JP4682043B2 - Borohydrofluoric acid scavenger and wastewater treatment method using the same - Google Patents
Borohydrofluoric acid scavenger and wastewater treatment method using the same Download PDFInfo
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- JP4682043B2 JP4682043B2 JP2005517818A JP2005517818A JP4682043B2 JP 4682043 B2 JP4682043 B2 JP 4682043B2 JP 2005517818 A JP2005517818 A JP 2005517818A JP 2005517818 A JP2005517818 A JP 2005517818A JP 4682043 B2 JP4682043 B2 JP 4682043B2
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- borohydrofluoric acid
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- 239000002253 acid Substances 0.000 title claims description 65
- 239000002516 radical scavenger Substances 0.000 title claims description 48
- 238000004065 wastewater treatment Methods 0.000 title claims description 13
- 239000002351 wastewater Substances 0.000 claims description 50
- 150000001875 compounds Chemical class 0.000 claims description 39
- 125000003342 alkenyl group Chemical group 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 27
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 26
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 26
- 229920006318 anionic polymer Polymers 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- -1 rare earth compounds Chemical class 0.000 claims description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 13
- 150000001450 anions Chemical class 0.000 claims description 13
- 125000000623 heterocyclic group Chemical group 0.000 claims description 13
- 229920002472 Starch Polymers 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 12
- 239000008107 starch Substances 0.000 claims description 11
- 235000019698 starch Nutrition 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229920000159 gelatin Polymers 0.000 claims description 10
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 10
- 108010010803 Gelatin Proteins 0.000 claims description 9
- 229920002125 Sokalan® Polymers 0.000 claims description 9
- 239000000783 alginic acid Substances 0.000 claims description 9
- 235000010443 alginic acid Nutrition 0.000 claims description 9
- 229920000615 alginic acid Polymers 0.000 claims description 9
- 229960001126 alginic acid Drugs 0.000 claims description 9
- 150000004781 alginic acids Chemical class 0.000 claims description 9
- 239000008273 gelatin Substances 0.000 claims description 9
- 235000019322 gelatine Nutrition 0.000 claims description 9
- 235000011852 gelatine desserts Nutrition 0.000 claims description 9
- 239000001814 pectin Substances 0.000 claims description 9
- 229920001277 pectin Polymers 0.000 claims description 9
- 235000010987 pectin Nutrition 0.000 claims description 9
- 239000004584 polyacrylic acid Substances 0.000 claims description 9
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 8
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 8
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000005909 Kieselgur Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000440 bentonite Substances 0.000 claims description 6
- 229910000278 bentonite Inorganic materials 0.000 claims description 6
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 239000011398 Portland cement Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 241001659321 ANME-2 cluster Species 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 22
- 239000011737 fluorine Substances 0.000 description 22
- 229910052731 fluorine Inorganic materials 0.000 description 22
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 17
- 229910052796 boron Inorganic materials 0.000 description 17
- 239000007788 liquid Substances 0.000 description 14
- 239000010802 sludge Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000013589 supplement Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 229940043430 calcium compound Drugs 0.000 description 4
- 150000001674 calcium compounds Chemical class 0.000 description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 3
- 229960001927 cetylpyridinium chloride Drugs 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007429 general method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- PYMYPHUHKUWMLA-UHFFFAOYSA-N 2,3,4,5-tetrahydroxypentanal Chemical compound OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- AEMOLEFTQBMNLQ-UHFFFAOYSA-N beta-D-galactopyranuronic acid Natural products OC1OC(C(O)=O)C(O)C(O)C1O AEMOLEFTQBMNLQ-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- GKQHIYSTBXDYNQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GKQHIYSTBXDYNQ-UHFFFAOYSA-M 0.000 description 1
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- AEMOLEFTQBMNLQ-DTEWXJGMSA-N D-Galacturonic acid Natural products O[C@@H]1O[C@H](C(O)=O)[C@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-DTEWXJGMSA-N 0.000 description 1
- AEMOLEFTQBMNLQ-BZINKQHNSA-N D-Guluronic Acid Chemical compound OC1O[C@H](C(O)=O)[C@H](O)[C@@H](O)[C@H]1O AEMOLEFTQBMNLQ-BZINKQHNSA-N 0.000 description 1
- AEMOLEFTQBMNLQ-VANFPWTGSA-N D-mannopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-VANFPWTGSA-N 0.000 description 1
- 241000276457 Gadidae Species 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- PMMYEEVYMWASQN-DMTCNVIQSA-N Hydroxyproline Chemical compound O[C@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-DMTCNVIQSA-N 0.000 description 1
- 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
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
- ZAHXYMFVNNUHCP-UHFFFAOYSA-N Naphazoline nitrate Chemical compound O[N+]([O-])=O.C=1C=CC2=CC=CC=C2C=1CC1=NCCN1 ZAHXYMFVNNUHCP-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- QPFYXYFORQJZEC-FOCLMDBBSA-N Phenazopyridine Chemical group NC1=NC(N)=CC=C1\N=N\C1=CC=CC=C1 QPFYXYFORQJZEC-FOCLMDBBSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- IAJILQKETJEXLJ-RSJOWCBRSA-N aldehydo-D-galacturonic acid Chemical compound O=C[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)C(O)=O IAJILQKETJEXLJ-RSJOWCBRSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001371 alpha-amino acids Chemical class 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229960000686 benzalkonium chloride Drugs 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride 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
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- UAKOZKUVZRMOFN-JDVCJPALSA-M dimethyl-bis[(z)-octadec-9-enyl]azanium;chloride Chemical compound [Cl-].CCCCCCCC\C=C/CCCCCCCC[N+](C)(C)CCCCCCCC\C=C/CCCCCCCC UAKOZKUVZRMOFN-JDVCJPALSA-M 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- PMMYEEVYMWASQN-UHFFFAOYSA-N dl-hydroxyproline Natural products OC1C[NH2+]C(C([O-])=O)C1 PMMYEEVYMWASQN-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229960002591 hydroxyproline Drugs 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000004492 methyl ester group Chemical group 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229940118915 privine Drugs 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- FGMPLJWBKKVCDB-UHFFFAOYSA-N trans-L-hydroxy-proline Natural products ON1CCCC1C(O)=O FGMPLJWBKKVCDB-UHFFFAOYSA-N 0.000 description 1
- SBHRWOBHKASWGU-UHFFFAOYSA-M tridodecyl(methyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(CCCCCCCCCCCC)CCCCCCCCCCCC SBHRWOBHKASWGU-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/12—Nature of the water, waste water, sewage or sludge to be treated from the silicate or ceramic industries, e.g. waste waters from cement or glass factories
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/346—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from semiconductor processing, e.g. waste water from polishing of wafers
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
本発明はホウフッ化水素酸塩を含有する排水の処理方法に使用する添加剤及びその処理方法に関するものであり、更に詳しくはホウフッ化水素酸塩を含有する排水を外部エネルギーで加熱することなく、且つ短時間で処理する処理方法に関するものである。 The present invention relates to an additive used for a method for treating wastewater containing borofluoride and a method for treating the same, and more specifically, without heating wastewater containing borofluoride with external energy, The present invention also relates to a processing method for processing in a short time.
フッ化水素酸を代表とするフッ素化合物は、化学工場や半導体製造、金属・ガラスの加工、メッキ加工等の業界に於いて大量に使用される有用な物質であるが、その人体・環境に対する有害性からそれらを含有する排水には排出基準値が設けられ、厳しい排出規制が行われている。
一般的な排水中のフッ素除去の方法としては、フッ素含有排水に消石灰、塩化カルシウム等のカルシウム化合物を添加し、更にｐＨを調整して難溶性のフッ化カルシウムを沈殿させ、固液分離する方法が採られている。
しかしながら排水中のフッ素化合物が、ホウフッ化水素酸塩として存在する場合、カルシウム化合物を添加しても難溶性の化合物は生成しないためフッ素の除去は困難である。
更に、ホウ素に関しても、その有害性から排出基準が設けられており、排出に当たっては、排水中からホウ素も除去する必要がある。
一般的なホウ素除去の方法は、カルシウム化合物とアルミニウム化合物により難溶性の化合物を生成し、沈降分離する方法が知られているが、これもフッ素と同様に、ホウ素がホウフッ化水素酸塩として存在する場合、ホウ素の除去は困難である。
これらの問題を解決するために、ホウフッ化水素酸塩の処理方法として、次のような技術が開示されている。
（１）アルミ化合物又は第２鉄塩を添加してホウフッ化水素酸塩を分解し、次いでカルシウム化合物を添加して生成したフッ化カルシウムを除去する方法（特公昭５４−１８０６４号公報参照）。
（２）アルミニウム化合物を添加して、ホウフッ化水素酸塩を酸性領域で熱分解した後、カルシウム化合物を加えて生成したフッ化カルシウムを除去する方法（特開昭６２−２２７４９６号公報参照）。
（３）ホウフッ化水素酸塩含有排水に硫酸アルミニウムを加えて５０℃以上で反応させてホウフッ化水素酸イオンを分解した後、炭酸カルシウムを添加してフッ素をカルシウムとして固定化・除去する方法（特開平７−３２８６４５号公報参照）。
然し、これらの方法はいずれもホウフッ化水素酸塩の分解を促進をするために加熱を必要とする。又、非加熱での処理に於いては長時間の分解時間を要する等の問題を抱えていた。
又、アルミニウム化合物を大過剰に使用すれば、フッ素の除去性は高まるが、これは大量のスラッジの原因となり、その処分方法が問題となる。Fluorine compounds such as hydrofluoric acid are useful substances that are used in large quantities in industries such as chemical factories, semiconductor manufacturing, metal / glass processing, and plating, but they are harmful to the human body and the environment. Because of their characteristics, wastewater containing them has emission standard values and strict emission regulations are in place.
As a general method for removing fluorine in wastewater, a calcium compound such as slaked lime or calcium chloride is added to fluorine-containing wastewater, and the pH is adjusted to precipitate poorly soluble calcium fluoride, followed by solid-liquid separation. Has been adopted.
However, when the fluorine compound in the wastewater is present as borohydrofluoride, it is difficult to remove fluorine because a poorly soluble compound is not formed even when a calcium compound is added.
Furthermore, emission standards are also set for boron because of its harmfulness, and it is necessary to remove boron from the waste water when discharging.
As a general method for removing boron, a method is known in which a poorly soluble compound is produced by a calcium compound and an aluminum compound, and then separated by sedimentation. As with fluorine, boron exists as a borohydrofluoride. In this case, boron removal is difficult.
In order to solve these problems, the following technique is disclosed as a method for treating borofluoride.
(1) A method in which an aluminum compound or a ferric salt is added to decompose borohydrofluoride and then a calcium compound is added to remove the generated calcium fluoride (see Japanese Patent Publication No. 54-18064).
(2) A method in which an aluminum compound is added to thermally decompose borohydrofluoride in an acidic region, and then calcium fluoride is added to remove the generated calcium fluoride (see Japanese Patent Application Laid-Open No. 62-22796).
(3) Method of fixing and removing fluorine as calcium by adding calcium carbonate after decomposing borohydrofluoric acid ions by adding aluminum sulfate to waste water containing borofluoride and reacting at 50 ° C or higher ( JP-A-7-328645).
However, both of these methods require heating to promote the decomposition of borofluoride. Further, the non-heating treatment has a problem that a long decomposition time is required.
Further, if the aluminum compound is used in a large excess, the fluorine removal property is enhanced, but this causes a large amount of sludge, and the disposal method becomes a problem.
本発明は、上記のような従来の処理方法の欠点を改善し、ホウフッ化水素酸塩含有排水を、大量のスラッジを発生させることなく、常温・短時間で処理することが可能な処理剤及び処理方法を提供することである。
本発明の目的は下記（１）〜（９）の手段によって解決される。
（１）排水からホウフッ化水素酸を除去する添加剤で、下記一般式（１）〜（４）で表される化合物の少なくとも１種よりなることを特徴とするホウフッ化水素酸捕捉剤。
一般式（１）
一般式（２）
一般式（３）
一般式（４）
（２）一般式（２）及び一般式（４）で表されるホウフッ化水素酸捕捉剤のＡが下記のＡ群から選ばれる構造を有することを特徴とする（１）の手段に記載のホウフッ化水素酸捕捉剤。
Ａ群：アルギン酸、ペクチン、ゼラチン、アニオン化でんぷん、カルボキシメチルセルロース、ポリアクリル酸、アクリルアミドとアクリル酸との共重合体
（３）４級アンモニウム塩１モルに対し、アニオン性高分子のアニオン性部位のモル数が０．０１〜５．０モルの割合で作成されたことを特徴とする（２）の手段に記載のホウフッ化水素酸捕捉剤。
（４）ホウフッ化水素酸塩を含有する排水からホウフッ化水素酸を除去する排水処理方法に関し、該排水へ下記一般式（１）又は一般式（３）で表されるホウフッ化水素酸捕捉剤の少なくとも１種を添加することを特徴とする排水処理方法。
一般式（１）
一般式（３）
（５）排水中に含まれるホウフッ化水素酸イオン１モル当たり０．１〜０．５モルの下記一般式（１）で表されるホウフッ化水素酸捕捉剤を添加することを特徴とする（４）の手段に記載の排水処理方法。
一般式（１）
（６）一般式（１）又は一般式（３）で表されるホウフッ化水素酸捕捉剤の少なくとも１種を添加した後、珪藻土、ベントナイト、カオリン、活性炭、ポルトランドセメント、親水性高分子化合物、多価金属類、希土類化合物から選択される１種以上の化合物を添加することを特徴とする（４）又は（５）の手段に記載の排水処理方法。
（７）該化合物の添加量は被処理水の０．０００５〜５．０重量％であることを特徴とする（６）の手段に記載の排水処理方法。
（８）ホウフッ化水素酸塩を含有する排水と、一般式（２）又は一般式（４）で表されるホウフッ化水素酸捕捉剤をｐＨ５未満で接触させることを特徴とする排水処理方法。
一般式（２）
Ａ群：アルギン酸、ペクチン、ゼラチン、アニオン化でんぷん、カルボキシメチルセルロース、ポリアクリル酸、アクリルアミドとアクリル酸との共重合体
一般式（４）
（９）下記一般式（２）又は一般式（４）で表されるホウフッ化水素酸捕捉剤の再生方法に関し、ホウフッ化水素酸を捕捉した捕捉剤をｐＨ８以上に調整した水溶液と接触させることで再生することを特徴とするホウフッ化水素酸捕捉剤の再生方法。
一般式（２）
一般式（４）
本発明請求項１，２，３のホウフッ化水素酸捕捉剤を使用することにより、ホウフッ化水素酸塩を含有する排水から、加熱等の外部エネルギーを使用することなく、少ないスラッジ量で短時間にフッ素及びホウ素を除去することができる。更に、２次処理（高度処理）のための槽を設置する等設備の増強の必要がなく、既存の１次処理設備のみで高度処理が可能となる。
又、本発明請求項４，５によれば、上述の効果をあげることが出きると共に、極めて簡単な操作及び従来設備そのままの使用で所期の目的を達成することができる。
又、本発明請求項６，７によれば、不活性化合物の沈降により、固溶分離を効率よく行うことが出来る。又、フロックの凝集性が高まり、スラッジの減容ができる。
又、本発明請求項８によれば、ｐＨ５未満で接触排水をすることにより、除去剤の効率を更に向上させることができる。
更に、本発明請求項９によれば、捕捉剤の再生が極めて効率よく行われ、極めて経済的なホウフッ化水素酸塩の分解処理が行える。
発明を実施する為の最良の形態
以下、本発明を詳細に説明する。
本発明の排水の処理方法は、ホウフッ化水素酸塩を含有した排水を対象とする。ホウフッ化水素酸塩を含有する排水は、例えばメッキ加工業者、ガラス加工業者、プリント基板加工業者、金属表面処理業者などから排出される。
本発明は、ホウフッ化水素酸塩を含有する排水に、下記一般式（１）〜（４）で表されるホウフッ化水素酸の捕捉剤を添加することを特徴とする。更には、ホウフッ化水素酸を捕捉した一般式（２）又は（４）で表される捕捉剤を、ｐＨ８以上に調整した水溶液と接触させることで再生する方法を特徴とする。
一般式（１）
一般式（３）
一般式（４）
本発明に使用される４級アンモニウム塩の具体例として、ジメチルステアリルベンジルアンモニウムクロライド、トリメチルラウリルアンモニウムクロライド、トリメチルセチルアクモウニムクロライド、トリメチルステアリルアンモニウムクロライド、ジメチルジステアリルアンモニウムクロライド、ジメチルジオレイルアンモニウムクロライド、メチルトリドデシルアンモニウムクロライド、塩化ベンザルコニウム、１−ステアリル−１，４，４−トリメチルピペラジニウム等を挙げることが出来るがこれに限定されるものではない。
一般式（１）のＸ−は陰イオンを表す。陰イオンとしては、Ｆ−、Ｃｌ−、Ｂ−、Ｉ−、ＳＯ４ ２−、ＮＯ３ ２−、ＣＯ３ ２−、ＰＯ４ ２−等を挙げることが出来る。
一般式（２）のＡはアニオン性高分子を表す。アニオン性高分子の具体例として、アルギン酸、ペクチン、ゼラチン、アニオン化でんぷん、カルボキシメチルセルロース、ポリアクリル酸、アクリルアミドとアクリル酸との共重合体等を挙げることが出来るが、一般式（２）で表される４級アンモニウム塩と対イオンを形成して難水溶性の固形物を形成できれば何でもよい。
一般式（３）
一般式（１）又は（３）で表されるホウフッ化水素酸捕捉剤の添加量は、排水中に含まれるホウフッ化水素酸イオン１モルあたり０．１〜５．０、好ましくは０．２５〜２．５モル、より好ましくは０．５〜２．０モルであり、所望のホウフッ化水素酸塩除去率に合せて添加すればよい。被処理水に一般式（１）又は（３）で表されるホウフッ化水素酸捕捉剤［Ｑ］＋Ｘ−を添加することにより、ホウフッ化水素酸と不溶性化合物を形成する。
［Ｑ］＋Ｘ−＋Ｎａ＋ＢＦ４ −→［Ｑ］＋ＢＦ４ −↓＋ＮａＸ
上記行程で処理した後、処理水と不溶性化合物に固液分離することにより、排水中からホウフッ化水素酸塩を除去することが可能となる。固液分離の方法としては、沈降分離、プレスろ過、遠心濾過、遠心分離等が用いられる。
本発明に於いて、ホウフッ化水素酸塩と４級アンモニウム塩の不溶性化合物を沈降させ、固液分離を効率よく行うために、珪藻土、ベントナイト、カオリン、活性炭、ポルトランドセメント、親水性高分子化合物、多価金属類、希土類化合物から選択される少なくとも１つの化合物を添加することが好ましい。これらの化合物は単独で用いてもよいし、複数の化合物を混合して用いてもよい。これらの化合物の添加量は、被処理水の０．０００５〜５．０重量％、好ましくは０．００１〜３．０重量％、より好ましくは０．００５〜２．０重量％である。
本発明に用いられる親水性高分子化合物の具体的な例として、アルギン酸、ペクチン、ゼラチン、寒天、アニオン化でんぷん、カルボキシメチルセルロース、ポリアクリル酸、ポリエチレンイミン、ポリアクリルアミド、アクリルアミドとアクリル酸との共重合体及びその金属塩、ポリ塩化アルミニウム、ポリ硫酸鉄、ポリ塩化鉄などが挙げられるが、これに限定されるものではない。天産品及び合成品の何れも使用できるが、環境保全の観点からは生分解性を有するものが好ましい。
本発明に用いられる多価金属としては、塩化鉄、硫酸鉄等の鉄化合物、塩化アルミニウム、硫酸バンド等のアルミニウム化合物、塩化亜鉛、硫酸亜鉛等の亜鉛化合物等が挙げられるが、これに限定されるものではない。
本発明に用いられる希土類化合物としては、セリウム、ランタン、ネオジウム、プラセオジウム、サマリウム、ガドリニウム、テルビウム、イットリウム等の塩化物、硫酸塩、硝酸塩、酢酸塩が挙げられるが、これに限定されるものではない。
これらの化合物を添加することにより、フロックの凝集性が高まり、スラッジの減容が可能となる。
一般式（２）又は（４）で表されるホウフッ化水素酸の捕捉剤は、直接排水に添加してもよいし、充填層を形成し、その中に排水を通過させてもよい。
一般式（２）又は（４）で表されるホウフッ化水素酸の捕捉剤は、一般式（１）又は（３）で表される４級アンモニウム塩の水溶液又は置換基によって４級化された窒素を持つ含窒素複素環化合物の水溶液と、アニオン性高分子を反応させることによって作成することができるが、特に一般式（２）のＡに相当するアニオン性高分子又はその水溶液が好適に使用でき、これらを混合し、生成した沈殿物を固液分離することで容易に得られる。
４級アンモニウム塩又は置換基によって４級化された窒素を持つ含窒素複素環化合物とアニオン性高分子は任意の割合で混合することができるが、好ましくは４級アンモニウム塩、又は含窒素複素環化合物１モルに対して、アニオン性の部位のモル数が０．０１モル〜５．０モルの割合、より好ましくは０．１モル〜２．５モルの割合で混合することによって、効率よく効果の高い捕捉剤を作成することができる。
アルギン酸としては、マンヌロン酸のみ、グルロン酸のみであっても、これらランダム体であってもよく、重合度２００〜８００程度のものが好適に用いられる。
ペクチンは、Ｄ−ガラクトウロン酸から成る直鎖状の多糖類であって、カルボキシルキの一部がメチルエステルになっている。本発明に於いて、エステル化度が５０％以上であるハイメトキシペクチンも、５０％以下であるローメトシキペクチンも好適に使用することができる。
ゼラチンはペプチド結合によって結合されたα−アミノ酸及びイミノ酸から構成されており、アミノ酸成分は種々あるが、グリシンとプロリン及びヒドロキシプロリンが分子量の１／２以上を占めている。平均分子量は２０，０００〜２００，０００以上であり、このうち５０，０００〜１５０，０００の分子量のものが特に好適である。
アニオン化でんぷんとしては、でんぷんのグルコース部分の水酸基にアニオン性の官能基を導入したものであって、カルボキシメチル基やホスホン酸基を導入した、カルボキシメチルでんぷんやリン酸化でんぷんなどが好適に使用できる。
カルボキシメチルセルロースとしては、特に指定はないが、グルコース単位あたり、カルボシキル置換度が０．５〜２．０のものが好適に使用できる。
ポリアクリル酸としては、アクリル酸及び／又はその塩を重合して得られる重合体が用いられる。アクリル酸を過硫酸アンモニウム、過硫酸カリウム等の過流酸塩、又は過流酸塩／還元剤を組合わせてなるレッドクス触媒によって重合することができる。又、可視光線、紫外線、電子線、又はγ線によって重合してもよい。又、ポリアクリル酸メチル等のポリアクリル酸エステルを苛性アルカリで鹸化することによって、製造した製品も好適に使用することができる。
アクリルアミドとアクリル酸との共重合体は、アクリルアミドをアクリル酸ナトリウム又はカチオン性モノマートと共重合して得られたものが好適に使用することができる。市販品としては、三洋化成工業株式会社から「サンフロック（登録商標）」の商品名で市販されている製品、三井サイナミッド株式会社から「スーパフロック（登録商標）」の商品名で市販されている製品などが挙げられる。
上記のような方法で得られた捕捉剤をｐＨ５未満に調整されたホウフッ化水素酸塩を含有する排水に直接投入してしばらく撹拌した後、被処理水と排出材に固液分離することで排水からホウフッ化水素酸塩の除去が可能となる。
又は、該捕捉剤を除去塔に充填し、ここにｐＨ５以下に調整されたホウフッ化水素酸塩を含有する排水を通水することでもホウフッ化水素酸塩の除去が可能となる。
ホウフッ化水素酸塩の除去に使用した一般式（２）又は一般式（４）の捕捉剤は、ｐＨ８以上に調整した溶液と接触させることでホウフッ化水素酸を脱着、繰返し捕捉剤として使用することができる。
尚、本発明の方法に於いて、ホウフッ化水素酸塩は除去できるが、フッ素、ホウ素は除去できない。排水中にホウフッ化水素酸塩と共に、フッ素、ホウ素を含有する場合は、一般的な方法であるカルシウム処理によりフッ素をカルシウムとアルミニウムによる処理でホウ素をそれぞれ除去した後、本発明の方法を適用してもよい。
排水中にホウフッ化水素を多量に含む廃液の場合は、本発明のホウフッ化水素酸補足剤を添加する前に、ホウフッ化酸と反応して塩を形成する化合物を添加してホウフッ化塩として析出させ除去を行なうことも出来る。ホウフッ化酸と反応して塩を形成する化合物としては、塩化カリウム、炭酸カリウム等のカリウム塩が挙げられ、これらの添加によって、排液中のホウフッ化水素酸をある程度低減でき、この操作で取り切れないホウフッ化酸を本発明の補足剤を使用する事で、補足剤を効率よく使用する事が出来る。
本発明のホウフッ化補足剤は必要量以上添加しても、ホウフッ化水素酸除去能力に問題は生じないが、排水中のＣＯＤ、ＢＯＤが高くなってしまう事がある。この場合、ホウフッ化水素酸除去処理後に４級アンモニウム捕捉剤を加えることによって、余剰のホウフッ化補足剤を除去する事が出来る。４級アンモニウム補足剤としては活性炭、ベントナイト、キプロガム等が挙げられ、排水中のホウフッ化水素酸除去後に、これらを添加する事によってＣＯＤ，ＢＯＤ値を抑えることが出来る。The present invention improves the drawbacks of the conventional treatment method as described above, and can treat a borofluoride-containing wastewater at room temperature and in a short time without generating a large amount of sludge, and It is to provide a processing method.
The object of the present invention is solved by the following means (1) to (9).
(1) An additive for removing borohydrofluoric acid from waste water, and comprising at least one compound represented by the following general formulas (1) to (4).
General formula (1)
General formula (2)
General formula (3)
General formula (4)
(2) The means of (1) characterized in that A of the borohydrofluoric acid scavenger represented by the general formula (2) and the general formula (4) has a structure selected from the following group A: Borohydrofluoric acid scavenger.
Group A: Alginic acid, pectin, gelatin, anionized starch, carboxymethylcellulose, polyacrylic acid, copolymer of acrylamide and acrylic acid (3) Anionic site of anionic polymer with respect to 1 mol of quaternary ammonium salt The borohydrofluoric acid scavenger according to the means (2), wherein the number of moles is 0.01 to 5.0 mol.
(4) A borofluoric acid scavenger represented by the following general formula (1) or general formula (3) in the wastewater treatment method for removing borohydrofluoric acid from wastewater containing borofluoride A wastewater treatment method comprising adding at least one of the following.
General formula (1)
General formula (3)
(5) 0.1 to 0.5 mol of borohydrofluoric acid scavenger represented by the following general formula (1) is added per mol of borohydrofluoric acid ions contained in the waste water ( The wastewater treatment method according to 4).
General formula (1)
(6) After adding at least one borohydrofluoric acid scavenger represented by general formula (1) or general formula (3), diatomaceous earth, bentonite, kaolin, activated carbon, Portland cement, hydrophilic polymer compound, One or more compounds selected from polyvalent metals and rare earth compounds are added. The method for treating waste water according to (4) or (5).
(7) The wastewater treatment method according to the means of (6), wherein the amount of the compound added is 0.0005 to 5.0% by weight of water to be treated.
(8) A wastewater treatment method comprising contacting a wastewater containing borohydrofluoric acid salt with a borohydrofluoric acid scavenger represented by the general formula (2) or the general formula (4) at a pH of less than 5.
General formula (2)
Group A: Alginic acid, pectin, gelatin, anionized starch, carboxymethylcellulose, polyacrylic acid, copolymer of acrylamide and acrylic acid, general formula (4)
(9) Regarding the regeneration method of the borohydrofluoric acid scavenger represented by the following general formula (2) or general formula (4), contacting the scavenger capturing borofluoric acid with an aqueous solution adjusted to pH 8 or more. A method for regenerating a borohydrofluoric acid scavenger, wherein
General formula (2)
General formula (4)
By using the borohydrofluoric acid scavenger of Claims 1, 2, and 3 of the present invention, it is possible to reduce the amount of sludge in a short time without using external energy such as heating from wastewater containing borofluoride. Fluorine and boron can be removed. Furthermore, it is not necessary to reinforce equipment such as installing a tank for secondary processing (advanced processing), and advanced processing can be performed only with existing primary processing equipment.
According to the fourth and fifth aspects of the present invention, the above-mentioned effects can be achieved, and the intended purpose can be achieved by using an extremely simple operation and using the conventional equipment as it is.
According to claims 6 and 7 of the present invention, solid solution separation can be efficiently performed by precipitation of the inert compound. In addition, flocs are more cohesive and sludge volume can be reduced.
Further, according to the eighth aspect of the present invention, the efficiency of the removing agent can be further improved by performing contact drainage at a pH of less than 5.
Furthermore, according to the ninth aspect of the present invention, the scavenger can be regenerated very efficiently, and a very economical decomposition treatment of borofluoride can be performed.
BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The waste water treatment method of the present invention is directed to waste water containing borohydrofluoride. Waste water containing borofluoride is discharged from, for example, a plating processor, a glass processor, a printed circuit board processor, a metal surface processor, or the like.
The present invention is characterized in that a scavenger for borohydrofluoric acid represented by the following general formulas (1) to (4) is added to wastewater containing borohydrofluoride. Furthermore, the method is characterized in that the scavenger represented by the general formula (2) or (4) capturing borohydrofluoric acid is regenerated by contacting with an aqueous solution adjusted to pH 8 or higher.
General formula (1)
General formula (3)
General formula (4)
Specific examples of the quaternary ammonium salt used in the present invention include dimethyl stearyl benzyl ammonium chloride, trimethyl lauryl ammonium chloride, trimethyl cetyl ammonium chloride, trimethyl stearyl ammonium chloride, dimethyl distearyl ammonium chloride, dimethyl dioleyl ammonium chloride, Examples thereof include, but are not limited to, methyl tridodecyl ammonium chloride, benzalkonium chloride, 1-stearyl-1,4,4-trimethylpiperazinium.
X − in the general formula (1) represents an anion. Examples of the anion include F − , Cl − , B − , I − , SO 4 2− , NO 3 2− , CO 3 2− , PO 4 2−, and the like.
A in the general formula (2) represents an anionic polymer. Specific examples of the anionic polymer include alginic acid, pectin, gelatin, anionized starch, carboxymethylcellulose, polyacrylic acid, a copolymer of acrylamide and acrylic acid, and the like, represented by the general formula (2). Any quaternary ammonium salt can be used as long as it can form a counter ion to form a hardly water-soluble solid.
General formula (3)
The addition amount of the borohydrofluoric acid scavenger represented by the general formula (1) or (3) is 0.1 to 5.0, preferably 0.25, per mol of borohydrofluoric acid ions contained in the waste water. It may be added in accordance with a desired removal rate of borofluoride, and is preferably -2.5 mol, more preferably 0.5-2.0 mol. By adding the borofluoric acid scavenger [Q] + X − represented by the general formula (1) or (3) to the water to be treated, borohydrofluoric acid and an insoluble compound are formed.
[Q] + X − + Na + BF 4 − → [Q] + BF 4 − ↓ + NaX
After the treatment in the above process, the borofluoride can be removed from the waste water by solid-liquid separation into treated water and an insoluble compound. As a method of solid-liquid separation, sedimentation separation, press filtration, centrifugal filtration, centrifugal separation and the like are used.
In the present invention, in order to precipitate an insoluble compound of borofluoride and quaternary ammonium salt and efficiently perform solid-liquid separation, diatomaceous earth, bentonite, kaolin, activated carbon, Portland cement, hydrophilic polymer compound, It is preferable to add at least one compound selected from polyvalent metals and rare earth compounds. These compounds may be used alone or in combination with a plurality of compounds. The addition amount of these compounds is 0.0005 to 5.0% by weight of water to be treated, preferably 0.001 to 3.0% by weight, and more preferably 0.005 to 2.0% by weight.
Specific examples of the hydrophilic polymer compound used in the present invention include alginic acid, pectin, gelatin, agar, anionized starch, carboxymethylcellulose, polyacrylic acid, polyethylenimine, polyacrylamide, co-polymerization of acrylamide and acrylic acid. A coalescence and a metal salt thereof, polyaluminum chloride, polyiron sulfate, polyiron chloride and the like can be mentioned, but are not limited thereto. Both natural products and synthetic products can be used, but those having biodegradability are preferred from the viewpoint of environmental conservation.
Examples of the polyvalent metal used in the present invention include iron compounds such as iron chloride and iron sulfate, aluminum compounds such as aluminum chloride and a sulfate band, and zinc compounds such as zinc chloride and zinc sulfate. It is not something.
Examples of rare earth compounds used in the present invention include, but are not limited to, chlorides such as cerium, lanthanum, neodymium, praseodymium, samarium, gadolinium, terbium, yttrium, sulfates, nitrates, and acetates. .
By adding these compounds, the flocs are increased in cohesiveness and sludge volume can be reduced.
The scavenger for borofluoric acid represented by the general formula (2) or (4) may be added directly to the waste water, or a packed bed may be formed and the waste water passed therethrough.
The borofluoric acid scavenger represented by the general formula (2) or (4) was quaternized with an aqueous solution or a substituent of a quaternary ammonium salt represented by the general formula (1) or (3). It can be prepared by reacting an aqueous solution of a nitrogen-containing heterocyclic compound having nitrogen with an anionic polymer, but in particular, an anionic polymer corresponding to A in the general formula (2) or an aqueous solution thereof is preferably used. They can be easily obtained by mixing them and separating the produced precipitate into solid and liquid.
The quaternary ammonium salt or the nitrogen-containing heterocyclic compound having nitrogen quaternized with a substituent and the anionic polymer can be mixed in any ratio, but preferably a quaternary ammonium salt or a nitrogen-containing heterocyclic ring By mixing at a ratio of the number of moles of anionic sites of 0.01 mol to 5.0 mol, more preferably 0.1 mol to 2.5 mol, with respect to 1 mol of the compound, the effect is efficiently obtained. High scavengers can be made.
As alginic acid, only mannuronic acid, guluronic acid alone or these random forms may be used, and those having a polymerization degree of about 200 to 800 are preferably used.
Pectin is a linear polysaccharide composed of D-galacturonic acid, and a part of the carboxyl group is a methyl ester. In the present invention, high methoxy pectin having a degree of esterification of 50% or more and low methoxy pectin having a degree of esterification of 50% or less can be preferably used.
Gelatin is composed of α-amino acids and imino acids linked by peptide bonds, and there are various amino acid components, but glycine, proline and hydroxyproline occupy more than half of the molecular weight. The average molecular weight is 20,000 to 200,000 or more, and a molecular weight of 50,000 to 150,000 is particularly preferred.
As anionized starch, an anionic functional group is introduced into the hydroxyl group of the glucose portion of starch, and carboxymethyl starch or phosphorylated starch into which carboxymethyl group or phosphonic acid group is introduced can be suitably used. .
The carboxymethyl cellulose is not particularly specified, but those having a carboxy substitution degree of 0.5 to 2.0 per glucose unit can be preferably used.
As polyacrylic acid, a polymer obtained by polymerizing acrylic acid and / or a salt thereof is used. Acrylic acid can be polymerized by a Redox catalyst comprising a persulfate such as ammonium persulfate or potassium persulfate, or a combination of a persulfate / reducing agent. Moreover, you may superpose | polymerize by visible light, an ultraviolet-ray, an electron beam, or a gamma ray. Moreover, the product manufactured by saponifying polyacrylic acid ester, such as polymethyl acrylate, with a caustic alkali can also be used suitably.
As the copolymer of acrylamide and acrylic acid, a copolymer obtained by copolymerizing acrylamide with sodium acrylate or a cationic monomer can be preferably used. Commercially available products are products sold by Sanyo Kasei Kogyo Co., Ltd. under the trade name “Sunfrock (registered trademark)”, and commercially available from Mitsui Sinamid Co., Ltd. under the product name “Superflock (registered trademark)”. Products.
By directly putting the scavenger obtained by the above method into wastewater containing borofluoride adjusted to a pH of less than 5 and stirring for a while, solid-liquid separation into treated water and discharged material Removal of borofluoride from the wastewater becomes possible.
Alternatively, it is possible to remove the borofluoride by filling the scavenger in a removal tower and passing the waste water containing the borofluoride adjusted to pH 5 or less.
The scavenger of general formula (2) or general formula (4) used for removing borofluoride is desorbed borohydrofluoric acid by contacting with a solution adjusted to pH 8 or more, and used as a scavenger repeatedly. be able to.
In the method of the present invention, borohydrofluoride can be removed, but fluorine and boron cannot be removed. When the wastewater contains fluorine and boron together with borofluoride, the method of the present invention is applied after removing fluorine by treatment with calcium and aluminum by calcium treatment, which is a general method. May be.
In the case of waste liquid containing a large amount of borofluoride in the wastewater, before adding the borofluoric acid scavenger of the present invention, a compound that reacts with borofluoric acid to form a salt is added to form a borofluoride salt. It can also be deposited and removed. Examples of the compounds that react with borofluoric acid to form salts include potassium salts such as potassium chloride and potassium carbonate. By adding these, borohydrofluoric acid in the effluent can be reduced to some extent. By using the supplement of the present invention for the unbreakable borofluoric acid, the supplement can be used efficiently.
Even if the borofluoride scavenger of the present invention is added more than the necessary amount, there is no problem in the ability to remove borofluoric acid, but the COD and BOD in the waste water may be increased. In this case, excess borofluoride scavenger can be removed by adding a quaternary ammonium scavenger after the borohydrofluoric acid removing treatment. Examples of quaternary ammonium scavengers include activated carbon, bentonite, and cypro gum, and the COD and BOD values can be suppressed by adding them after removing borohydrofluoric acid from the waste water.
本発明の一般式（２）、一般式（４）のホウフッ化捕捉剤について以下の実施例に基き詳細に説明する。
［実施例１］
一般式（２）、一般式（４）で表される化合物として、捕捉剤を以下のように作成した。１，０００ｍｌの水に４級アンモニウム塩又は置換基によって４級化された窒素を持つ含窒素複素環化合物を下記表１に示される量を溶解し、別にアニオン性高分子化合物を、１，０００ｍｌの水に表１に示される量を溶解し、この２つの水溶液を混合して生成した沈殿物を採取してホウフッ化水素酸捕捉剤を作成した。
ペクチン（ドイツヘルプシュトライト社製ＬＭペクチン）
ゼラチン（新田ゼラチン株式会社製ゼラチン）
アニオン化でんぷん（日本澱粉株式会社製プリバインＰ−６３）
カルボシキメチルセルロース（第一工業製薬株式会社製セロゲン）
ポリアクリル酸（東亜合成株式会社製アロン）
アクリルアミドとアクリル酸との共重合体（ラサフロック工業株式会社製ＲＡ−５１）
次に処理方法の実施例について詳細に説明する。
処理水中のフッ素の分析は、ＪＩＳ Ｋ ０１０２に定めるランタン−アリザリンコンプレキソン法、ホウ素の分析は同じくＪＩＳ Ｋ ０１０２に定めるメチレンブルー吸光光度法により測定した。
処理方法の実施に試用した排水は、メッキ工場から排出されたホウフッ化水素酸塩を含有する排水を使用した。
この排水は、ホウフッ化水素酸塩が１１４ｐｐｍ（１．３×１０−３ｍｏｌ／ｌ；フッ素として１００ｐｐｍ、ホウ素として１４ｐｐｍ）含まれており、ｐＨは２．８であった。
［実施例２］
排水１，０００ｍｌに表２に示すように一般式（１）、一般式（３）の化合物を添加して５分間撹拌した後、静置した。このとき処理水には白濁が見られたため、更に５Ａの濾紙で濾過した。濾過液についてフッ素、ホウ素の分析を行った。尚、比較例として一般式（１）の化合物を使用しないで同様の処理を行った。その処理結果を表２に示す。
［実施例３］
排水１，０００ｍｌに一般式（１）で表される化合物として、トリメチルステアリルアンモニウムクロライドを１．４×１０−３ｍｏｌ／ｌ添加して５分間撹拌した後、凝集助剤として珪藻土、ベントナイト、アルギン酸ナトリウムを夫々１ｇ／ｌ添加し、更に水溶性高分子凝集剤としてアクリルアミドとアクリル酸との共重合体（ラサフロック工業株式会社製ＲＡ−５１）を添加して５分間撹拌後、静置した。この時のスラッジの沈降速度（上澄み液が澄明になるまでの時間）を目視により比較した。その結果を表３に示す。
［実施例４］
排水１，０００ｍｌに一般式（１）で表される化合物として、トリメチルステアリルアンモニウムクロライド（表３中ＴＭＳＡＣ）を１．４×１０−３ｍｏｌ／ｌ、一般式（３）で表される化合物として、セチルピリニジウムクロライド（表３中ＣＰＣ）１．４×１０−３ｍｏｌ／ｌを夫々添加して５分間撹拌、凝集助剤として珪藻土を１ｇ／ｌ添加して５分間撹拌した後、更に多価金属化合物として塩化鉄、希土類化合物として硫酸セリウムを夫々５ｐｐｍ添加した。水溶性高分子凝集剤としてアクリルアミドとアクリル酸との共重合体（ラサフロック工業株式会社製ＲＡ−５１）を添加して５分間撹拌後、静置した。この時のスラッジの層厚を比較した。その結果を表３に示す。
スラッジの層厚：処理工程終了１０分後のスラッジの厚さを目視で確認した。（スラッジの厚さ／排水の液までの高さ）で割合を記載。
表３に示す通り、凝集助剤を使用することでホウフッ化水素酸塩と一般式（１）又は一般式（３）で表される化合物で生成する難溶性物質を速やかに凝集・沈降することが可能となる。更に多価金属類／希土類化合物を併用することにより沈降速度を速め、スラッジ量を減容することが可能となる。
［実施例５］
一般式（２）で表される化合物として、トリメチルステアリルアンモニウムクロライドを３５ｇを１，０００ｍｌの水に溶解し、更にアニオン性高分子化合物としてキミツアルギン２０ｇを１，０００ｍｌの水に溶解し、この２つの水溶液を混合して生成した沈殿物を採取してホウフッ化水素酸捕捉剤１、１５を作成した。
排水１，０００ｍｌにホウフッ化水素酸捕捉剤１を表４に示す通り添加して、１時間撹拌後、固液分離を行い、フッ素濃度、ホウ素濃度の測定を行った。比較例として、排水のｐＨをＮａＯＨで、７．５に夫々調整して同様の操作を行った。その結果を表４に示す。
同様に、その他の捕捉剤２〜１４を使用してメッキ工場排水の処理を行った。メッキ工場排水のｐＨは２．８、捕捉剤の使用量はすべて１０ｇ／排水１ｌとして処理を行い、フッ素濃度、ホウ素濃度の測定を行った。その結果を表５に示す。
［実施例６］
ホウフッ化水素酸捕捉剤１を充填槽に５００ｇ充填して、ここに毎分１，０００ｍｌの排水を通水した。１００ｌ処理する毎に得られた処理水のフッ素濃度、ホウ素濃度の測定を行った。その結果を表６に示す。
次に、ホウフッ化水素酸捕捉剤の再生方法について詳細に説明する。
［実施例７］
実施例６で７００ｌの排水を処理した後、充填槽にｐＨ１０に調整したＮａＨＯ溶液を満たした。３０分後、ＮａＯＨ溶液を廃棄した後、水で洗浄し再生を行った。再度この充填槽を使用して実施例５に従い排水の処理を行った。その結果を表７に示す。
［実施例８］
フッ素として１０ｇ／Ｌのホウフッ化物含有排水１０００ｍｌに塩化カリウムを添加して反応後、ホウフッ化カリウムとして析出した沈殿物を除去した液に一般式（１）で表される化合物として、トリメチルステアリルアンモニウムクロライドを、一般式（３）で表される化合物として、セチルピリジウムクロライドを各々添加して５分間攪拌、凝集助剤として珪藻土１ｇ／Ｌ添加して５分間攪拌した後、水溶性高分子凝集剤としてアクリルアミドとアクリル酸との共重合体（ラサフロック工業株式会社製ＲＡ−５１）を添加して５分間攪拌後、静置した。上澄み中のフッ素濃度を測定した結果、フッ素は８ｐｐｍ以下となった。その結果を表８に示す。
［実施例９］
排水１０００ｍｌに一般式（１）で表される化合物として、トリメチルステアリルアンモニウムクロライドを１．４×１０−３ｍｏｌ／Ｌ添加して５分攪拌、凝集助剤として珪藻土１ｇ／Ｌ添加して５分間攪拌した後、水溶性高分子凝集剤としてアクリルアミドとアクリル酸との共重合体（ラサフロック工業株式会社製ＲＡ−５１）を添加して５分間攪拌後、固液分離した。濾液に４級アンモニウム捕捉剤として活性炭、ベントナイト、キプロガムを各々添加し５分攪拌後、固液分離した液のＣＯＤを比較した。その結果を表９に示す。
[Example 1]
As the compounds represented by the general formula (2) and the general formula (4), a scavenger was prepared as follows. In 1,000 ml of water, dissolve the quaternary ammonium salt or nitrogen-containing heterocyclic compound having nitrogen quaternized with a substituent in the amount shown in Table 1 below, and separately add an anionic polymer compound in 1,000 ml. The amount shown in Table 1 was dissolved in water, and the precipitate formed by mixing the two aqueous solutions was collected to prepare a borohydrofluoric acid scavenger.
Pectin (LM Pectin, manufactured by German Help Stolite)
Gelatin (gelatin manufactured by Nitta Gelatin Co., Ltd.)
Anionized starch (Privine P-63 manufactured by Nippon Starch Co., Ltd.)
Carboxymethylcellulose (Serogen, Daiichi Kogyo Seiyaku Co., Ltd.)
Polyacrylic acid (Aron by Toa Gosei Co., Ltd.)
Copolymer of acrylamide and acrylic acid (RA-51 manufactured by Rasa Flock Industrial Co., Ltd.)
Next, an embodiment of the processing method will be described in detail.
Fluorine in the treated water was analyzed by a lanthanum-alizarin complexone method defined in JIS K 0102, and boron was analyzed by a methylene blue absorptiometric method also defined in JIS K 0102.
The wastewater used for the treatment method was wastewater containing borofluoride discharged from a plating plant.
This wastewater contained 114 ppm (1.3 × 10 −3 mol / l; 100 ppm as fluorine, 14 ppm as boron) of borohydrofluoride, and had a pH of 2.8.
[Example 2]
As shown in Table 2, the compounds of general formula (1) and general formula (3) were added to 1,000 ml of waste water and stirred for 5 minutes, and then allowed to stand. At this time, since white turbidity was observed in the treated water, it was further filtered through a 5A filter paper. The filtrate was analyzed for fluorine and boron. In addition, the same process was performed without using the compound of General formula (1) as a comparative example. The processing results are shown in Table 2.
[Example 3]
As a compound represented by the general formula (1) in 1,000 ml of waste water, 1.4 × 10 −3 mol / l of trimethylstearyl ammonium chloride was added and stirred for 5 minutes, and then diatomaceous earth, bentonite, alginic acid as a coagulant aid. Sodium was added in an amount of 1 g / l, and a copolymer of acrylamide and acrylic acid (RA-51 manufactured by Rasa Flock Industrial Co., Ltd.) was further added as a water-soluble polymer flocculant. The mixture was stirred for 5 minutes and allowed to stand. The sludge settling speed (time until the supernatant liquid becomes clear) at this time was compared visually. The results are shown in Table 3.
[Example 4]
As a compound represented by general formula (1) in 1,000 ml of waste water, 1.4 × 10 −3 mol / l of trimethylstearyl ammonium chloride (TMSAC in Table 3), as a compound represented by general formula (3) Cetylpyridinium chloride (CPC in Table 3) 1.4 × 10 −3 mol / l was added and stirred for 5 minutes, 1 g / l of diatomaceous earth was added as an agglomeration aid, and the mixture was stirred for 5 minutes. 5 ppm each of iron chloride as the polyvalent metal compound and cerium sulfate as the rare earth compound was added. As a water-soluble polymer flocculant, a copolymer of acrylamide and acrylic acid (RA-51 manufactured by Rasa Flock Industrial Co., Ltd.) was added and stirred for 5 minutes, and then allowed to stand. The layer thickness of the sludge at this time was compared. The results are shown in Table 3.
Sludge layer thickness: The thickness of the sludge 10 minutes after the completion of the treatment step was visually confirmed. The ratio is described as (thickness of sludge / height up to drainage liquid).
As shown in Table 3, by using an agglomeration aid, quickly flocculate and settle a poorly soluble substance produced from a compound represented by general formula (1) or general formula (3). Is possible. Further, by using a polyvalent metal / rare earth compound in combination, it is possible to increase the sedimentation rate and reduce the amount of sludge.
[Example 5]
As a compound represented by the general formula (2), 35 g of trimethylstearyl ammonium chloride is dissolved in 1,000 ml of water, and 20 g of Kimiargin as an anionic polymer compound is dissolved in 1,000 ml of water. Precipitates formed by mixing aqueous solutions were collected to prepare borohydrofluoric acid scavengers 1 and 15.
The borohydrofluoric acid scavenger 1 was added to 1,000 ml of waste water as shown in Table 4, and after stirring for 1 hour, solid-liquid separation was performed to measure the fluorine concentration and the boron concentration. As a comparative example, the same operation was performed by adjusting the pH of the waste water to 7.5 with NaOH. The results are shown in Table 4.
Similarly, other scavengers 2-14 were used to treat plating factory effluent. The plating factory effluent was treated at a pH of 2.8, and the amount of scavenger used was 10 g / l of effluent, and the fluorine concentration and boron concentration were measured. The results are shown in Table 5.
[Example 6]
500 g of the borohydrofluoric acid scavenger 1 was filled in a filling tank, and 1,000 ml of waste water was passed therethrough per minute. The fluorine concentration and boron concentration of the treated water obtained every 100 l were measured. The results are shown in Table 6.
Next, a method for regenerating the borohydrofluoric acid scavenger will be described in detail.
[Example 7]
After 700 l of waste water was treated in Example 6, the filling tank was filled with a NaHO solution adjusted to pH 10. After 30 minutes, the NaOH solution was discarded, followed by washing with water for regeneration. Using this filling tank again, the waste water was treated according to Example 5. The results are shown in Table 7.
[Example 8]
After adding potassium chloride to 1000 ml of borofluoride-containing wastewater containing 10 g / L as fluorine and reacting it, trimethylstearylammonium chloride as a compound represented by the general formula (1) is obtained by removing the precipitate deposited as potassium borofluoride. As a compound represented by the general formula (3), cetylpyridinium chloride was added to each of them and stirred for 5 minutes, and 1 g / L of diatomaceous earth was added as a coagulant aid and stirred for 5 minutes. A copolymer of acrylamide and acrylic acid (RA-51 manufactured by Rasa Flock Industrial Co., Ltd.) was added and stirred for 5 minutes, and then allowed to stand. As a result of measuring the fluorine concentration in the supernatant, fluorine was 8 ppm or less. The results are shown in Table 8.
[Example 9]
As a compound represented by the general formula (1) in 1000 ml of waste water, 1.4 × 10 −3 mol / L of trimethylstearyl ammonium chloride is added and stirred for 5 minutes, and 1 g / L of diatomaceous earth is added as a coagulant aid for 5 minutes. After stirring, a copolymer of acrylamide and acrylic acid (RA-51 manufactured by Rasa Flock Industrial Co., Ltd.) was added as a water-soluble polymer flocculant, and the mixture was stirred for 5 minutes, and then solid-liquid separation was performed. Activated carbon, bentonite, and cyprogum were added to the filtrate as quaternary ammonium scavengers, respectively, and after stirring for 5 minutes, the CODs of the liquids separated into solid and liquid were compared. The results are shown in Table 9.
以上のように、本発明にかかるホウフッ化水素酸塩を含有する排水の処理方法に使用する添加剤及びその処理方法は、ホウフッ化水素酸塩を含有する排水から、加熱等の外部エネルギーを使用することなく、少ないスラッジ量で短時間にフッ素及びホウ素を除去することができるので有用である。更に、２次処理（高度処理）のための槽を設置する等設備の増強の必要がなく、既存の１次処理設備のみで高度処理が可能となるので有用である。 As described above, the additive used in the method of treating wastewater containing borohydrofluoride according to the present invention and the treatment method use external energy such as heating from wastewater containing borohydrofluoride. This is useful because fluorine and boron can be removed in a short time with a small amount of sludge. Furthermore, there is no need to increase facilities such as installing a tank for secondary processing (advanced processing), and it is useful because advanced processing can be performed only with existing primary processing facilities.
Claims (9)
一般式（１）
一般式（２）
一般式（３）
一般式（４）
General formula (1)
General formula (2)
General formula (3)
General formula (4)
Ａ群：アルギン酸、ペクチン、ゼラチン、アニオン化でんぷん、カルボキシメチルセルロース、ポリアクリル酸、アクリルアミドとアクリル酸との共重合体The borohydrofluoric acid scavenger according to claim 1, wherein A of the borohydrofluoric acid scavenger represented by the general formula (2) and the general formula (4) has a structure selected from the following group A. Agent.
Group A: Alginic acid, pectin, gelatin, anionized starch, carboxymethylcellulose, polyacrylic acid, copolymer of acrylamide and acrylic acid
一般式（１）
一般式（３）
General formula (1)
General formula (3)
一般式（１）
General formula (1)
一般式（２）
Ａ群：アルギン酸、ペクチン、ゼラチン、アニオン化でんぷん、カルボキシメチルセルロース、ポリアクリル酸、アクリルアミドとアクリル酸との共重合体
一般式（４）
General formula (2)
Group A: Alginic acid, pectin, gelatin, anionized starch, carboxymethylcellulose, polyacrylic acid, copolymer of acrylamide and acrylic acid, general formula (4)
一般式（２）
一般式（４）
General formula (2)
General formula (4)
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| JP2004033970 | 2004-02-10 | ||
| JP2004033970 | 2004-02-10 | ||
| PCT/JP2005/001984 WO2005075363A1 (en) | 2004-02-10 | 2005-02-03 | Borofluoric acid-trapping agent and method of treating wastewater with the same |
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| JPWO2005075363A1 JPWO2005075363A1 (en) | 2008-01-10 |
| JP4682043B2 true JP4682043B2 (en) | 2011-05-11 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54144764A (en) * | 1978-05-02 | 1979-11-12 | Hitachi Plant Eng & Constr Co Ltd | Method of treating borofluoride in waste water |
| JPS56129083A (en) * | 1980-11-27 | 1981-10-08 | Hitachi Plant Eng & Constr Co Ltd | Disposal of borofluoride in waste water |
| JPS5976592A (en) * | 1982-10-22 | 1984-05-01 | Hitachi Plant Eng & Constr Co Ltd | Treatment of waste water |
| JPH03119189A (en) * | 1989-10-03 | 1991-05-21 | Nippon Kamiparupu Kenkyusho:Kk | Treatment of white liquor of paper mill |
| JPH07195085A (en) * | 1994-01-12 | 1995-08-01 | Electric Power Dev Co Ltd | Treatment of dithionic acid ion-containing water |
| JP2003299953A (en) * | 2002-04-08 | 2003-10-21 | Japan Science & Technology Corp | Absorbing material for acidic substance and separation method using the same |
| JP2004033812A (en) * | 2002-06-28 | 2004-02-05 | Jfe Engineering Kk | Cleaning method of polluted soil or the like and cleaning equipment |
-
2005
- 2005-02-03 JP JP2005517818A patent/JP4682043B2/en active Active
- 2005-02-03 WO PCT/JP2005/001984 patent/WO2005075363A1/en active Application Filing
- 2005-02-03 TW TW94103429A patent/TW200535555A/en unknown
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54144764A (en) * | 1978-05-02 | 1979-11-12 | Hitachi Plant Eng & Constr Co Ltd | Method of treating borofluoride in waste water |
| JPS56129083A (en) * | 1980-11-27 | 1981-10-08 | Hitachi Plant Eng & Constr Co Ltd | Disposal of borofluoride in waste water |
| JPS5976592A (en) * | 1982-10-22 | 1984-05-01 | Hitachi Plant Eng & Constr Co Ltd | Treatment of waste water |
| JPH03119189A (en) * | 1989-10-03 | 1991-05-21 | Nippon Kamiparupu Kenkyusho:Kk | Treatment of white liquor of paper mill |
| JPH07195085A (en) * | 1994-01-12 | 1995-08-01 | Electric Power Dev Co Ltd | Treatment of dithionic acid ion-containing water |
| JP2003299953A (en) * | 2002-04-08 | 2003-10-21 | Japan Science & Technology Corp | Absorbing material for acidic substance and separation method using the same |
| JP2004033812A (en) * | 2002-06-28 | 2004-02-05 | Jfe Engineering Kk | Cleaning method of polluted soil or the like and cleaning equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200535555A (en) | 2005-11-01 |
| WO2005075363A1 (en) | 2005-08-18 |
| JPWO2005075363A1 (en) | 2008-01-10 |
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