JP5143440B2 - Method and apparatus for separating and recovering acid components from waste liquid containing hydrofluoric acid, hydrochloric acid and silicohydrofluoric acid - Google Patents
Method and apparatus for separating and recovering acid components from waste liquid containing hydrofluoric acid, hydrochloric acid and silicohydrofluoric acid Download PDFInfo
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- hydrochloric acid
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims description 201
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims description 143
- 239000002253 acid Substances 0.000 title claims description 91
- 239000007788 liquid Substances 0.000 title claims description 61
- 239000002699 waste material Substances 0.000 title claims description 54
- 238000000034 method Methods 0.000 title claims description 26
- 238000004821 distillation Methods 0.000 claims description 48
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 9
- TXBSWQWDLFJQMU-UHFFFAOYSA-N 4-(chloromethyl)-1,2-diethoxybenzene Chemical compound CCOC1=CC=C(CCl)C=C1OCC TXBSWQWDLFJQMU-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229940104869 fluorosilicate Drugs 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 3
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 238000003486 chemical etching Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- -1 aluminum compound Chemical class 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 238000005530 etching Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000005407 aluminoborosilicate glass Substances 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 4
- 229940043430 calcium compound Drugs 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002440 industrial waste Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 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
- 239000000498 cooling water Substances 0.000 description 2
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003100 immobilizing effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 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 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- CPGKMLVTFNUAHL-UHFFFAOYSA-N [Ca].[Ca] Chemical compound [Ca].[Ca] CPGKMLVTFNUAHL-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 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
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 229940032158 sodium silicate Drugs 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Description
近年、電子産業の発展とともに、フラットパネルディスプレイやウェハーなどケイ酸を主成分とする材料のケミカルエッチングやケミカルクリーニング等の分野で、フッ化水素酸またはフッ化水素酸に他の酸類を配合した溶液の使用が増大している。
それとともに、使用後の廃酸量も増加しており、地球環境保全の観点からその適切な処理、とりわけ廃酸中に残留している未反応酸や反応生成物などの有価物を、効率的に回収・再利用できる技術の確立が望まれている。
In recent years, with the development of the electronics industry, hydrofluoric acid or solutions containing other acids in hydrofluoric acid in fields such as chemical etching and chemical cleaning of materials based on silicic acid such as flat panel displays and wafers The use of is increasing.
At the same time, the amount of waste acid after use has increased, and from the viewpoint of global environmental protection, appropriate treatment, in particular, valuable materials such as unreacted acids and reaction products remaining in the waste acid can be efficiently used. Therefore, establishment of technology that can be recovered and reused is desired.
本発明は、これらの用途から排出される、フッ化水素酸、塩酸およびケイフッ化水素酸を含有する廃液の処理方法とその装置に関し、特に、蒸留法によりフッ化水素酸と塩酸を主成分とする留分と、塩酸をほとんど含まずフッ化水素酸とケイフッ化水素酸を主成分とする留分とに分離して回収し、工業的に再利用可能な有価成分を分離・回収する方法とその装置に関する。 The present invention relates to a method and apparatus for treating waste liquid containing hydrofluoric acid, hydrochloric acid and silicohydrofluoric acid discharged from these uses, and in particular, hydrofluoric acid and hydrochloric acid as main components by distillation. And a method for separating and recovering valuable components that can be industrially reused by separating and recovering them into fractions that contain almost no hydrochloric acid and fractions containing hydrofluoric acid and silicohydrofluoric acid as main components, and It relates to the device.
一般にフッ化水素酸やフッ素化合物を含む廃液の処理には、水酸化カルシウム、酸化カルシウム、炭酸カルシウムなどのカルシウム化合物と反応させ、難溶性のフッ化カルシウムとして固定化する方法が用いられる。廃液にホウ素を含有する場合には、カルシウム化合物による処理だけではホウフッ化物は固定化できないため、アルミニウム化合物を用いたホウフッ化物の分解処理（例えば、特許文献１参照）が必要となる。 In general, for treatment of a waste liquid containing hydrofluoric acid or a fluorine compound, a method of reacting with a calcium compound such as calcium hydroxide, calcium oxide, or calcium carbonate and immobilizing it as hardly soluble calcium fluoride is used. When boron is contained in the waste liquid, borofluoride cannot be fixed only by treatment with a calcium compound, and therefore, borofluoride decomposition treatment using an aluminum compound (for example, see Patent Document 1) is required.
しかし、このような処理で生成したフッ化カルシウムなどは、粒径が非常に細かく、そのままではほとんど濾過できないため凝集剤を用いてフロックにし、シックナーなどで沈降分離したのち、沈降したスラリーはフィルタープレスなどの濾過を行っている。濾過後の水分が５０〜６０％もあり、さらに、不純物を多量に含むため産業用として再利用できないだけでなく、そのボリュームも大きいためその処分が問題となっている。 However, the calcium fluoride produced by such treatment has a very fine particle size and can hardly be filtered as it is, so it is made floc using a flocculant and settled and separated with a thickener, etc., and the precipitated slurry is filtered with a filter press. Etc. are filtered. The water content after filtration is as high as 50 to 60%. Further, since it contains a large amount of impurities, it cannot be reused for industrial use, and its disposal is problematic due to its large volume.
また、特許文献２には、フッ化水素酸とケイフッ化水素酸を含む使用後のガラス洗浄液に、ナトリウム化合物やカリウム化合物を加え、難溶性のケイフッ化ナトリウムやケイフッ化カリウムを析出させて分離し、処理後の液をガラス洗浄液として再生させる方法が開示されている。しかし、この方法は、ガラス洗浄液として再生・再利用するには有効であるが、分離回収したケイフッ化ナトリウムやケイフッ化カリウムは不純物を含んでおり、工業的に再利用するのは困難なため、結局産業廃棄物として処分せざるをえないという問題がある。
さらに、特許文献３には、フッ化水素酸とケイフッ化水素酸やホウフッ化水素酸等を含む廃液のフッ素処理方法として、該廃液に塩化ナトリウムや塩化カリウムを加え、ケイフッ化水素酸を難溶性のケイフッ化物として固定化した後、カルシウム塩を加えてフッ素を固定化するか、ホウフッ化水素酸を含む場合は、あらかじめアルミニウム化合物を加えてホウフッ化物をホウ酸とフッ化物に分解した後、カルシウム塩を加えてフッ素を除去する方法が開示されている。
Furthermore, in
しかしながら、この方法は、フッ素含有廃液からフッ素を除去する方法としては有効であるが、特許文献２と同様の理由で、固定化分離したフッ素のカルシウム化合物の再利用が困難で、産業廃棄物として処分するしかないという問題がある。
However, this method is effective as a method for removing fluorine from a fluorine-containing waste liquid. However, for the same reason as in
一方、最近、ガラスのケミカルエッチング廃液からフッ化水素酸を分離・回収する手段として、蒸留法を適用する試みが特許文献４や特許文献５に開示されている。
しかしながら、これらの文献では、塩酸が共存する場合やケイフッ化水素酸が共存する場合の蒸留特性などについては言及されていない。
On the other hand, recently, attempts to apply a distillation method as means for separating and collecting hydrofluoric acid from glass chemical etching waste liquid are disclosed in
However, these documents do not mention the distillation characteristics in the case where hydrochloric acid coexists or in the case where hydrofluoric acid coexists.
本発明は、以上のような化学的処理を主体とする背景技術では成し得ず、かつ背景技術で述べた問題点を解消し、フッ化水素酸、塩酸およびケイフッ化水素酸を含有する廃液から、再利用可能なフッ化水素酸および塩酸ならびにケイフッ化水素酸を効率よく分離・回収する方法とその装置とを提供することを目的とする。 The present invention can not be achieved by the background art mainly composed of the chemical treatment as described above, solves the problems described in the background art, and contains a waste liquid containing hydrofluoric acid, hydrochloric acid and silicohydrofluoric acid. Therefore, an object of the present invention is to provide a method and an apparatus for efficiently separating and recovering reusable hydrofluoric acid, hydrochloric acid and silicohydrofluoric acid.
一般に、ガラスのケミカルエッチングには、フッ化水素酸やフッ化アンモニウム等のフッ化物を主成分とし、これに塩酸、硫酸、硝酸、リン酸等の無機酸を配合したエッチング液が多く用いられる。これら各種成分の種類や配合比はエッチングメーカーのノウハウとしてブラックボックス化されているが、いずれの場合も、決められた成分の濃厚原液を決められた濃度となるように混合して、すなわち、エッチング液を調整して用いるのが一般的である。 In general, for chemical etching of glass, an etchant containing a fluoride such as hydrofluoric acid or ammonium fluoride as a main component and an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or the like is often used. The types and mixing ratios of these various components are black boxed as an etching manufacturer's know-how, but in each case, a concentrated stock solution of a predetermined component is mixed to a predetermined concentration, that is, etched. In general, the liquid is used after being adjusted.
本発明では、これらのうちフッ化水素酸と塩酸を主要成分とするケミカルエッチング液の使用済み廃液を主たる対象とし、各成分の配合比には左右されずに未反応成分や有価物を分離・回収できる方法とその装置とを提供するものである。 In the present invention, among these, used waste liquid of chemical etching liquids mainly composed of hydrofluoric acid and hydrochloric acid is mainly targeted, and unreacted components and valuable materials are separated regardless of the mixing ratio of each component. Provided are a recoverable method and an apparatus therefor.
一方、本発明では、ケミカルエッチングの対象となるガラスの種類は特に限定されるものではなく、例えば、フラットパネルディスプレイ用に用いられるアルミノホウケイ酸ガラスのケミカルエッチング廃液に適用できる。 On the other hand, in the present invention, the type of glass to be subjected to chemical etching is not particularly limited, and can be applied to, for example, chemical etching waste liquid of aluminoborosilicate glass used for flat panel displays.
アルミノホウケイ酸ガラスの構成成分は、ＳｉＯ２、Ａｌ２Ｏ３、Ｂ２Ｏ３、ＣａＯ、ＭｇＯ、ＢａＯ、ＳｒＯなどから成り、それらをフッ化水素酸を含む液でエッチングすると、次式のような反応により各種のフッ素化合物を生成する。
（反応式）
ＳｉＯ２ ＋ ６ＨＦ → Ｈ２ＳｉＦ６ ＋ ２Ｈ２Ｏ （１）
Ｂ２Ｏ３ ＋ ８ＨＦ → ２ＨＢＦ４ ＋ ３Ｈ２Ｏ （２）
Ａｌ２Ｏ３ ＋ ６ＨＦ → ２ＡｌＦ３ ＋ ３Ｈ２Ｏ （３）
ＭｇＯ ＋ ２ＨＦ → ＭｇＦ２ ＋ Ｈ２Ｏ （４）
ＣａＯ ＋ ２ＨＦ → ＣａＦ２ ＋ Ｈ２Ｏ （５）
ＳｒＯ ＋ ２ＨＦ → ＳｒＦ２ ＋ Ｈ２Ｏ （６）
The constituents of aluminoborosilicate glass are composed of SiO 2 , Al 2 O 3 , B 2 O 3 , CaO, MgO, BaO, SrO, etc. When etched with a liquid containing hydrofluoric acid, the following formula is obtained: Various fluorine compounds are produced by a simple reaction.
(Reaction formula)
SiO 2 + 6HF → H 2 SiF 6 + 2H 2 O (1)
B 2 O 3 + 8HF → 2HBF 4 + 3H 2 O (2)
Al 2 O 3 + 6HF → 2AlF 3 + 3H 2 O (3)
MgO + 2HF → MgF 2 + H 2 O (4)
CaO + 2HF → CaF 2 + H 2 O (5)
SrO + 2HF → SrF 2 + H 2 O (6)
これらフッ素化合物のうち、Ａｌ、Ｃａ、Ｍｇ、Ｓｒ、Ｂａのフッ素化合物の一部もしくはほとんどは難溶性塩として析出するが、ケイフッ化水素酸（Ｈ２ＳｉＦ６）および四フッ化ホウ素酸（ＨＢＦ４）は、析出することなくエッチング廃液中に溶解した状態で存在することになる。したがって、本発明においては、ケミカルエッチング廃液中の未反応のフッ化水素酸や塩酸を分離・回収するとともに、有価物であるケイフッ化水素酸を純度の高い状態で分離・回収することも重要な課題となる。 Among these fluorine compounds, some or most of the fluorine compounds of Al, Ca, Mg, Sr, and Ba are precipitated as hardly soluble salts. However, hydrofluoric acid (H 2 SiF 6 ) and tetrafluoroboric acid (HBF) 4 ) will exist in the state which melt | dissolved in the etching waste liquid, without depositing. Therefore, in the present invention, it is also important to separate and recover unreacted hydrofluoric acid and hydrochloric acid in the chemical etching waste liquid and to separate and recover valuable hydrosilicofluoric acid in a high purity state. It becomes a problem.
一般に、フッ化水素酸や塩酸のような揮発性の酸は、他の不揮発性の酸例えば硫酸やリン酸または塩類が共存することにより、揮発しやすさ（揮発度）が変化することが知られている。そこで、本発明者らはこの知見に着目し、蒸留法による揮発分離特性を鋭意検討した結果、上記ケミカルエッチング廃液中にケイフッ化水素酸が共存することによっても、フッ化水素酸や塩酸の揮発特性が変化することを見出し、本発明を完成させるに至った。 In general, volatile acids such as hydrofluoric acid and hydrochloric acid are known to change their volatility (volatility) due to the presence of other non-volatile acids such as sulfuric acid, phosphoric acid or salts. It has been. Therefore, the present inventors paid attention to this knowledge, and as a result of intensive studies on the volatilization separation characteristics by the distillation method, the volatilization of hydrofluoric acid and hydrochloric acid is also caused by the presence of hydrofluoric acid in the chemical etching waste liquid. The inventors have found that the characteristics are changed and have completed the present invention.
すなわち、模擬廃液として、フッ化水素酸５％、塩酸２％およびケイフッ化水素酸１０％を含有する溶液を、市販の各酸の濃厚原液を用いて調製し、フッ素樹脂製の単蒸留装置を用い大気圧下で蒸留試験を行った結果、表１に示すデータを得た。 That is, as a simulated waste liquid, a solution containing 5% hydrofluoric acid, 2% hydrochloric acid and 10% silicofluoric acid was prepared using a concentrated concentrated stock solution of each acid, and a single distillation apparatus made of a fluororesin was prepared. As a result of performing a distillation test under atmospheric pressure, data shown in Table 1 was obtained.
表１の留分１と留分２の酸濃度組成を比較すれば明らかなように、塩酸は、蒸留初期（留分１）はフッ化水素酸より揮発しにくいが、被蒸留液中のケイフッ化水素酸が濃縮された状態で蒸留された留分２では、塩酸とフッ化水素酸の濃度が逆転し、フッ化水素酸より塩酸の方が揮発しやすくなっていることが分かる。
As is clear from the comparison of the acid concentration compositions of
さらに蒸留を続けると、留分３ではフッ化水素酸や塩酸とともにケイフッ化水素酸の揮発が起こり、最後に残った釜残には塩酸はほとんどなく、フッ化水素酸と高濃度のケイフッ化水素酸が残ることが確認され、留分分画をさらに最適化することにより、所望の酸を選択的に含む留分を効率的に分離・回収できる可能性を見出した。また、表１と同一組成の調製液にホウフッ化水素酸を１％添加して単蒸留した結果、表１とほぼ同様の結果が得られ、ホウフッ化水素酸は揮発せずに釜残中に残ることも確認することができた。
If distillation continues further, hydrofluoric acid and hydrochloric acid will volatilize together with hydrofluoric acid and hydrochloric acid in
これらの結果を基に、本発明（第１の発明）では、フッ化水素酸、塩酸およびケイフッ化水素酸を含む廃液から酸成分を分離・回収するに当って、前記廃液を常圧もしくは減圧下における蒸留操作によって、酸をほとんど含まない水主体の留分、ケイフッ化水素酸をほとんど含まずフッ化水素酸と塩酸を主成分として含む留分、ならびに塩酸をほとんど含まずフッ化水素酸とケイフッ化水素酸を主成分として含む釜残とに、順次分離して回収する。 Based on these results, in the present invention (first invention), in separating and recovering the acid component from the waste liquid containing hydrofluoric acid, hydrochloric acid and silicohydrofluoric acid, the waste liquid is subjected to normal pressure or reduced pressure. by distillation under, fractions containing almost no water mainly acid, and silicic hydrofluoric acid fraction containing as little contain not composed mainly of hydrofluoric acid and hydrochloric acid, and containing almost no hydrofluoric acid hydrochloride fluorosilicate Kamizu periodate in the bottoms containing as a main component, it is recovered sequentially separated.
蒸留は常圧もしくは減圧のいずれの条件で行なうことができるが、温度を８０℃以下で操作できる減圧条件（１００ｍｍＨｇ以下）で実施すれば、フッ素樹脂等の高価な装置材料を必要とせず、ポリエチレン、ポリプロピレンや耐熱ポリ塩化ビニール等の安価な材料を選択できるので有利である。 Distillation can be carried out under normal pressure or reduced pressure, but if it is carried out under reduced pressure conditions (100 mmHg or less) that can be operated at a temperature of 80 ° C. or less, it does not require expensive equipment materials such as fluororesin and polyethylene. It is advantageous because inexpensive materials such as polypropylene and heat-resistant polyvinyl chloride can be selected.
なお、本発明では、フッ化水素酸、塩酸およびケイフッ化水素酸を含む廃液を蒸留する場合において、前記廃液が酸をほとんど含まない水主体の留分となる温度まで蒸留して得た留分を、「初留」という。また、前記廃液がケイフッ化水素酸をほとんど含まずフッ化水素酸と塩酸を主成分として含む留分となる温度まで蒸留して得た留分を、「主留」という。さらに、前記廃液がフッ化水素酸、塩酸とともにケイフッ化水素酸の揮発が起こる温度まで蒸留して得た留分を、「後留」という。そして、上記３段階の蒸留後において、塩酸をほとんど含まずフッ化水素酸とケイフッ化水素酸が残った状況を、「釜残」という。In the present invention, when the waste liquid containing hydrofluoric acid, hydrochloric acid and silicofluoric acid is distilled, a fraction obtained by distillation to a temperature at which the waste liquid becomes a water-based fraction containing almost no acid. Is called "Hatsuru". The fraction obtained by distillation to a temperature at which the waste liquid contains a fraction containing silicohydrofluoric acid and containing hydrofluoric acid and hydrochloric acid as main components is referred to as “main fraction”. Further, a fraction obtained by distilling the waste liquid to a temperature at which volatilization of hydrofluoric acid with hydrofluoric acid and hydrochloric acid occurs is referred to as “post distillation”. Then, after the above three-stage distillation, the situation in which hydrofluoric acid and silicohydrofluoric acid remain without any hydrochloric acid is referred to as “bottle residue”.
前記の場合において、前記塩酸をほとんど含まずフッ化水素酸とケイフッ化水素酸を主成分として含む釜残に、硫酸またはリン酸の一種もしくは二種を添加して常圧または減圧下で蒸留し、初留分を分離・回収した後、塩酸含有量がさらに少なくフッ化水素酸とケイフッ化水素酸を主成分として含む留分を分離・回収するとよい。 In the above case, one or two kinds of sulfuric acid or phosphoric acid are added to the residue of the kettle which contains almost no hydrochloric acid and contains hydrofluoric acid and silicohydrofluoric acid as main components, and distilled under normal pressure or reduced pressure. After separating and collecting the initial fraction, it is preferable to separate and collect the fraction having a smaller content of hydrochloric acid and containing hydrofluoric acid and silicohydrofluoric acid as main components.
これらの場合において、釜残液に硫酸および／またはリン酸を加え、揮発成分の揮発度を高めて蒸留することにより、残留しているほとんどの塩酸およびフッ化水素酸の一部を初留分として分離除去し、フッ化水素酸とケイフッ化水素酸を主成分として含む留分を回収することができる。添加する硫酸または／およびリン酸の濃度は、合計で５〜５０％、好ましくは５〜３０％でよく、硫酸およびリン酸は不揮性であってそのまま釜残に残るので、繰り返し利用することも可能である。 In these cases, sulfuric acid and / or phosphoric acid is added to the kettle residue to increase the volatility of the volatile components and distill. The fraction containing hydrofluoric acid and silicohydrofluoric acid as main components can be recovered. The concentration of sulfuric acid and / or phosphoric acid to be added may be 5 to 50% in total, preferably 5 to 30%. Since sulfuric acid and phosphoric acid are non-volatile and remain in the kettle, use them repeatedly. Is also possible.
ここに、フッ化水素酸、塩酸およびケイフッ化水素酸を含む前記廃液を本発明の方法によって処理した後の「釜残」を蒸留する場合において、前記釜残中に含まれる塩酸のほとんどを留出させる温度まで蒸留して得た留分を、「初留」という。また、大半の塩酸留出後、フッ化水素酸とケイフッ化水素酸を主成分として含む留分となる温度まで蒸留して得た留分を、「主留」という。そして、上記２段階の蒸留後において、塩酸をほとんど含まずフッ化水素酸とケイフッ化水素酸およびホウフッ酸が残った状況を、「釜残」という。When distilling the “bottle residue” after treating the waste liquid containing hydrofluoric acid, hydrochloric acid and silicohydrofluoric acid by the method of the present invention, most of the hydrochloric acid contained in the kettle residue is distilled. The fraction obtained by distillation up to the temperature to be discharged is referred to as “first distillation”. Further, a fraction obtained by distillation after distillation of most of hydrochloric acid to a temperature at which a fraction containing hydrofluoric acid and silicohydrofluoric acid as main components is obtained is referred to as “main fraction”. The situation in which hydrofluoric acid, silicohydrofluoric acid, and borofluoric acid remain substantially free of hydrochloric acid after the two-stage distillation is referred to as “bottle residue”.
また、本発明（第２の発明）では、前記の場合において分離・回収した、塩酸をほとんど含まずフッ化水素酸とケイフッ化水素酸を主成分として含む釜残もしくは留分に、酸化ケイ素を加え、共存するフッ化水素酸をケイフッ化水素酸に変換して、ケイフッ化水素酸を主成分とする溶液を調製する。 In the present invention (second invention), silicon oxide is added to the residue or fraction which is separated and recovered in the above-described case and contains almost no hydrochloric acid and contains hydrofluoric acid and silicohydrofluoric acid as main components. In addition, the coexisting hydrofluoric acid is converted to silicohydrofluoric acid to prepare a solution containing silicohydrofluoric acid as a main component.
すなわち、第２の発明は、分離・回収するケイフッ化水素酸溶液の純度と濃度を高めることを目的としており、フッ化水素酸と酸化ケイ素との反応によりケイフッ化水素酸が生成することを利用している。添加する酸化ケイ素は、溶存するフッ化水素酸との反応等量分で十分である。 That is, the second invention aims to increase the purity and concentration of the hydrofluoric acid solution to be separated / recovered, and utilizes the fact that silicofluoric acid is generated by the reaction of hydrofluoric acid and silicon oxide. doing. The amount of silicon oxide to be added is sufficient for the reaction equivalent with dissolved hydrofluoric acid.
前記いずれかの場合において、廃液中にアルミニウムを含有する系で蒸留により濃縮されて発生し釜残に析出するフッ化アルミニウム・３水和物を濾過手段により分離して有価物を回収することができる。回収したフッ化アルミニウム・３水和物は、純度が高いので工業的に再利用が可能である。 In any of the above cases, the aluminum fluoride trihydrate generated by concentration in the waste liquid by distillation in the system and precipitated in the kettle residue is separated by filtration means to recover valuable materials. it can. Since the recovered aluminum fluoride trihydrate has a high purity, it can be reused industrially.
本発明による蒸留法により分離された、フッ化水素酸と塩酸を含む回収酸は、工業用酸原液と同等の酸液として再利用が可能であり、実際にケミカルエッチング液に問題なく適用できることが確認されている。 The recovered acid containing hydrofluoric acid and hydrochloric acid separated by the distillation method according to the present invention can be reused as an acid solution equivalent to an industrial acid stock solution, and can be applied to a chemical etching solution without any problem. It has been confirmed.
前記いずれかの場合において、フッ化水素酸、塩酸およびケイフッ化水素酸を含む廃液は、ガラスのケミカルエッチング廃液として利用することができる。これらの場合において回収されたフッ化水素酸および塩酸を主成分とする回収酸は、ガラスのケミカルエッチング液として再利用することができる。 In any of the above cases, the waste liquid containing hydrofluoric acid, hydrochloric acid, and silicohydrofluoric acid can be used as a chemical etching waste liquid for glass. The recovered acid mainly composed of hydrofluoric acid and hydrochloric acid recovered in these cases can be reused as a chemical etching solution for glass.
一方、本発明（第３の発明）は、フッ化水素酸、塩酸およびケイフッ化水素酸を含む廃液から酸成分を分離・回収するための常圧または減圧蒸留装置であって、蒸発缶、精留塔、初留受器、フッ化水素酸および塩酸の混合酸回収槽ならびに後留受器を備えたことを特徴とする。 On the other hand, the present invention (third invention) is an atmospheric or vacuum distillation apparatus for separating and recovering an acid component from a waste liquid containing hydrofluoric acid, hydrochloric acid, and silicohydrofluoric acid. A distillation column, an initial distillation receiver, a mixed acid recovery tank of hydrofluoric acid and hydrochloric acid, and a post distillation receiver are provided.
この場合において、釜残液に含まれる固形物を濾別する手段を備えていることが好ましい。この装置を用いて分離・回収される固形物は、高純度のフッ化アルミニウム・３水和物であり、工業的に再利用が可能である。 In this case, it is preferable to provide a means for filtering off the solids contained in the residual liquor. Solids separated and recovered using this apparatus are high-purity aluminum fluoride trihydrate and can be reused industrially.
そして、前記固形物を濾別する手段の後段に、濾液に硫酸またはリン酸の一種もしくは二種を添加して蒸留する蒸発缶、精留塔、初留受器ならびにケイフッ化水素酸回収槽を備えていることが望ましい。 Then, after the means for filtering out the solid matter, an evaporator, a rectifying column, an initial distillation receiver, and a hydrofluoric acid recovery tank for adding and distilling one or two kinds of sulfuric acid or phosphoric acid to the filtrate are provided. It is desirable to have it.
請求項１〜５のいずれかに記載の方法および請求項６〜８のいずれかに記載の装置を用いて、フッ化水素酸、塩酸およびケイフッ化水素酸を含む廃液から酸成分を分離・回収することにより、少なくともフッ化水素酸と塩酸を含む酸を効率よく回収することができる。この回収酸はケミカルエッチング液はもとより工業用酸液として再利用でき、高濃度・高純度のケイフッ化水素酸含有酸および高純度のフッ化アルミニウム・３水和物は工業的に再利用が可能であるとともに、産業廃棄物の量を著しく低減することができ、環境対策に大きく貢献できる。
Using the method according to any one of
供試液として、フッ化水素酸６．０％、塩酸２．３％およびケイフッ化水素酸１１．５％、ホウフッ化水素酸１．１％などを含むアルミノホウケイ酸ガラスのケミカルエッチング廃液を使用した。
図１は、ケミカルエッチング廃液の蒸留処理のためのベンチプラント図を示す。
ケミカルエッチング廃液を蒸発缶１に約５ｋｇを仕込み、凝縮器３および凝縮器４に冷却水を流す。真空ポンプ９を作動させて系内を８０ｍｍＨｇに保持したのち、蒸発缶１の熱交換器に０．１ＭＰａに減圧したスチームを一定速度で流して加熱して減圧蒸留を開始した。留出物は精留塔２に入り、凝縮器３および４で凝縮される。凝縮液の一部は精留塔２に戻して還流させ、残りは初留受器５、ＨＣｌ−ＨＦ回収槽６、後留受器７の順に抜き出した。蒸留後、真空ポンプ９を停止し、系内を常圧に戻す。初留受器５中の液は酸分が１％以下でありそのまま通常の排水処理を行った。ＨＣｌ−ＨＦ回収槽６中の液はケイフッ化水素酸をほとんど含まずフッ化水素酸と塩酸を主成分として含んでおり、抜き出した後、塩酸とフッ化水素酸濃度を調整してケミカルエッチング液として再利用する。後留受器７中の液は相当量のケイフッ化水素酸を含んでいるため、好ましくは蒸発缶１に戻して再度蒸留する。蒸発缶１に残った釜残は、フッ化アルミニウム・３水和物を含むスラリーで、濾過器１０でフッ化アルミニウム・３水和物を濾別・回収し、塩酸をほとんど含まずフッ化水素酸とケイフッ化水素酸を主成分として含む濾液を粗製Ｈ２ＳｉＦ６貯槽１１に回収する。
As a test solution, a chemical etching waste solution of aluminoborosilicate glass containing 6.0% hydrofluoric acid, 2.3% hydrochloric acid, 11.5% silicofluoric acid, 1.1% borohydrofluoric acid and the like was used. .
FIG. 1 shows a bench plant diagram for distillation treatment of chemical etching waste liquid.
About 5 kg of chemical etching waste liquid is charged into the
図２は、エッチング廃液の蒸留処理で釜残として回収した粗製Ｈ２ＳｉＦ６の蒸留処理のためのベンチプラント図を示す。
ケミカルエッチング廃液の蒸留処理で得られた、塩酸をほとんど含まずフッ化水素酸とケイフッ化水素酸を主成分として含む粗製Ｈ２ＳｉＦ６４．０Ｋｇと硫酸またはリン酸の一種もしくは二種を１．０ｋｇテフロン（登録商標）製熱交換器を備えた蒸発缶１３に仕込み、凝縮器１５および凝縮器１６に冷却水を流す。真空ポンプ２０を作動させて系内を８０ｍｍＨｇに保持したのち、蒸発缶１３の熱交換器に０．１ＭＰａに減圧したスチームを一定速度で流して加熱して減圧蒸留を開始した。留出物は精留塔１４に入り、凝縮器１５および１６で凝縮される。凝縮液の一部は蒸発缶１３に戻して還流させ、残りは初留受器１７、Ｈ２ＳｉＦ６回収槽１８の順に抜き出した。蒸留後、真空ポンプ２０を停止し、系内を常圧に戻す。初留受器１７中の液は０．５〜２．０％の塩酸を含んでおり、ケイフッ化水素酸の原料に使用できないため、蒸発缶１３に戻しエッチング廃液と共に再蒸留する。Ｈ２ＳｉＦ６回収槽１８中の液は塩酸含量０．０１％以下であり抜き出してから酸化ケイ素ＳｉＯ２を加え、共存するフッ化水素酸をケイフッ化水素酸に変換して、ケイフッ化水素酸溶液を調製する。
FIG. 2 shows a bench plant diagram for the distillation treatment of crude H 2 SiF 6 recovered as a residue in the etching waste liquid distillation treatment.
Crude H 2 SiF 6 ( 4.0 kg) containing almost no hydrochloric acid and containing hydrofluoric acid and silicohydrofluoric acid as main components, and one or two kinds of sulfuric acid or phosphoric acid obtained by distillation treatment of the chemical etching waste liquid An
（実施例１：請求項１および請求項４の実施例）
図１に示す装置を用い、フッ化水素酸６．０％、塩酸２．３％およびケイフッ化水素酸１１．５％、ホウフッ化水素酸１．１％などを含むアルミノホウケイ酸ガラスのケミカルエッチング実廃液５．０ｋｇの蒸留試験を、８０ｍｍＨｇの減圧下、５０〜７０℃の条件で行った。得られた留分および釜残の分析結果を、表２に示す。
表２から分かるように、フッ化水素酸と塩酸の合計濃度が約１％の初留分１，４６０ｇと、フッ化水素酸と塩酸の合計濃度が約１２％の主留分１，９９０ｇおよびケイフッ化水素酸を主成分とする後留および釜残とに分離・回収することができている。このときの釜残液の組成は、塩酸０.２％で、フッ化水素酸１０．２％、ケイフッ化水素酸は３８．３％と高濃度を有していた。さらに釜残には、スラリー状で高純度のフッ化アルミニウム・３水和物が含まれ、これを通常の濾過操作で２７ｇを容易に回収することができた。
(Example 1: Examples of
Using the apparatus shown in FIG. 1, chemical etching of aluminoborosilicate glass containing 6.0% hydrofluoric acid, 2.3% hydrochloric acid, 11.5% silicofluoric acid, 1.1% borohydrofluoric acid, etc. A distillation test of 5.0 kg of actual waste liquid was conducted under conditions of 50 to 70 ° C. under reduced pressure of 80 mmHg. Table 2 shows the analysis results of the obtained fraction and residue.
As can be seen from Table 2, 1,460 g of the initial fraction having a total concentration of hydrofluoric acid and hydrochloric acid of about 1%, 1,990 g of the main fraction having a total concentration of hydrofluoric acid and hydrochloric acid of about 12%, and It can be separated and recovered into a bottom fraction and a kettle residue mainly composed of silicofluoric acid. At this time, the composition of the residue in the kettle was 0.2% hydrochloric acid, 10.2% hydrofluoric acid, and 38.3% hydrosilicic acid. Further, the residue of the kettle contained high purity aluminum fluoride trihydrate in a slurry state, and 27 g of this could be easily recovered by a normal filtration operation.
新たな供試液４．５ｋｇに前回の後留分６５０ｇを加えて蒸留を行い、発生した後留分を次に回す操作を繰り返し計１８回の減圧蒸留を行った。得られた留分および釜残の分析結果を、表３に示す。 Distillation was performed by adding 650 g of the previous fractional fraction to 4.5 kg of the new test solution, and repeating the operation of turning the generated fractional fraction next to perform vacuum distillation a total of 18 times. Table 3 shows the analysis results of the obtained fraction and residue.
主留分を回収し、フッ酸および水を加えて、塩酸２．５％、フッ化水素酸２０％、ケイフッ化水素酸０．６％を含む溶液を調製し、アルミノホウケイ酸ガラスのケミカルエッチング剤に供した結果、何ら問題は見られなかった。 Collect the main fraction, add hydrofluoric acid and water to prepare a solution containing 2.5% hydrochloric acid, 20% hydrofluoric acid, and 0.6% silicofluoric acid. Chemical etching of aluminoborosilicate glass As a result of applying to the agent, no problem was found.
（実施例２：請求項３の実施例と釜残中の塩酸の低減）
実施例１で得た、釜残５．０ｋｇを図２に示す蒸発缶１３に仕込み、８０ｍｍＨｇの減圧下で蒸留した。得られた留分および釜残の分析結果を、表４に示す。
(Example 2: Example of
The remaining kettle (5.0 kg) obtained in Example 1 was charged into the
主留分のフッ化水素分を当量のＳｉＯ２を加えて反応させてケイフッ化水素酸に変換し、水を加えて４０％ケイフッ化水素酸を調製した。塩素分が２００ｐｐｍと少し高い以外は市販品として問題はなかった。 Hydrogen fluoride in the main fraction is reacted by adding SiO 2 eq converted to silicic hydrofluoric acid was prepared 40% silicic hydrofluoric acid was added water. There was no problem as a commercial product except that the chlorine content was as high as 200 ppm.
（実施例３：請求項２および請求項３の実施例）
実施例２で得たケイフッ化水素酸よりも塩酸含量を減らす目的で、塩酸の揮発度を増加させるために不揮発酸として９８％硫酸５００ｇと実施例１で得た釜残５．０ｋｇを蒸発缶１３に仕込み、８０ｍｍＨｇの減圧下で蒸留した。得られた留分および釜残の分析結果を表５に示す。
(Embodiment 3: Embodiments of
In order to reduce the content of hydrochloric acid compared to the hydrofluoric acid obtained in Example 2, 500 g of 98% sulfuric acid as non-volatile acid and 5.0 kg of the kettle remaining obtained in Example 1 were evaporated to increase the volatility of hydrochloric acid. 13 and distilled under reduced pressure of 80 mmHg. Table 5 shows the analysis results of the obtained fraction and residue.
主留分のフッ化水素分を当量のＳｉＯ２を加えて反応させてケイフッ化水素酸に変換し、水を加えて４０％ケイフッ化水素酸を調製した。不純物の分析結果、すべて市販用の高純度ケイフッ化水素酸の規格内であった。 Hydrogen fluoride in the main fraction is reacted by adding SiO 2 eq converted to silicic hydrofluoric acid was prepared 40% silicic hydrofluoric acid was added water. As a result of analysis of impurities, all were within the specifications of commercially available high purity hydrofluoric acid.
１ 蒸発缶
２ 精留塔
３ 凝縮器
４ 凝縮器
５ 初留受器
６ ＨＣｌ−ＨＦ回収槽
７ 後留受器
８ バッファータンク
９ 真空ポンプ
１０ 濾過器
１１ 粗製Ｈ２ＳｉＦ６貯槽
１２ 送液ポンプ
１３ 蒸発缶
１４ 精留塔
１５ 凝縮器
１６ 凝縮器
１７ 初留受器
１８ Ｈ２ＳｉＦ６回収槽
１９ バッファータンク
２０ 真空ポンプ
1
10
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| JP5341634B2 (en) * | 2009-06-22 | 2013-11-13 | 株式会社 電硝エンジニアリング | Method for recovering mixed acid with increased hydrochloric acid concentration from hydrochloric acid-hydrofluoric acid mixed acid waste liquid |
| JP5421088B2 (en) * | 2009-12-15 | 2014-02-19 | 森田化学工業株式会社 | Method for producing valuable materials and hydrochloric acid from waste liquid |
| JP5661389B2 (en) * | 2010-09-09 | 2015-01-28 | 株式会社ササクラ | Acid recovery method |
| JP2012183457A (en) * | 2011-03-03 | 2012-09-27 | Seiko Epson Corp | Separation method and separation device |
| KR101288822B1 (en) * | 2011-08-25 | 2013-07-23 | 주식회사 전영 | On-site recycling method for the high efficient recovery of waste generating from glass etching process |
| FR2981060B1 (en) | 2011-10-06 | 2014-10-17 | Arkema France | PROCESS FOR THE VALORISATION OF THE EFFLUENTS OF CHLOROFLUORHYDRIC ACID |
| JP6162625B2 (en) * | 2014-02-27 | 2017-07-12 | 株式会社日立製作所 | Crystal growth crucible, crystal growth apparatus and crystal growth method provided therewith |
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| TWI759787B (en) * | 2020-07-07 | 2022-04-01 | 環創源科技股份有限公司 | Method for processing waste polishing solution and waste solution containing hydrofluoric acid |
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