JP6660812B2 - 廃液の処理方法及び廃液の処理装置 - Google Patents
廃液の処理方法及び廃液の処理装置 Download PDFInfo
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- JP6660812B2 JP6660812B2 JP2016108463A JP2016108463A JP6660812B2 JP 6660812 B2 JP6660812 B2 JP 6660812B2 JP 2016108463 A JP2016108463 A JP 2016108463A JP 2016108463 A JP2016108463 A JP 2016108463A JP 6660812 B2 JP6660812 B2 JP 6660812B2
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- waste liquid
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- fluorine
- calcium
- boron
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- 239000007788 liquid Substances 0.000 title claims description 114
- 239000002699 waste material Substances 0.000 title claims description 97
- 238000000034 method Methods 0.000 title claims description 20
- 239000007787 solid Substances 0.000 claims description 72
- 238000002156 mixing Methods 0.000 claims description 64
- 229910052731 fluorine Inorganic materials 0.000 claims description 50
- 239000011737 fluorine Substances 0.000 claims description 50
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 46
- 229940043430 calcium compound Drugs 0.000 claims description 44
- 150000001674 calcium compounds Chemical class 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 44
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 36
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 35
- 229910052796 boron Inorganic materials 0.000 claims description 35
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 31
- 229910052710 silicon Inorganic materials 0.000 claims description 31
- 239000010703 silicon Substances 0.000 claims description 31
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 15
- 239000012295 chemical reaction liquid Substances 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000920 calcium hydroxide Substances 0.000 claims description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [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 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- -1 ammonium ions Chemical class 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 239000003929 acidic solution Substances 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 6
- 238000004065 wastewater treatment Methods 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 46
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 44
- 238000002347 injection Methods 0.000 description 32
- 239000007924 injection Substances 0.000 description 32
- 239000007789 gas Substances 0.000 description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 7
- 229910001634 calcium fluoride Inorganic materials 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 208000005156 Dehydration Diseases 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 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 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 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
- 159000000007 calcium salts Chemical class 0.000 description 1
- YPSVSPBXPRTRQF-UHFFFAOYSA-N calcium;oxygen(2-);hydrate Chemical class O.[O-2].[Ca+2] YPSVSPBXPRTRQF-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001039 duplex stainless steel Inorganic materials 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- CUPFNGOKRMWUOO-UHFFFAOYSA-N hydron;difluoride Chemical compound F.F CUPFNGOKRMWUOO-UHFFFAOYSA-N 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
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- Water Treatment By Sorption (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Description
Claims (8)
- 硫酸イオンの存在下で、フッ素、ホウ素及びケイ素のうち少なくともいずれか1種を含む廃液とアルミニウム塩とカルシウム化合物とを混合し、固形物を生成する廃液の処理方法であって、
前記混合中に生じる反応熱を利用して、前記固形物を含む反応液を蒸発させ、濃縮又は脱水した固形物を得、前記濃縮又は脱水した固形物を押出機にて脱液することを特徴とする廃液の処理方法。 - 前記アルミニウム塩は硫酸アルミニウム溶液又はその酸性溶液であり、前記カルシウム化合物は、水酸化カルシウム、酸化カルシウム、またはそれらの混合物の粉末であることを特徴とする請求項1に記載の廃液の処理方法。
- 前記廃液と混合する前記カルシウム化合物の量は、前記廃液中のフッ素、ホウ素及びケイ素の総モル量に対してカルシウムのモル量で0.6倍以上であり、前記アルミニウム塩の量は、前記廃液中のフッ素、ホウ素及びケイ素の総モル量に対してアルミニウムのモル量で0.07倍以上であることを特徴とする請求項1又は2に記載の廃液の処理方法。
- 前記廃液はアンモニア又はアンモニウムイオンを含み、
前記固形物を含む反応液を蒸発させる際に生成するアンモニアガスを分解処理することを特徴とする請求項1〜3のいずれか1項に記載の廃液の処理方法。 - 硫酸イオンの存在下で、フッ素、ホウ素及びケイ素のうち少なくともいずれか1種を含む廃液とアルミニウム塩とカルシウム化合物とを混合し、固形物を生成する廃液の処理装置であって、
前記混合中に生じる反応熱を利用して、前記固形物を含む反応液を蒸発させることにより、濃縮又は脱水した固形物が得られ、前記濃縮又は脱水した固形物を押出機にて脱液することを特徴とする廃液の処理装置。 - 前記アルミニウム塩は硫酸アルミニウム溶液又はその酸性溶液であり、前記カルシウム化合物は、水酸化カルシウム、酸化カルシウム、またはそれらの混合物の粉末であることを特徴とする請求項5に記載の廃液の処理装置。
- 前記廃液と混合する前記カルシウム化合物の量は、前記廃液中のフッ素、ホウ素及びケイ素の総モル量に対してカルシウムのモル量で0.6倍以上であり、前記アルミニウム塩の量は、前記廃液中のフッ素、ホウ素及びケイ素の総モル量に対してアルミニウムのモル量で0.07倍以上であることを特徴とする請求項5又は6に記載の廃液の処理装置。
- 前記廃液はアンモニア又はアンモニウムイオンを含み、
前記固形物を含む反応液を蒸発させる際に生成するアンモニアガスを分解処理するアンモニアガス処理手段を備えることを特徴とする請求項5〜7のいずれか1項に記載の廃液の処理装置。
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