目的は、フッ素含有廃水からフッ素を極力回収
すると共に回収フッ素企イｆ効に利用でさるような廃水
処理方法ひ提供することにある。An object of the present invention is to provide a wastewater treatment method that can recover as much fluorine as possible from fluorine-containing wastewater and can effectively utilize the recovered fluorine.
この目的を達成するため本発明の方法は、フッ素含有廃
水にアルミニウム塩をＦ／ｌｄモル比が３以下となるよ
うに添加して該廃水を加熱し、発生蒸気企該廃水加熱系
から分離して冷却凝縮する点に特徴がある。To achieve this objective, the method of the present invention involves adding an aluminum salt to fluorine-containing wastewater so that the F/ld molar ratio is 3 or less, heating the wastewater, and separating the generated steam from the wastewater heating system. It is characterized by being cooled and condensed.
本発明法において、廃水にアルミニウム塩を添加するの
は廃水中のフッ素が蒸発するのを抑制するためであり、
加熱前の廃水中にＦ／ｈ１モル比が３以下となるように
添加する必要がある。In the method of the present invention, aluminum salt is added to wastewater in order to suppress evaporation of fluorine in wastewater.
It is necessary to add it to the wastewater before heating so that the F/h1 molar ratio is 3 or less.
アルミニウム塩の添加量が少ない即ち’ｐ’７Ａｔモル
比がこれより太さいと、フッ素の蒸発を効果的に防止で
さないからである。アルミニウム塩として、水酸化アル
ミニウム、塩化アルミニウム、硫酸アルミニウム、硝酸
アルミニウム等を用いることができるが、水酸化アルミ
ニウムが最も好ましい。This is because if the amount of aluminum salt added is small, that is, if the 'p'7At molar ratio is larger than this, evaporation of fluorine cannot be effectively prevented. As the aluminum salt, aluminum hydroxide, aluminum chloride, aluminum sulfate, aluminum nitrate, etc. can be used, but aluminum hydroxide is most preferred.
廃水の加熱蒸発手段は特に限定されず、種々の公知の手
段が適用できる。発生した蒸気はこの廃水加熱系から分
離して冷却凝縮する。発生蒸気ひ凝縮するのは蒸気に随
伴する物質を制御下におくためである。例えば廃水中に
硝酸が含まれていると窒素酸化物を発生するが、これは
蒸気の凝縮に伴なって回収される。The means for heating and evaporating waste water is not particularly limited, and various known means can be applied. The generated steam is separated from this wastewater heating system and is cooled and condensed. The reason why the generated steam is condensed is to keep the substances accompanying the steam under control. For example, if wastewater contains nitric acid, it generates nitrogen oxides, which are recovered as steam condenses.
加熱蒸発？続けると廃水中のフッ素とアルミニウムの濃
度が増し、蒸発乾固すればＡＩＰ とＡ４（０！（）３
が残る。前に述べたようなＡｌＦ 回収設備がある場
合には、ある程度濃縮した段階で濃厚廃水をＡＩＦ
回収設備に送ってこ＼でＡＩＦ ｉ回収するのが望ま
しい。このように丁れば、利用しにくいＡｌＦ 、 Ａ
ｌ（ＯＨ） 混合物の発生が避けられるからである。Heating evaporation? If this continues, the concentration of fluorine and aluminum in the wastewater will increase, and if it evaporates to dryness, AIP and A4(0!()3
remains. If there is an AIF recovery facility like the one mentioned above, the concentrated wastewater can be converted to AIF after it has been concentrated to a certain extent.
It is preferable to send it to a recovery facility for AIF i recovery. If you hang it like this, it will be difficult to use AlF, A.
This is because generation of a l(OH) mixture can be avoided.
本発明法により得られる凝縮水はフッ素濃度が極めて小
さく、プロセス水としても利用でさるし、何らかの処理
を施して系外へ排出することもてさる０
〔実施例〕
Ｆ ５ ｇ／Ｊ 、 ＡＩ １．２ｇ、／ｌ （Ｆ／
Ａ４モル比５．９）の廃水３１に水酸化アルミニウム粉
末５０ ｇを添加して２７１１モル比を１．０７に調整
し、単蒸留装置Ｇこよって加熱蒸発と凝縮を行なった。The condensed water obtained by the method of the present invention has an extremely low fluorine concentration, so it can be used as process water, or it can be treated in some way and then discharged from the system.0 [Example] F 5 g/J, AI 1.2g, /l (F/
50 g of aluminum hydroxide powder was added to the waste water 31 with an A4 molar ratio of 5.9) to adjust the 2711 molar ratio to 1.07, and heat evaporation and condensation were performed using simple distillation apparatus G.
凝縮水の受器を適時取り替え、受器から各５０ ｍｌを
採取して、フッ素濃度を測定した。結果を第１表Ｇこ示
す。The condensed water receivers were replaced at appropriate times, and 50 ml of each receiver was sampled to measure the fluorine concentration. The results are shown in Table 1.
第 １ 表
受器屋凝縮水（ｍ／）フッ素含有量（ｇ）フ・ン素濃度
（ｐｐｍ）１ １３００ ０．０００１
０．０Ｂ２ ９００ ０．０００１
０．１３ ４００ ０．０００４ １
４ １ｏ０ ０．０００２ ２５
５０ ０．０００４ ８（合計 ２７５
０ ０．００１２ 平均０．４２）第１表の結果
からフッ素と水の分離力τ極めて効果的に行なわれてい
ることが判る。Table 1 Receiver condensed water (m/) Fluorine content (g) Fluorine concentration (ppm) 1 1300 0.0001
0.0B2 900 0.0001
0.13 400 0.0004 1
4 1o0 0.0002 25
50 0.0004 8 (total 275
0 0.0012 Average 0.42) From the results in Table 1, it can be seen that the separation force τ of fluorine and water is extremely effective.
なお、比較のため同じ廃水をそのま＼で蒸留装置に供し
たところ、初期の凝縮水中の７′ノ素濃度が２００ ｐ
ｐｍ程度もあり、Ｆ／Ａｔモル比？適切に５４整しない
とフッ真の蒸発を抑制できないこと３示している。For comparison, when the same wastewater was directly subjected to a distillation device, the initial concentration of 7' nomine in the condensed water was 200 p.
There is also a pm level, and the F/At molar ratio? It is shown that evaporation of fluorine cannot be suppressed unless proper adjustment is made.
本発明法によりフッ素含有廃水から水とフッ素を効率よ
く分離でさるようになり、しかも該フッ素ご殆んど利用
可能なＡＩＦ として回収できるようになった。By the method of the present invention, water and fluorine can be efficiently separated from fluorine-containing wastewater, and most of the fluorine can be recovered as usable AIF.
出願人 住友金属鉱山株式会社 ゝ・、′−・ ゝ（−″Applicant: Sumitomo Metal Mining Co., Ltd. ゝ・、′−・ ゝ(−″
Claims (1)
比が３以下となるように添加して該廃水を加熱し、発生
蒸気を該廃水加熱系から分離して冷却凝縮することを特
徴とするフッ素含有廃水の処理方法。(1) A method characterized by adding an aluminum salt to fluorine-containing wastewater so that the F/Al molar ratio is 3 or less, heating the wastewater, separating the generated steam from the wastewater heating system, and cooling and condensing it. Method for treating fluorine-containing wastewater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21043986A JPS6365991A (en) | 1986-09-05 | 1986-09-05 | Treatment of waste water containing fluorine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21043986A JPS6365991A (en) | 1986-09-05 | 1986-09-05 | Treatment of waste water containing fluorine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6365991A true JPS6365991A (en) | 1988-03-24 |
Family
ID=16589347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21043986A Pending JPS6365991A (en) | 1986-09-05 | 1986-09-05 | Treatment of waste water containing fluorine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6365991A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001160478A (en) * | 1999-10-09 | 2001-06-12 | Eads Airbus Gmbh | Heater equipped with connecting element and/or terminating element and its manufacturing method |
-
1986
- 1986-09-05 JP JP21043986A patent/JPS6365991A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001160478A (en) * | 1999-10-09 | 2001-06-12 | Eads Airbus Gmbh | Heater equipped with connecting element and/or terminating element and its manufacturing method |
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