TW202415629A - Fluidized bed homogeneous crystallization method for treating pollutant ion in wastewater and equipment thereof having a good pollutant ions removal rate and a good crystallization rate of crystalline precipitated particles - Google Patents
Fluidized bed homogeneous crystallization method for treating pollutant ion in wastewater and equipment thereof having a good pollutant ions removal rate and a good crystallization rate of crystalline precipitated particles Download PDFInfo
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- TW202415629A TW202415629A TW111137701A TW111137701A TW202415629A TW 202415629 A TW202415629 A TW 202415629A TW 111137701 A TW111137701 A TW 111137701A TW 111137701 A TW111137701 A TW 111137701A TW 202415629 A TW202415629 A TW 202415629A
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- Prior art keywords
- ions
- crystallizer
- solution
- pollutant
- fluidized bed
- Prior art date
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- 150000002500 ions Chemical class 0.000 title claims abstract description 237
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 236
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 236
- 239000002245 particle Substances 0.000 title claims abstract description 177
- 238000002425 crystallisation Methods 0.000 title claims abstract description 156
- 230000008025 crystallization Effects 0.000 title claims abstract description 140
- 239000002351 wastewater Substances 0.000 title claims abstract description 93
- 239000000243 solution Substances 0.000 claims abstract description 180
- 239000007788 liquid Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 51
- 239000011259 mixed solution Substances 0.000 claims abstract description 34
- 238000001914 filtration Methods 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 239000000706 filtrate Substances 0.000 claims abstract description 14
- -1 aluminum ions Chemical class 0.000 claims description 70
- 239000003795 chemical substances by application Substances 0.000 claims description 66
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 36
- 238000000926 separation method Methods 0.000 claims description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 30
- 239000013078 crystal Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 17
- 229910001431 copper ion Inorganic materials 0.000 claims description 17
- 239000008213 purified water Substances 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 16
- 229910001453 nickel ion Inorganic materials 0.000 claims description 16
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 229910001424 calcium ion Inorganic materials 0.000 claims description 15
- 235000021317 phosphate Nutrition 0.000 claims description 15
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 13
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 13
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 11
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 229910052755 nonmetal Inorganic materials 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 238000005342 ion exchange Methods 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims 1
- 239000002244 precipitate Substances 0.000 description 58
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 40
- 229940039748 oxalate Drugs 0.000 description 21
- 229910000029 sodium carbonate Inorganic materials 0.000 description 20
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 17
- 239000010452 phosphate Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011667 zinc carbonate Substances 0.000 description 12
- 235000004416 zinc carbonate Nutrition 0.000 description 12
- 229910000010 zinc carbonate Inorganic materials 0.000 description 12
- 230000032258 transport Effects 0.000 description 11
- 238000000265 homogenisation Methods 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 6
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 6
- 235000019799 monosodium phosphate Nutrition 0.000 description 6
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 description 6
- 239000001488 sodium phosphate Substances 0.000 description 6
- 235000011008 sodium phosphates Nutrition 0.000 description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 4
- 229940039790 sodium oxalate Drugs 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- GMTYREVWZXJPLF-AFHUBHILSA-N butorphanol D-tartrate Chemical compound OC(=O)[C@@H](O)[C@H](O)C(O)=O.N1([C@@H]2CC3=CC=C(C=C3[C@@]3([C@]2(CCCC3)O)CC1)O)CC1CCC1 GMTYREVWZXJPLF-AFHUBHILSA-N 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000012085 test solution Substances 0.000 description 3
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-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
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000907663 Siproeta stelenes Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 1
- ZVCNBVJYXBEKTC-UHFFFAOYSA-L azanium;zinc;phosphate Chemical compound [NH4+].[Zn+2].[O-]P([O-])([O-])=O ZVCNBVJYXBEKTC-UHFFFAOYSA-L 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 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
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- QENHCSSJTJWZAL-UHFFFAOYSA-N magnesium sulfide Chemical compound [Mg+2].[S-2] QENHCSSJTJWZAL-UHFFFAOYSA-N 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical class O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本發明是有關於一種廢水的處理方法及設備，特別是指一種處理廢水中汙染物離子的流體化床均質結晶方法及其設備。The present invention relates to a method and equipment for treating wastewater, and more particularly to a fluidized bed homogeneous crystallization method and equipment for treating pollutant ions in wastewater.
在現有的工業及高科技產業中，常常需要為了製程需求而使用大量的水資源，所以也伴隨著產生含有大量汙染物質(例如重金屬離子、草酸根離子或磷酸根離子)的廢水，而隨著目前大眾對於環保議題的重視，許多業者會藉由對廢水進行淨化處理去除廢水中的汙染物質，從而避免直接排放廢水對環境造成危害。In existing industries and high-tech industries, a large amount of water resources are often needed for process requirements, so wastewater containing a large amount of pollutants (such as heavy metal ions, oxalate ions or phosphate ions) is also generated. With the public's current attention to environmental protection issues, many companies will purify wastewater to remove pollutants in wastewater, thereby avoiding direct discharge of wastewater to cause harm to the environment.
目前常見用於去除廢水中的汙染物質的方法例如化學混凝法、吸附法或流體化床結晶技術等。其中，流體化床結晶技術是透過將含有汙染物質的廢水，以及能夠使汙染物質形成結晶的藥劑導入一個內部具有由例如矽砂或磚粉等有別於廢水中的汙染物質的成分所組成的異質擔體的流體化床反應槽，以使汙染物質在與藥劑反應後能夠於異質擔體上形成結晶，藉此達到去除廢水中的汙染物質的目的。Common methods for removing pollutants from wastewater include chemical coagulation, adsorption or fluidized bed crystallization. Among them, fluidized bed crystallization is to introduce wastewater containing pollutants and reagents that can crystallize pollutants into a fluidized bed reaction tank having a heterogeneous carrier composed of components different from the pollutants in the wastewater, such as silica sand or brick powder, so that the pollutants can form crystals on the heterogeneous carrier after reacting with the reagent, thereby achieving the purpose of removing pollutants from the wastewater.
台灣公告專利第I644857B號揭示一種以流體化床結晶技術合成均質含鋅結晶物之方法，且是將含鋅廢水與造粒藥劑引入流體化床反應槽內混合，使得含鋅廢水中的鋅離子與造粒藥劑反應以產生均質含鋅結晶物。雖然上述方法能夠透過不採用異質擔體的方式來去除含鋅廢水中的鋅離子，同時提高含鋅結晶物的純度，但，上述方法所排放出的經處理的廢水中仍會殘留有未能沉澱於流體化床反應槽內的含鋅結晶懸浮顆粒及尚未與造粒藥劑反應的鋅離子等汙染物質，因此，上述方法仍存在有需要改善的問題。Taiwan Patent Publication No. I644857B discloses a method for synthesizing homogeneous zinc-containing crystals using fluidized bed crystallization technology, wherein zinc-containing wastewater and a granulation agent are introduced into a fluidized bed reaction tank for mixing, so that zinc ions in the zinc-containing wastewater react with the granulation agent to produce homogeneous zinc-containing crystals. Although the above method can remove zinc ions from zinc-containing wastewater without using a heterogeneous carrier and improve the purity of zinc-containing crystals, the treated wastewater discharged by the above method still contains pollutants such as zinc-containing crystal suspended particles that have not settled in the fluidized bed reactor and zinc ions that have not reacted with the granulation agent. Therefore, the above method still has problems that need to be improved.
因此，本發明的第一目的，即在提供一種能有效地去除汙染物且幾乎不會排放出含有汙染物質的經處理的廢水的處理廢水中汙染物離子的流體化床均質結晶方法。Therefore, the first object of the present invention is to provide a fluidized bed homogeneous crystallization method for treating wastewater, which can effectively remove pollutants and almost does not discharge treated wastewater containing pollutants.
於是，本發明處理廢水中汙染物離子的流體化床均質結晶方法是進行兩次以上的處理程序，且每一次處理程序包括一步驟(a)、一步驟(b)、一步驟(c)、一步驟(d)及一步驟(e)。Therefore, the fluidized bed homogenization crystallization method for treating pollutant ions in wastewater of the present invention is to carry out more than two treatment procedures, and each treatment procedure includes step (a), step (b), step (c), step (d) and step (e).
該步驟(a)使包含廢水的待處理溶液與包含結晶劑的結晶劑溶液在一不包含異質擔體的流體化床結晶裝置混合，其中，該廢水包括汙染物離子，且該待處理溶液與該結晶劑溶液混合後的pH值落在一預定pH值範圍，以使該待處理溶液中的汙染物離子與該結晶劑溶液中的結晶劑在該預定pH值範圍下反應形成結晶沉澱顆粒，並獲得包含結晶懸浮顆粒及未與該結晶劑反應的汙染物離子的混合溶液。The step (a) mixes a solution to be treated containing wastewater with a crystallizer solution containing a crystallizer in a fluidized bed crystallization device that does not contain a heterogeneous carrier, wherein the wastewater contains pollutant ions, and the pH value of the solution to be treated and the crystallizer solution after mixing falls within a predetermined pH range, so that the pollutant ions in the solution to be treated react with the crystallizer in the crystallizer solution within the predetermined pH range to form crystallized precipitated particles, and obtain a mixed solution containing crystallized suspended particles and pollutant ions that have not reacted with the crystallizer.
該步驟(b)將該混合溶液進行過濾處理，獲得包含該結晶懸浮顆粒的殘留物及包含未與該結晶劑反應的該汙染物離子的濾液。In step (b), the mixed solution is filtered to obtain a residue containing the crystallized suspended particles and a filtrate containing the pollutant ions that have not reacted with the crystallizing agent.
該步驟(c)將該殘留物輸送回該流體化床結晶裝置中，並使該殘留物中的結晶懸浮顆粒與該結晶劑溶液中的結晶劑反應形成結晶沉澱顆粒。In step (c), the residue is transported back to the fluidized bed crystallization device, and the crystallized suspended particles in the residue are reacted with the crystallizing agent in the crystallizing agent solution to form crystallized precipitated particles.
該步驟(d)將該濾液進行分離處理，以從該濾液中分離出未與該結晶劑反應的該汙染物離子，並獲得淨化水及包含未與該結晶劑反應的該汙染物離子的處理液，其中，該處理液中的未與該結晶劑反應的該汙染物離子的濃度大於該濾液中的未與該結晶劑反應的該汙染物離子的濃度。In step (d), the filter liquid is subjected to a separation treatment to separate the pollutant ions that have not reacted with the crystallization agent from the filter liquid, and purified water and a treatment liquid containing the pollutant ions that have not reacted with the crystallization agent are obtained, wherein the concentration of the pollutant ions that have not reacted with the crystallization agent in the treatment liquid is greater than the concentration of the pollutant ions that have not reacted with the crystallization agent in the filter liquid.
該步驟(e)將當次處理程序的該處理液與下一批次的廢水混合，而成為下一次處理程序的待處理溶液。In step (e), the treated solution of the current treatment process is mixed with the next batch of wastewater to form a solution to be treated in the next treatment process.
本發明的第二目的，即在提供一種流體化床均質結晶設備。The second object of the present invention is to provide a fluidized bed homogeneous crystallization equipment.
於是，本發明流體化床均質結晶設備，適用於處理一包含廢水的待處理溶液，且該廢水包括汙染物離子，該流體化床均質結晶設備包含一結晶劑供應裝置、一流體化床結晶裝置、一過濾裝置、一迴流裝置及一分離裝置。Therefore, the fluidized bed homogenization crystallization equipment of the present invention is suitable for treating a solution to be treated including wastewater, and the wastewater includes pollutant ions. The fluidized bed homogenization crystallization equipment includes a crystallizing agent supply device, a fluidized bed crystallization device, a filtering device, a reflux device and a separation device.
該結晶劑供應裝置用以提供包含能與該待處理溶液中的汙染物離子進行結晶反應且形成結晶的結晶劑的結晶劑溶液。The crystallizing agent supply device is used to provide a crystallizing agent solution containing a crystallizing agent capable of reacting with pollutant ions in the solution to be treated to form crystals.
該流體化床結晶裝置與該結晶劑供應裝置連通，且不包括異質擔體並界定出一反應空間，該反應空間用以供該待處理溶液與來自該結晶劑供應裝置的該結晶劑溶液混合，且該待處理溶液與該結晶劑溶液混合後的pH值落在一預定pH值範圍，以使該待處理溶液中的汙染物離子與該結晶劑溶液中的結晶劑在該預定pH值範圍下反應形成結晶沉澱顆粒，並獲得包含結晶懸浮顆粒及未與該結晶劑反應的汙染物離子的混合溶液。The fluidized bed crystallization device is connected to the crystallizer supply device, does not include a heterogeneous carrier and defines a reaction space, wherein the reaction space is used for mixing the solution to be treated with the crystallizer solution from the crystallizer supply device, and the pH value of the solution to be treated and the crystallizer solution after mixing falls within a predetermined pH value range, so that the pollutant ions in the solution to be treated react with the crystallizer in the crystallizer solution within the predetermined pH value range to form crystallized precipitated particles, and a mixed solution containing crystallized suspended particles and pollutant ions that have not reacted with the crystallizer is obtained.
該過濾裝置設置於該流體化床結晶裝置的下游，並用以對來自該流體化床結晶裝置的該混合溶液進行過濾，獲得包含該結晶懸浮顆粒的殘留物及包含未與該結晶劑反應的該汙染物離子的濾液。The filtering device is arranged downstream of the fluidized bed crystallization device and is used for filtering the mixed solution from the fluidized bed crystallization device to obtain a filtrate containing the residue of the crystallization suspended particles and the pollutant ions that have not reacted with the crystallization agent.
該迴流裝置設置於該過濾裝置的下游，並與該流體化床結晶裝置連通，並用以將該殘留物輸送回該反應空間內，以使該殘留物中的結晶懸浮顆粒與該結晶劑溶液中的結晶劑反應形成結晶沉澱顆粒。The reflux device is arranged downstream of the filtering device and communicated with the fluidized bed crystallization device, and is used to transport the residue back to the reaction space so that the crystallized suspended particles in the residue react with the crystallizing agent in the crystallizing agent solution to form crystallized precipitated particles.
該分離裝置與該過濾裝置連通，並用以對來自該過濾裝置的該濾液進行分離處理，以從該濾液中分離出未與該結晶劑反應的該汙染物離子，獲得淨化水及包含未與該結晶劑反應的該汙染物離子的處理液，並將該處理液輸送至該流體化床結晶裝置中，其中，該處理液中的未與該結晶劑反應的該汙染物離子的濃度大於該濾液中的未與該結晶劑反應的該汙染物離子的濃度。The separation device is connected to the filtering device and is used to perform separation treatment on the filter liquid from the filtering device to separate the pollutant ions that have not reacted with the crystallizer from the filter liquid, obtain purified water and a treatment liquid containing the pollutant ions that have not reacted with the crystallizer, and transport the treatment liquid to the fluidized bed crystallization device, wherein the concentration of the pollutant ions that have not reacted with the crystallizer in the treatment liquid is greater than the concentration of the pollutant ions that have not reacted with the crystallizer in the filter liquid.
本發明的功效在於：本發明的方法透過將該混合溶液進行該過濾處理，獲得包含結晶懸浮顆粒的該殘留物及包含未與該結晶劑反應的汙染物離子的該濾液，以及將該殘留物輸送回流體化床結晶裝置，及將該濾液進行該分離處理後輸送回流體化床結晶裝置，讓結晶懸浮顆粒及未與該結晶劑反應的汙染物離子也能夠回到該流體化床結晶裝置與結晶劑及下一批次的廢水反應而生成結晶沉澱顆粒，從而使本發明的方法所排放出的淨化水中幾乎不含有汙染物離子及結晶懸浮顆粒，而具有高的汙染物離子去除率及高的結晶沉澱顆粒結晶率。另外，本發明流體化床均質結晶設備透過該結晶劑供應裝置、該流體化床結晶裝置、該過濾裝置、該迴流裝置及該分離裝置的相互配合，尤其是該過濾裝置、該迴流裝置及該分離裝置，從而能夠有效地將廢水中的汙染物離子轉變成純度高的結晶沉澱顆粒，以達到去除廢水中的汙染物離子之目的。The utility model is that: the method of the present invention obtains the residue containing the crystallized suspended particles and the filter liquid containing the pollutant ions that have not reacted with the crystallizer by filtering the mixed solution, and transports the residue back to the fluidized bed crystallization device, and transports the filter liquid back to the fluidized bed crystallization device after the separation treatment, so that the crystallized suspended particles are The particles and pollutant ions that have not reacted with the crystallizer can also return to the fluidized bed crystallization device to react with the crystallizer and the next batch of wastewater to generate crystallized precipitated particles, so that the purified water discharged by the method of the present invention contains almost no pollutant ions and crystallized suspended particles, and has a high pollutant ion removal rate and a high crystallization rate of crystallized precipitated particles. In addition, the fluidized bed homogenization crystallization equipment of the present invention can effectively transform pollutant ions in wastewater into crystallized precipitated particles with high purity through the cooperation of the crystallizer supply device, the fluidized bed crystallization device, the filtering device, the reflux device and the separation device, especially the filtering device, the reflux device and the separation device, so as to achieve the purpose of removing pollutant ions in wastewater.
以下對本發明進行詳細說明。The present invention is described in detail below.
參閱圖1，本發明流體化床均質結晶設備的第一實施例，適用於處理一包含廢水的待處理溶液，且該廢水包括汙染物離子。該汙染物離子例如但不限於金屬離子或非金屬離子。在本發明的一些實施態樣中，該汙染物離子是選自於金屬離子或非金屬離子。該金屬離子例如但不限於鋅離子、鎳離子、鋁離子、銅離子、鈷離子、鈣離子、鎂離子或鐵離子等。在本發明的一些實施態樣中，該金屬離子是選自於鋅離子、鎳離子、鋁離子、銅離子、鈷離子、鈣離子、鎂離子或鐵離子。在本發明的一些實施態樣中，該金屬離子是選自於鋅離子、鎳離子、鋁離子或銅離子。該非金屬離子例如但不限於草酸根離子、磷酸根離子、硫酸根離子、硫離子或銨離子。在本發明的一些實施態樣中，該非金屬離子是選自於草酸根離子、磷酸根離子、硫酸根離子、硫離子或銨離子。在本發明的一些實施態樣中，該非金屬離子是選自於草酸根離子或磷酸根離子。Referring to FIG. 1 , the first embodiment of the fluidized bed homogeneous crystallization apparatus of the present invention is suitable for treating a solution to be treated comprising wastewater, and the wastewater includes pollutant ions. The pollutant ions are, for example, but not limited to, metal ions or non-metal ions. In some embodiments of the present invention, the pollutant ions are selected from metal ions or non-metal ions. The metal ions are, for example, but not limited to, zinc ions, nickel ions, aluminum ions, copper ions, cobalt ions, calcium ions, magnesium ions, or iron ions. In some embodiments of the present invention, the metal ion is selected from zinc ions, nickel ions, aluminum ions, copper ions, cobalt ions, calcium ions, magnesium ions or iron ions. In some embodiments of the present invention, the metal ion is selected from zinc ions, nickel ions, aluminum ions or copper ions. The non-metal ions are, for example but not limited to, oxalate ions, phosphate ions, sulfate ions, sulfur ions or ammonium ions. In some embodiments of the present invention, the non-metal ions are selected from oxalate ions, phosphate ions, sulfate ions, sulfur ions or ammonium ions. In some embodiments of the present invention, the non-metal ions are selected from oxalate ions or phosphate ions.
該流體化床均質結晶設備包含一結晶劑供應裝置1、一流體化床結晶裝置2、一過濾裝置3、一迴流裝置4，及一分離裝置5。The fluidized bed homogeneous crystallization equipment comprises a crystallizing
該結晶劑供應裝置1用以提供包含能與該待處理溶液中的汙染物離子進行結晶反應且形成結晶的結晶劑及用以溶解該結晶劑的水的結晶劑溶液。該結晶劑的種類是配合該汙染物離子的種類來選擇。當該汙染物離子為金屬離子時，該結晶劑例如但不限於能夠提供與該金屬離子反應而產生水難溶性沉澱結晶的陰離子的水可溶性化合物。在本發明的一些實施態樣中，當該汙染物離子為金屬離子時，該結晶劑是選自於水可溶性碳酸鹽、水可溶性磷酸鹽、水可溶性氫氧化物、水可溶性硫化物或水可溶性草酸鹽。當該汙染物離子為非金屬離子時，該結晶劑例如但不限於能夠提供與該非金屬離子反應而產生水難溶性沉澱結晶的陽離子的水可溶性化合物。在本發明的一些實施態樣中，當該汙染物離子為非金屬離子時，該結晶劑是選自於能夠提供鈣離子的水可溶性鈣源、能夠提供鎂離子的水可溶性鎂源，或能夠提供鋇離子的水可溶性鋇源。該水可溶性鈣源例如但不限於氯化鈣或硝酸鈣，該水可溶性鎂源例如但不限於氯化鎂或硝酸鎂，該水可溶性鋇源例如但不限於氯化鋇或硝酸鋇。The
該流體化床結晶裝置2與該結晶劑供應裝置1連通，且不包括異質擔體並界定出一反應空間21。該反應空間21用以供該待處理溶液與來自該結晶劑供應裝置1的該結晶劑溶液混合，且該待處理溶液與該結晶劑溶液混合後的pH值落在一預定pH值範圍，以使該待處理溶液中的汙染物離子與該結晶劑溶液中的結晶劑在該預定pH值範圍下反應，獲得結晶沉澱顆粒及混合溶液。該預定pH值範圍能夠用於使該汙染物離子與該結晶劑進行結晶反應且形成結晶。該預定pH值範圍是依據該汙染物離子的種類進行調整，於本發明中並沒有特別限制。該結晶沉澱顆粒為該汙染物離子與該結晶劑經反應所產生的水難溶性結晶沉澱顆粒，且該結晶沉澱顆粒在該流體化床結晶裝置2中流動的過程不會被該待處理溶液、該結晶劑溶液或該混合溶液沖走而離開該流體化床結晶裝置2。該混合溶液包含結晶懸浮顆粒及未與該結晶劑反應的汙染物離子。該結晶懸浮顆粒為該汙染物離子與該結晶劑經反應所產生的水難溶性結晶懸浮顆粒，且該結晶懸浮顆粒在該流體化床結晶裝置2中流動的過程會被該待處理溶液、該結晶劑溶液或該混合溶液沖走而離開該流體化床結晶裝置2。該結晶沉澱顆粒的粒徑大於該結晶懸浮顆粒的粒徑。The fluidized
要說明的是，由於該結晶沉澱顆粒是由該汙染物離子及結晶劑經反應所形成，所以該結晶沉澱顆粒中不包含其他非源自於該汙染物離子及該結晶劑的物質，因此，在本發明中，該結晶沉澱顆粒還能夠在該流體化床結晶裝置2中作為一種均質擔體，且該均質擔體不會對後續於該均質擔體的表面所生成之結晶沉澱顆粒的純度造成負面影響，藉此供未反應的汙染物離子及結晶懸浮顆粒能夠附著於該均質擔體的表面，從而形成新的結晶沉澱顆粒。It should be noted that, since the crystallized precipitate particles are formed by the reaction of the pollutant ions and the crystallizer, the crystallized precipitate particles do not contain other substances that are not derived from the pollutant ions and the crystallizer. Therefore, in the present invention, the crystallized precipitate particles can also serve as a homogeneous carrier in the fluidized
更具體地說，當該汙染物離子為鋅離子時，該結晶劑溶液的pH值例如但不限於9至11，該預定pH值範圍為7至9，該結晶劑為水可溶性碳酸鹽、水可溶性磷酸鹽、水可溶性氫氧化物或水可溶性硫化物，該水難溶性結晶沉澱顆粒相應為碳酸鋅結晶沉澱顆粒、磷酸鋅結晶沉澱顆粒、氫氧化鋅結晶沉澱顆粒或硫化鋅結晶沉澱顆粒。其中，該水可溶性碳酸鹽例如但不限於碳酸鈉或碳酸氫鈉，該水可溶性磷酸鹽例如但不限於磷酸鈉、磷酸一氫鈉或磷酸二氫鈉，該水可溶性氫氧化物例如但不限於氫氧化鈉。More specifically, when the pollutant ions are zinc ions, the pH value of the crystallizer solution is, for example but not limited to, 9 to 11, the predetermined pH value range is 7 to 9, the crystallizer is a water-soluble carbonate, a water-soluble phosphate, a water-soluble hydroxide or a water-soluble sulfide, and the poorly water-soluble crystallized precipitate particles are correspondingly zinc carbonate crystallized precipitate particles, zinc phosphate crystallized precipitate particles, zinc hydroxide crystallized precipitate particles or zinc sulfide crystallized precipitate particles. The water-soluble carbonate is, for example but not limited to, sodium carbonate or sodium bicarbonate; the water-soluble phosphate is, for example but not limited to, sodium phosphate, sodium monohydrogen phosphate or sodium dihydrogen phosphate; the water-soluble hydroxide is, for example but not limited to, sodium hydroxide.
當該汙染物離子為鎳離子時，該結晶劑溶液的pH值例如但不限於9至14，該預定pH值範圍為7至12，較佳地，該預定pH值範圍為8至10，該結晶劑為水可溶性碳酸鹽，該水難溶性結晶沉澱顆粒為碳酸鎳結晶沉澱顆粒。其中，該水可溶性碳酸鹽例如但不限於碳酸鈉或碳酸氫鈉。When the pollutant ions are nickel ions, the pH value of the crystallizer solution is, for example but not limited to, 9 to 14, the predetermined pH value range is 7 to 12, preferably, the predetermined pH value range is 8 to 10, the crystallizer is a water-soluble carbonate, and the water-insoluble crystallization precipitate particles are nickel carbonate crystallization precipitate particles. Wherein, the water-soluble carbonate is, for example but not limited to, sodium carbonate or sodium bicarbonate.
當該汙染物離子為鋁離子時，該結晶劑溶液的pH值例如但不限於9至14，該預定pH值範圍為7至12.5，該結晶劑為水可溶性氫氧化物，該水難溶性結晶沉澱顆粒為氫氧化鋁結晶沉澱顆粒。其中，該水可溶性氫氧化物例如但不限於氫氧化鈉。When the pollutant ions are aluminum ions, the pH value of the crystallizer solution is, for example but not limited to, 9 to 14, the predetermined pH value range is 7 to 12.5, the crystallizer is a water-soluble hydroxide, and the water-insoluble crystallization precipitate particles are aluminum hydroxide crystallization precipitate particles. The water-soluble hydroxide is, for example but not limited to, sodium hydroxide.
當該汙染物離子為銅離子時，該結晶劑溶液的pH值例如但不限於7至12，該預定pH值範圍為5至10，該結晶劑為水可溶性碳酸鹽，該水難溶性結晶沉澱顆粒為鹼式碳酸銅[malachite，Cu 2(OH) 2CO 3]結晶沉澱顆粒或氧化銅(II)結晶沉澱顆粒。其中，該水可溶性碳酸鹽例如但不限於碳酸鈉。 When the pollutant ions are copper ions, the pH value of the crystallizer solution is, for example but not limited to, 7 to 12, the predetermined pH value range is 5 to 10, the crystallizer is a water-soluble carbonate, and the water-insoluble crystallization precipitate particles are alkaline copper carbonate [malachite, Cu 2 (OH) 2 CO 3 ] crystallization precipitate particles or copper (II) oxide crystallization precipitate particles. The water-soluble carbonate is, for example but not limited to, sodium carbonate.
當該汙染物離子為鈷離子時，該結晶劑溶液的pH值例如但不限於8.5至11，該預定pH值範圍為6.5至9，該結晶劑為水可溶性碳酸鹽、水可溶性磷酸鹽、水可溶性草酸鹽或水可溶性硫離子，該水難溶性結晶沉澱顆粒相應為碳酸鈷結晶沉澱顆粒、磷酸鈷結晶沉澱顆粒、草酸鈷結晶沉澱顆粒或硫化鈷結晶沉澱顆粒。其中，該水可溶性碳酸鹽例如但不限於碳酸鈉或碳酸氫鈉，該水可溶性磷酸鹽例如但不限於磷酸鈉、磷酸一氫鈉或磷酸二氫鈉，該水可溶性草酸鹽例如但不限於草酸鈉，該水可溶性硫離子例如但不限於硫化鈉。When the pollutant ions are cobalt ions, the pH value of the crystallizer solution is, for example but not limited to, 8.5 to 11, the predetermined pH value range is 6.5 to 9, the crystallizer is a water-soluble carbonate, a water-soluble phosphate, a water-soluble oxalate or a water-soluble sulfur ion, and the water-insoluble crystallized precipitate particles are correspondingly cobalt carbonate crystallized precipitate particles, cobalt phosphate crystallized precipitate particles, cobalt oxalate crystallized precipitate particles or cobalt sulfide crystallized precipitate particles. Among them, the water-soluble carbonate is, for example, but not limited to, sodium carbonate or sodium bicarbonate, the water-soluble phosphate is, for example, but not limited to, sodium phosphate, sodium monohydrogen phosphate or sodium dihydrogen phosphate, the water-soluble oxalate is, for example, but not limited to, sodium oxalate, and the water-soluble sulfur ion is, for example, but not limited to, sodium sulfide.
當該汙染物離子為鈣離子時，該結晶劑溶液的pH值例如但不限於8.5至12，該預定pH值範圍為6.5至10，該結晶劑為水可溶性碳酸鹽、水可溶性磷酸鹽、水可溶性草酸鹽或水可溶性硫離子，該水難溶性結晶沉澱顆粒相應為碳酸鈣結晶沉澱顆粒、磷酸鈣結晶沉澱顆粒、草酸鈣結晶沉澱顆粒或硫化鈣結晶沉澱顆粒。其中，該水可溶性碳酸鹽例如但不限於碳酸鈉或碳酸氫鈉，該水可溶性磷酸鹽例如但不限於磷酸鈉、磷酸一氫鈉或磷酸二氫鈉，該水可溶性草酸鹽例如但不限於草酸鈉，該水可溶性硫離子例如但不限於硫化鈉。When the pollutant ions are calcium ions, the pH value of the crystallizer solution is, for example but not limited to, 8.5 to 12, the predetermined pH value range is 6.5 to 10, the crystallizer is a water-soluble carbonate, a water-soluble phosphate, a water-soluble oxalate or a water-soluble sulfur ion, and the poorly water-soluble crystallized precipitate particles are correspondingly calcium carbonate crystallized precipitate particles, calcium phosphate crystallized precipitate particles, calcium oxalate crystallized precipitate particles or calcium sulfide crystallized precipitate particles. Among them, the water-soluble carbonate is, for example, but not limited to, sodium carbonate or sodium bicarbonate, the water-soluble phosphate is, for example, but not limited to, sodium phosphate, sodium monohydrogen phosphate or sodium dihydrogen phosphate, the water-soluble oxalate is, for example, but not limited to, sodium oxalate, and the water-soluble sulfur ion is, for example, but not limited to, sodium sulfide.
當該汙染物離子為鎂離子時，該結晶劑溶液的pH值例如但不限於8.5至12，該預定pH值範圍為6.5至10，該結晶劑為水可溶性碳酸鹽、水可溶性磷酸鹽、水可溶性草酸鹽或水可溶性硫離子，該水難溶性結晶沉澱顆粒相應為碳酸鎂結晶沉澱顆粒、磷酸鎂結晶沉澱顆粒、草酸鎂結晶沉澱顆粒或硫化鎂結晶沉澱顆粒。其中，該水可溶性碳酸鹽例如但不限於碳酸鈉或碳酸氫鈉，該水可溶性磷酸鹽例如但不限於磷酸鈉、磷酸一氫鈉或磷酸二氫鈉，該水可溶性草酸鹽例如但不限於草酸鈉，該水可溶性硫離子例如但不限於硫化鈉。When the pollutant ions are magnesium ions, the pH value of the crystallizer solution is, for example but not limited to, 8.5 to 12, the predetermined pH value range is 6.5 to 10, the crystallizer is a water-soluble carbonate, a water-soluble phosphate, a water-soluble oxalate or a water-soluble sulfur ion, and the poorly water-soluble crystallized precipitate particles are correspondingly magnesium carbonate crystallized precipitate particles, magnesium phosphate crystallized precipitate particles, magnesium oxalate crystallized precipitate particles or magnesium sulfide crystallized precipitate particles. Among them, the water-soluble carbonate is, for example, but not limited to, sodium carbonate or sodium bicarbonate, the water-soluble phosphate is, for example, but not limited to, sodium phosphate, sodium monohydrogen phosphate or sodium dihydrogen phosphate, the water-soluble oxalate is, for example, but not limited to, sodium oxalate, and the water-soluble sulfur ion is, for example, but not limited to, sodium sulfide.
當該汙染物離子為鐵離子時，該結晶劑溶液的pH值例如但不限於6至11，該預定pH值範圍為4至9，該結晶劑為水可溶性碳酸鹽、水可溶性磷酸鹽、水可溶性草酸鹽或水可溶性硫離子，該水難溶性結晶沉澱顆粒相應為氫氧化鐵結晶沉澱顆粒、磷酸鐵結晶沉澱顆粒、草酸鐵結晶沉澱顆粒或硫化鐵結晶沉澱顆粒。其中，該水可溶性碳酸鹽例如但不限於碳酸鈉或碳酸氫鈉，該水可溶性磷酸鹽例如但不限於磷酸鈉、磷酸一氫鈉或磷酸二氫鈉，該水可溶性草酸鹽例如但不限於草酸鈉，該水可溶性硫離子例如但不限於硫化鈉。When the pollutant ions are iron ions, the pH value of the crystallizer solution is, for example but not limited to, 6 to 11, the predetermined pH value range is 4 to 9, the crystallizer is a water-soluble carbonate, a water-soluble phosphate, a water-soluble oxalate or a water-soluble sulfur ion, and the poorly water-soluble crystallized precipitate particles are correspondingly iron hydroxide crystallized precipitate particles, iron phosphate crystallized precipitate particles, iron oxalate crystallized precipitate particles or iron sulfide crystallized precipitate particles. Among them, the water-soluble carbonate is, for example, but not limited to, sodium carbonate or sodium bicarbonate, the water-soluble phosphate is, for example, but not limited to, sodium phosphate, sodium monohydrogen phosphate or sodium dihydrogen phosphate, the water-soluble oxalate is, for example, but not limited to, sodium oxalate, and the water-soluble sulfur ion is, for example, but not limited to, sodium sulfide.
當該汙染物離子為草酸根離子時，該結晶劑溶液的pH值例如但不限於6.5至10.5，該預定pH值範圍為4.5至8.5，該結晶劑為能夠提供鈣離子的水可溶性鈣源，且該水可溶性鈣源例如但不限於氯化鈣，該水難溶性結晶沉澱顆粒為草酸鈣結晶沉澱顆粒。When the pollutant ions are oxalate ions, the pH value of the crystallizer solution is, for example but not limited to, 6.5 to 10.5, the predetermined pH value range is 4.5 to 8.5, the crystallizer is a water-soluble calcium source capable of providing calcium ions, and the water-soluble calcium source is, for example but not limited to, calcium chloride, and the poorly water-soluble crystalline precipitate particles are calcium oxalate crystalline precipitate particles.
當該汙染物離子為磷酸根離子時，該結晶劑溶液的pH值例如但不限於8至11，該預定pH值範圍為6至9，該結晶劑為能夠提供鈣離子的水可溶性鈣源，且該水可溶性鈣源例如但不限於氯化鈣，該水難溶性結晶沉澱顆粒為磷酸鈣結晶沉澱顆粒。When the pollutant ions are phosphate ions, the pH value of the crystallizer solution is, for example but not limited to, 8 to 11, the predetermined pH value range is 6 to 9, the crystallizer is a water-soluble calcium source capable of providing calcium ions, and the water-soluble calcium source is, for example but not limited to, calcium chloride, and the water-insoluble crystalline precipitate particles are calcium phosphate crystalline precipitate particles.
當該汙染物離子為硫酸根離子時，該結晶劑溶液的pH值例如但不限於8至12，該預定pH值範圍為6至10，該結晶劑為能夠提供鈣離子的水可溶性鈣源或能夠提供鎂離子的水可溶性鎂源，且該水可溶性鈣源例如但不限於氯化鈣或硝酸鈣，該水可溶性鎂源例如但不限於氯化鎂或硝酸鎂，該水難溶性結晶沉澱顆粒相應為硫酸鈣結晶沉澱顆粒或硫酸鎂結晶沉澱顆粒。When the pollutant ions are sulfate ions, the pH value of the crystallizer solution is, for example but not limited to, 8 to 12, the predetermined pH value range is 6 to 10, the crystallizer is a water-soluble calcium source capable of providing calcium ions or a water-soluble magnesium source capable of providing magnesium ions, and the water-soluble calcium source is, for example but not limited to, calcium chloride or calcium nitrate, the water-soluble magnesium source is, for example but not limited to, magnesium chloride or magnesium nitrate, and the poorly water-soluble crystallized precipitate particles are correspondingly calcium sulfate crystallized precipitate particles or magnesium sulfate crystallized precipitate particles.
當該汙染物離子為硫離子時，該結晶劑溶液的pH值例如但不限於6至11，該預定pH值範圍為4至9，該結晶劑為能夠提供二價金屬離子的水可溶性化合物，該二價金屬離子例如但不限於鐵離子、銅離子、鎳離子、鈷離子、鈣離子、鋅離子或鉛離子，該水難溶性結晶沉澱顆粒相應為硫化鐵結晶沉澱顆粒、硫化銅結晶沉澱顆粒、硫化鎳結晶沉澱顆粒、硫化鈷結晶沉澱顆粒、硫化鈣結晶沉澱顆粒、硫化鋅結晶沉澱顆粒或硫酸鉛結晶沉澱顆粒。其中，提供二價鐵離子的水可溶性化合物例如但不限於氯化鐵、硝酸鐵或硫酸鐵，提供二價銅離子的水可溶性化合物例如但不限於氯化銅、硝酸銅或硫酸銅，提供二價鎳離子的水可溶性化合物例如但不限於氯化鎳、硝酸鎳或硫酸鎳，提供二價鈷離子的水可溶性化合物例如但不限於氯化鈷、硝酸鈷或硫酸鈷，提供二價鈣離子的水可溶性化合物例如但不限於氯化鈣或硝酸鈣，提供二價鋅離子的水可溶性化合物例如但不限於氯化鋅、硝酸鋅或硫酸鋅，提供二價鉛離子的水可溶性化合物例如但不限於氯化鉛、硝酸鉛或硫酸鉛。When the pollutant ions are sulfur ions, the pH value of the crystallizer solution is, for example but not limited to, 6 to 11, the predetermined pH value range is 4 to 9, and the crystallizer is a water-soluble compound capable of providing divalent metal ions, such as but not limited to iron ions, copper ions, nickel ions, cobalt ions, ions, calcium ions, zinc ions or lead ions, and the water-insoluble crystalline precipitated particles are correspondingly iron sulfide crystalline precipitated particles, copper sulfide crystalline precipitated particles, nickel sulfide crystalline precipitated particles, cobalt sulfide crystalline precipitated particles, calcium sulfide crystalline precipitated particles, zinc sulfide crystalline precipitated particles or lead sulfate crystalline precipitated particles. Among them, water-soluble compounds providing divalent iron ions include, but are not limited to, iron chloride, iron nitrate or iron sulfate, water-soluble compounds providing divalent copper ions include, but are not limited to, copper chloride, copper nitrate or copper sulfate, water-soluble compounds providing divalent nickel ions include, but are not limited to, nickel chloride, nickel nitrate or nickel sulfate, water-soluble compounds providing divalent cobalt ions include, but are not limited to, cobalt chloride, cobalt nitrate or cobalt sulfate, water-soluble compounds providing divalent calcium ions include, but are not limited to, calcium chloride or calcium nitrate, water-soluble compounds providing divalent zinc ions include, but are not limited to, zinc chloride, zinc nitrate or zinc sulfate, and water-soluble compounds providing divalent lead ions include, but are not limited to, lead chloride, lead nitrate or lead sulfate.
當該汙染物離子為銨離子時，該結晶劑溶液的pH值例如但不限於8至11，該預定pH值範圍為6至9，該結晶劑為水可溶性磷酸鹽及能夠提供鎂離子的水可溶性鎂源，或是，水可溶性磷酸鹽及能夠提供鋅離子的水可溶性鋅源，該水難溶性結晶沉澱顆粒相應為磷酸銨鎂結晶沉澱顆粒或磷酸銨鋅結晶沉澱顆粒。其中，該水可溶性磷酸鹽例如但不限於磷酸鈉、磷酸一氫鈉或磷酸二氫鈉，該水可溶性鎂源例如但不限於氯化鎂或硝酸鎂，該水可溶性鋅源例如但不限於氯化鎂、硝酸鎂或硫酸鋅。When the pollutant ions are ammonium ions, the pH value of the crystallizer solution is, for example but not limited to, 8 to 11, and the predetermined pH value range is 6 to 9. The crystallizer is a water-soluble phosphate and a water-soluble magnesium source capable of providing magnesium ions, or a water-soluble phosphate and a water-soluble zinc source capable of providing zinc ions. The poorly water-soluble crystallized precipitate particles are correspondingly ammonium-magnesium phosphate crystallized precipitate particles or ammonium-zinc phosphate crystallized precipitate particles. The water-soluble phosphate may be, but not limited to, sodium phosphate, sodium monohydrogen phosphate or sodium dihydrogen phosphate; the water-soluble magnesium source may be, but not limited to, magnesium chloride or magnesium nitrate; and the water-soluble zinc source may be, but not limited to, magnesium chloride, magnesium nitrate or zinc sulfate.
該過濾裝置3設置於該流體化床結晶裝置2的下游，並用以對來自該流體化床結晶裝置2的該混合溶液進行過濾，獲得包含該結晶懸浮顆粒的殘留物及包含未與該結晶劑反應的該汙染物離子的濾液。要說明的是，透過該過濾裝置3，能夠收集來自該流體化床結晶裝置2中未與該結晶劑反應的結晶懸浮顆粒及汙染物離子，藉此將結晶懸浮顆粒及未與該結晶劑反應的汙染物離子導入不同裝置中進行後續處理，以確保廢水中的汙染物離子能夠順利地被轉變成結晶沉澱顆粒。The
該迴流裝置4設置於該過濾裝置3的下游，並與該流體化床結晶裝置2連通，並用以將該殘留物輸送回該反應空間21內，以使該殘留物中的結晶懸浮顆粒與該結晶劑溶液中的結晶劑反應形成結晶沉澱顆粒。The
要說明的是，透過該迴流裝置4將該殘留物輸送回該流體化床結晶裝置2，能夠使該結晶懸浮顆粒附著在位於該反應空間21的結晶沉澱顆粒(即均質擔體)的表面，藉此使該結晶懸浮顆粒與該結晶劑進行反應，從而於該結晶沉澱顆粒的表面形成新的結晶沉澱顆粒，以提高結晶沉澱顆粒的總產率。此外，由於該迴流裝置4能夠將結晶懸浮顆粒輸送回該反應空間21進行反應，因此，該迴流裝置4的設置亦能夠確保該流體化床均質結晶設備幾乎不會排放出包含結晶懸浮顆粒的淨化水，從而達到近乎零汙染物排放的功效。It should be noted that by transporting the residue back to the fluidized
該分離裝置5與該過濾裝置3連通，並用以對來自該過濾裝置3的該濾液進行分離處理，以從該濾液中分離出未與該結晶劑反應的該汙染物離子，獲得淨化水及包含未與該結晶劑反應的該汙染物離子的處理液，並將該處理液輸送回該流體化床結晶裝置2中，以使該處理液與該結晶劑溶液及下一批次的包含廢水的待處理溶液混合，從而使該處理液中的未與該結晶劑反應的汙染物離子、該結晶劑溶液中的結晶劑及該下一批次的待處理溶液中的汙染物離子反應，進而形成結晶沉澱顆粒。其中，該處理液中的未與該結晶劑反應的汙染物離子的濃度大於該濾液中的未與該結晶劑反應的汙染物離子的濃度。該分離裝置5例如但不限於包括離子交換樹脂的處理裝置、用於進行薄膜濃縮法的處理裝置、用於進行吸附法的處理裝置或用於進行蒸發法的處理裝置。在本發明的一些實施態樣中，該分離裝置5為包括離子交換樹脂的處理裝置。The
要說明的是，透過該分離裝置5對該濾液進行分離處理，能夠有效地從該濾液中分離出未與該結晶劑反應的該汙染物離子，從而使該淨化水中幾乎不含有汙染物離子，因此，該分離裝置5的設置能夠確保該流體化床均質結晶設備排放出幾乎不含有汙染物離子的淨化水，從而達到近乎零汙染物排放的功效。此外，透過該分離裝置5還能夠將該濾液中的未與該結晶劑反應的該汙染物離子的濃度提高至足以與該結晶劑溶液中的結晶劑進行反應並形成結晶沉澱顆粒的程度，因此，藉由該分離裝置5來獲得該處理液，能夠有效地將該濾液中由該過濾裝置3所收集到的未與該結晶劑反應的汙染物離子的濃度提高，並將包含未與該結晶劑反應的該汙染物離子的該處理液再次輸送回該流體化床結晶裝置2中，使該處理液中的未與該結晶劑反應的該汙染物離子在與該結晶劑進行反應後形成結晶沉澱顆粒，藉此提高結晶沉澱顆粒的總產率。It should be noted that the separation treatment of the filter liquid by the
參閱圖2，本發明流體化床均質結晶設備的第二實施例，與該第一實施例的不同之處在於：該流體化床均質結晶設備還包含一酸鹼值調整裝置6。該酸鹼值調整裝置6與該流體化床結晶裝置2連通，並用以調整該待處理溶液的pH值。具體地說，當該待處理溶液的pH值過低，以至於該待處理溶液與該結晶劑溶液混合後的pH值無法落在該預定pH值範圍時，透過該酸鹼值調整裝置6來調整該待處理溶液的pH值，能夠確保該待處理溶液與該結晶劑溶液在該流體化床結晶裝置2中混合後的pH值落在該預定pH值範圍內，從而獲得結晶沉澱顆粒。Referring to FIG. 2 , the second embodiment of the fluidized bed homogeneous crystallization device of the present invention is different from the first embodiment in that the fluidized bed homogeneous crystallization device further comprises a pH
使用該酸鹼值調整裝置6時，是依據不同種類的汙染物離子所對應的預定pH值範圍來調整該待處理溶液的pH值。當該汙染物離子為鋅離子時，是將該待處理溶液的pH值範圍調整為5至7，當該汙染物離子為鎳離子時，是將該待處理溶液的pH值範圍調整為5至10，當該汙染物離子為鋁離子時，是將該待處理溶液的pH值範圍調整為5至10.5，當該汙染物離子為銅離子時，是將該待處理溶液的pH值範圍調整為3至8，當該汙染物離子為鈷離子時，是將該待處理溶液的pH值範圍調整為4.5至7，當該汙染物離子為鈣離子時，是將該待處理溶液的pH值範圍調整為4.5至8，當該汙染物離子為鎂離子時，是將該待處理溶液的pH值範圍調整為4.5至8，當該汙染物離子為鐵離子時，是將該待處理溶液的pH值範圍調整為2至7，當該汙染物離子為草酸根離子時，是將該待處理溶液的pH值範圍調整為2.5至6.5，當該汙染物離子為磷酸根離子時，是將該待處理溶液的pH值範圍調整為4至7，當該汙染物離子為硫酸根離子時，是將該待處理溶液的pH值範圍調整為4至8，當該汙染物離子為硫離子時，是將該待處理溶液的pH值範圍調整為2至7，當該汙染物離子為銨離子時，是將該待處理溶液的pH值範圍調整為4至7。When the acid-base
參閱圖3，本發明流體化床均質結晶設備的第三實施例，與該第二實施例的不同之處在於：該分離裝置5是與該過濾裝置3及該酸鹼值調整裝置6連通。在該第三實施例中，該分離裝置5是將該處理液輸送至該酸鹼值調整裝置6中與下一批次的廢水混合，而成為下一批次的待處理溶液。Referring to FIG. 3 , the third embodiment of the fluidized bed homogenization crystallization apparatus of the present invention is different from the second embodiment in that the
參閱圖4，本發明流體化床均質結晶設備的第四實施例，與該第三實施例的不同之處在於：該迴流裝置4還與該酸鹼值調整裝置6連通，並用以將來自該過濾裝置3的該殘留物輸送至該酸鹼值調整裝置6中。當該殘留物與該結晶劑溶液混合後的pH值不落在該預定pH值範圍內時，透過將該殘留物輸送至該酸鹼值調整裝置6與下一批次的廢水進行混合而成為下一批次的待處理溶液，並藉由該酸鹼值調整裝置6調整該下一批次的待處理溶液的pH值，而有助於該下一批次的待處理溶液與該結晶劑溶液混合後的pH值能落在該預定pH值範圍內，以使存在於該下一批次的待處理溶液中來自於該殘留物的結晶懸浮顆粒能夠有效益地與該結晶劑進行反應以形成結晶沉澱顆粒，從而進一步提高結晶沉澱顆粒的總產率。要說明的是，該殘留物是否要經由該迴流裝置4被輸送至該酸鹼值調整裝置6，可以依據該殘留物與該結晶劑溶液混合後的pH值是否落在該預定pH值範圍來決定。Referring to FIG. 4 , the fourth embodiment of the fluidized bed homogenizing crystallization apparatus of the present invention is different from the third embodiment in that the
本發明還提供一種處理廢水中汙染物離子的流體化床均質結晶方法，包含以下步驟： 進行兩次以上的處理程序，且每一次處理程序包括， (a)使包含廢水的待處理溶液與包含結晶劑的結晶劑溶液在一不包含異質擔體的流體化床結晶裝置混合，其中，該廢水包括汙染物離子，且該待處理溶液與該結晶劑溶液混合後的pH值落在一預定pH值範圍，以使該待處理溶液中的汙染物離子與該結晶劑溶液中的結晶劑在該預定pH值範圍下反應形成結晶沉澱顆粒，並獲得包含結晶懸浮顆粒及未與該結晶劑反應的汙染物離子的混合溶液； (b)將該混合溶液進行過濾處理，獲得包含該結晶懸浮顆粒的殘留物及包含未與該結晶劑反應的該汙染物離子的濾液； (c)將該殘留物輸送回該流體化床結晶裝置中，並使該殘留物中的結晶懸浮顆粒與該結晶劑溶液中的結晶劑反應形成結晶沉澱顆粒； (d)將該濾液進行分離處理，以從該濾液中分離出未與該結晶劑反應的該汙染物離子，並獲得淨化水及包含未與該結晶劑反應的該汙染物離子的處理液，其中，該處理液中的未與該結晶劑反應的該汙染物離子的濃度大於該濾液中的未與該結晶劑反應的該汙染物離子的濃度；及 (e)將當次處理程序的該處理液與下一批次的廢水混合，而成為下一次處理程序的待處理溶液。 The present invention also provides a fluidized bed homogeneous crystallization method for treating pollutant ions in wastewater, comprising the following steps: Carrying out two or more treatment procedures, and each treatment procedure includes, (a) mixing a solution to be treated containing wastewater with a crystallizer solution containing a crystallizer in a fluidized bed crystallization device that does not contain a heterogeneous carrier, wherein the wastewater contains pollutant ions, and the pH value of the solution to be treated and the crystallizer solution after mixing falls within a predetermined pH range, so that the pollutant ions in the solution to be treated react with the crystallizer in the crystallizer solution within the predetermined pH range to form crystallized precipitated particles, and obtain a mixed solution containing crystallized suspended particles and pollutant ions that have not reacted with the crystallizer; (b) filtering the mixed solution to obtain a residue containing the crystallized suspended particles and a filtrate containing the pollutant ions that have not reacted with the crystallizer; (c) transporting the residue back to the fluidized bed crystallization device, and allowing the crystallized suspended particles in the residue to react with the crystallizer in the crystallizer solution to form crystallized precipitated particles; (d) subjecting the filtered liquid to a separation treatment to separate the pollutant ions that have not reacted with the crystallizer from the filtered liquid, and obtaining purified water and a treatment liquid containing the pollutant ions that have not reacted with the crystallizer, wherein the concentration of the pollutant ions that have not reacted with the crystallizer in the treatment liquid is greater than the concentration of the pollutant ions that have not reacted with the crystallizer in the filtered liquid; and (e) mixing the treatment liquid of the current treatment process with the next batch of wastewater to form a solution to be treated for the next treatment process.
在該步驟(a)中，該汙染物離子如上所述，故不再贅述。要說明的是，為了進一步提高該待處理溶液中的汙染物離子的去除率及結晶沉澱顆粒的結晶率，在本發明的一些實施態樣中，是將該待處理溶液中的汙染物離子的濃度控制在一預定濃度範圍。詳細地說，當該汙染物離子為鋅離子時，該待處理溶液中的鋅離子濃度範圍為50mg/L至500mg/L；當該汙染物離子為鎳離子時，該待處理溶液中的鎳離子濃度為300mg/L；當該汙染物離子為鋁離子時，該待處理溶液中的鋁離子濃度範圍為100mg/L至400mg/L；當該汙染物離子為銅離子時，該待處理溶液中的銅離子濃度範圍為100mg/L至2000mg/L；當該汙染物離子為鈷離子時，該待處理溶液中的鈷離子濃度範圍為200mg/L至500mg/L；當該汙染物離子為鈣離子時，該待處理溶液中的鈣離子濃度範圍為100mg/L至500mg/L；當該汙染物離子為鎂離子時，該待處理溶液中的鎂離子濃度範圍為100mg/L至500mg/L；當該汙染物離子為鐵離子時，該待處理溶液中的鐵離子濃度範圍為100mg/L至500mg/L；當該汙染物離子為草酸根離子時，該待處理溶液中的草酸根離子濃度範圍為150mg/L至450mg/L；當該汙染物離子為磷酸根離子時，該待處理溶液中的磷酸根離子濃度範圍為1000mg/L至1500mg/L；當該汙染物離子為硫酸根離子時，該待處理溶液中的硫酸根離子濃度範圍為200mg/L至500mg/L；當該汙染物離子為硫離子時，該待處理溶液中的硫離子濃度範圍為50mg/L至500mg/L；當該汙染物離子為銨離子時，該待處理溶液中的銨離子濃度範圍為200mg/L至500mg/L。In the step (a), the pollutant ions are as described above, so they are not described in detail. It should be noted that in order to further improve the removal rate of the pollutant ions in the solution to be treated and the crystallization rate of the crystallized precipitated particles, in some embodiments of the present invention, the concentration of the pollutant ions in the solution to be treated is controlled within a predetermined concentration range. Specifically, when the pollutant ions are zinc ions, the concentration of zinc ions in the solution to be treated is in the range of 50 mg/L to 500 mg/L; when the pollutant ions are nickel ions, the concentration of nickel ions in the solution to be treated is 300 mg/L; when the pollutant ions are aluminum ions, the concentration of aluminum ions in the solution to be treated is in the range of 100 mg/L to 400 mg/L; when the pollutant ions are copper ions, the concentration of The concentration of copper ions in the solution to be treated ranges from 100 mg/L to 2000 mg/L; when the pollutant ions are cobalt ions, the concentration of cobalt ions in the solution to be treated ranges from 200 mg/L to 500 mg/L; when the pollutant ions are calcium ions, the concentration of calcium ions in the solution to be treated ranges from 100 mg/L to 500 mg/L; when the pollutant ions are magnesium ions, the concentration of magnesium ions in the solution to be treated ranges from 10 0mg/L to 500mg/L; when the pollutant ions are iron ions, the iron ion concentration in the solution to be treated is in the range of 100mg/L to 500mg/L; when the pollutant ions are oxalate ions, the oxalate ion concentration in the solution to be treated is in the range of 150mg/L to 450mg/L; when the pollutant ions are phosphate ions, the phosphate ion concentration in the solution to be treated is in the range of 1000mg/L to 500mg/L. L to 1500 mg/L; when the pollutant ions are sulfate ions, the sulfate ion concentration in the solution to be treated ranges from 200 mg/L to 500 mg/L; when the pollutant ions are sulfur ions, the sulfur ion concentration in the solution to be treated ranges from 50 mg/L to 500 mg/L; when the pollutant ions are ammonium ions, the ammonium ion concentration in the solution to be treated ranges from 200 mg/L to 500 mg/L.
該預定pH值範圍可依據該汙染物離子的種類進行調整，於本發明中並沒有特別限制。在本發明的一些實施態樣中，該汙染物離子為鋅離子、鎳離子、鋁離子、銅離子、草酸根離子或磷酸根離子，而上述不同種類的汙染物離子所適用的預定pH值範圍如上所述，故不再贅述。The predetermined pH range can be adjusted according to the type of the pollutant ions, and is not particularly limited in the present invention. In some embodiments of the present invention, the pollutant ions are zinc ions, nickel ions, aluminum ions, copper ions, oxalate ions or phosphate ions, and the predetermined pH ranges applicable to the above different types of pollutant ions are as described above, so they are not repeated.
該結晶劑如上所述，故不再贅述。在本發明的一些實施態樣中，該汙染物離子為鋅離子、鎳離子、鋁離子、銅離子、草酸根離子或磷酸根離子，而上述種類的汙染物離子所適用的結晶劑種類如上所述，故不再贅述。要說明的是，為了進一步提高該待處理溶液中的汙染物離子的去除率及結晶沉澱顆粒的結晶率，在本發明的一些實施態樣中，是將該結晶劑與該待處理溶液中的汙染物離子的莫耳比值(例如，碳酸根離子與汙染物離子的莫耳比值)控制在一預定比值範圍。更具體地說，當該汙染物離子為鋅離子時，該結晶劑與該廢水中的鋅離子的莫耳比值範圍為0.8至2；當該汙染物離子為鎳離子時，該結晶劑與該廢水中的鎳離子的莫耳比值範圍為0.8至2；當該汙染物離子為鋁離子時，該結晶劑與該廢水中的鋁離子的莫耳比值範圍為0.8至2；當該汙染物離子為銅離子時，該結晶劑與該廢水中的銅離子的莫耳比值範圍為0.8至1.8；當該汙染物離子為鈷離子時，該結晶劑與該廢水中的鈷離子的莫耳比值範圍為0.5至2；當該汙染物離子為鈣離子時，該結晶劑與該廢水中的鈣離子的莫耳比值範圍為0.5至2；當該汙染物離子為鎂離子時，該結晶劑與該廢水中的鎂離子的莫耳比值範圍為0.5至2；當該汙染物離子為鐵離子時，該結晶劑與該廢水中的鐵離子的莫耳比值範圍為0.5至2；當該汙染物離子為草酸根離子時，該結晶劑與該廢水中的草酸根離子的莫耳比值範圍為0.5至2；當該汙染物離子為磷酸根離子時，該結晶劑與該廢水中的磷酸根離子的莫耳比值範圍為0.6至2；當該汙染物離子為硫酸根離子時，該結晶劑與該廢水中的硫酸根離子的莫耳比值範圍為0.5至2；當該汙染物離子為硫離子時，該結晶劑與該廢水中的硫離子的莫耳比值範圍為0.5至2；當該汙染物離子為銨離子時，該結晶劑與該廢水中的銨離子的莫耳比值範圍為0.5至2。The crystallization agent is as described above, so it is not repeated here. In some embodiments of the present invention, the pollutant ions are zinc ions, nickel ions, aluminum ions, copper ions, oxalate ions or phosphate ions, and the types of crystallization agents applicable to the above types of pollutant ions are as described above, so it is not repeated here. It should be noted that in order to further improve the removal rate of pollutant ions in the solution to be treated and the crystallization rate of crystallization precipitation particles, in some embodiments of the present invention, the molar ratio of the crystallization agent to the pollutant ions in the solution to be treated (for example, the molar ratio of carbonate ions to pollutant ions) is controlled within a predetermined ratio range. More specifically, when the pollutant ions are zinc ions, the molar ratio of the crystallizer to the zinc ions in the wastewater is in the range of 0.8 to 2; when the pollutant ions are nickel ions, the molar ratio of the crystallizer to the nickel ions in the wastewater is in the range of 0.8 to 2; when the pollutant ions are aluminum ions, the molar ratio of the crystallizer to the aluminum ions in the wastewater is in the range of 0.8 to 2; when the pollutant ions are copper ions, the molar ratio of the crystallizer to the aluminum ions in the wastewater is in the range of 0.8 to 2. When the pollutant ions are copper ions, the molar ratio of the crystallizer to the copper ions in the wastewater is in the range of 0.8 to 1.8; when the pollutant ions are cobalt ions, the molar ratio of the crystallizer to the cobalt ions in the wastewater is in the range of 0.5 to 2; when the pollutant ions are calcium ions, the molar ratio of the crystallizer to the calcium ions in the wastewater is in the range of 0.5 to 2; when the pollutant ions are magnesium ions, the molar ratio of the crystallizer to the magnesium ions in the wastewater is in the range of 0.5 to 2. The molar ratio of the crystallizer to the magnesium ions in the wastewater is in the range of 0.5 to 2; when the pollutant ions are iron ions, the molar ratio of the crystallizer to the iron ions in the wastewater is in the range of 0.5 to 2; when the pollutant ions are oxalate ions, the molar ratio of the crystallizer to the oxalate ions in the wastewater is in the range of 0.5 to 2; when the pollutant ions are phosphate ions, the molar ratio of the crystallizer to the phosphate ions in the wastewater is in the range of 0.5 to 2. The molar ratio of the crystallizer to the sulfate ions in the wastewater is in the range of 0.6 to 2; when the pollutant ions are sulfate ions, the molar ratio of the crystallizer to the sulfate ions in the wastewater is in the range of 0.5 to 2; when the pollutant ions are sulfur ions, the molar ratio of the crystallizer to the sulfur ions in the wastewater is in the range of 0.5 to 2; when the pollutant ions are ammonium ions, the molar ratio of the crystallizer to the ammonium ions in the wastewater is in the range of 0.5 to 2.
該結晶沉澱顆粒及不同種類的汙染物離子所對應形成的結晶沉澱顆粒種類如上所述，故不再贅述。The crystallized precipitate particles and the types of crystallized precipitate particles corresponding to different types of pollutant ions are as described above, so they will not be described in detail.
在該步驟(b)中，透過該過濾處理能夠有效地將結晶懸浮顆粒的濃度提高50倍至100倍，也就是說，該殘留物中的結晶懸浮顆粒與該混合溶液中的結晶懸浮顆粒的濃度比值為50至100。In the step (b), the concentration of the crystallized suspended particles can be effectively increased by 50 to 100 times through the filtration treatment, that is, the concentration ratio of the crystallized suspended particles in the residue to the crystallized suspended particles in the mixed solution is 50 to 100.
在該步驟(d)中，該分離處理例如但不限於離子交換法、薄膜濃縮法、吸附法或蒸發法。在本發明的一些實施態樣中，是利用離子交換法對該濾液進行該分離處理，藉此使該淨化水中幾乎不含有汙染物離子，同時，該處理液的獲得相當於是提高未與該結晶劑反應的該汙染物離子的濃度，從而有助於使未與該結晶劑反應的該汙染物離子能夠與該結晶劑反應。具體地說，透過該分離處理能夠有效地將未與該結晶劑反應的該汙染物離子的濃度提高50倍至100倍，也就是說，該處理液中的未與該結晶劑反應的該汙染物離子與該濾液中的未與該結晶劑反應的該汙染物離子的濃度比值為50至100。In the step (d), the separation treatment is, for example, but not limited to, an ion exchange method, a membrane concentration method, an adsorption method, or an evaporation method. In some embodiments of the present invention, the filtrate is subjected to the separation treatment by an ion exchange method, thereby making the purified water almost free of pollutant ions. At the same time, the treatment solution is obtained by increasing the concentration of the pollutant ions that have not reacted with the crystallizer, thereby helping the pollutant ions that have not reacted with the crystallizer to react with the crystallizer. Specifically, the concentration of the pollutant ions that have not reacted with the crystallization agent can be effectively increased by 50 to 100 times through the separation treatment, that is, the concentration ratio of the pollutant ions that have not reacted with the crystallization agent in the treatment solution to the pollutant ions that have not reacted with the crystallization agent in the filter solution is 50 to 100.
要說明的是，由於每一次處理程序均有進行步驟(b)至步驟(e)，從而能夠將每一次處理程序中的殘留物及處理液輸送回流體化床結晶裝置，進而能夠確保排放出的淨化水中幾乎不會含有結晶懸浮顆粒及未與該結晶劑反應的汙染物離子。It should be noted that since each treatment process includes steps (b) to (e), the residues and the treated liquid in each treatment process can be transported back to the fluidized bed crystallization device, thereby ensuring that the discharged purified water will contain almost no crystallized suspended particles and pollutant ions that have not reacted with the crystallizing agent.
在本發明的一些實施態樣中，當該待處理溶液的pH值過低，以至於該待處理溶液與該結晶劑溶液混合後的pH值無法落在該預定pH值範圍時，在該步驟(a)中，是透過調整該待處理溶液的pH值後，再使經調整過pH值的待處理溶液與結晶劑溶液混合，以使該經調整過pH值的待處理溶液與該結晶劑溶液混合後的pH值落在該預定pH值範圍。關於包含不同種類的汙染物離子的經調整過pH值的待處理溶液的pH值範圍如上所述，故不再贅述。In some embodiments of the present invention, when the pH value of the solution to be treated is too low so that the pH value of the solution to be treated after mixing with the crystallizer solution cannot fall within the predetermined pH value range, in step (a), the pH value of the solution to be treated after adjusting the pH value is mixed with the crystallizer solution, so that the pH value of the solution to be treated after adjusting the pH value and the crystallizer solution after mixing falls within the predetermined pH value range. The pH value range of the solution to be treated after adjusting the pH value containing different types of pollutant ions is as described above, so it is not repeated.
為了確保該殘留物中的結晶懸浮顆粒被輸送回該流體化床結晶裝置時能夠與該結晶劑反應，從而形成結晶沉澱顆粒以提高結晶沉澱顆粒的總產率，在本發明的一些實施態樣中，在該步驟(c)中，是將該殘留物與下一批次的廢水進行混合而成為下一次處理程序的待處理溶液，並藉由調整該下一次處理程序的待處理溶液的pH值來控制該殘留物的pH值，以使該下一次處理程序的待處理溶液被輸送回該流體化床結晶裝置中與該結晶劑溶液混合後的pH值落在該預定pH值範圍，進而使存在於該下一次處理程序的待處理溶液中的該殘留物的結晶懸浮顆粒能夠與該結晶劑溶液中的結晶劑在該預定pH值範圍下反應。In order to ensure that the crystallized suspended particles in the residue can react with the crystallizing agent when being transported back to the fluidized bed crystallization device to form crystallized precipitated particles to improve the total yield of crystallized precipitated particles, in some embodiments of the present invention, in step (c), the residue is mixed with the next batch of wastewater to form a solution to be treated in the next treatment process, and the next treatment process is adjusted. The pH value of the residue is controlled by the pH value of the solution to be treated, so that the pH value of the solution to be treated in the next treatment process after being transported back to the fluidized bed crystallization device and mixed with the crystallization agent solution falls within the predetermined pH value range, thereby enabling the crystallized suspended particles of the residue in the solution to be treated in the next treatment process to react with the crystallization agent in the crystallization agent solution within the predetermined pH value range.
本發明處理廢水中汙染物離子的流體化床均質結晶方法可以藉由上述流體化床均質結晶設備來完成，且將就以下實施例來作進一步說明，但應瞭解的是，所述實施例僅為例示說明之用，而不應被解釋為本發明實施之限制。The fluidized bed homogenization crystallization method for treating pollutant ions in wastewater of the present invention can be accomplished by the above-mentioned fluidized bed homogenization crystallization equipment, and will be further described with reference to the following examples. However, it should be understood that the examples are only for illustrative purposes and should not be construed as limitations on the implementation of the present invention.
[實施例1][Example 1]
利用氫氧化鈉調整包含濃度為300mg/L的鋅離子的廢水(作為待處理溶液)的pH值，獲得包含鋅離子且pH值為5至7的第一溶液(即，經調整過pH值的待處理溶液)，並將該第一溶液與一包含濃度為330mg/L的碳酸鈉及水且pH值為9至11的結晶劑溶液輸送至一不包含異質擔體的流體化床結晶裝置中進行混合且混合後的pH值為7.2，以使該第一溶液中的鋅離子與該結晶劑溶液中的碳酸鈉在pH值為7.2下反應，獲得碳酸鋅結晶沉澱顆粒及混合溶液，該混合溶液包含未與該碳酸鈉反應的鋅離子及碳酸鋅結晶懸浮顆粒。其中，該結晶劑中的碳酸根離子與該廢水中的鋅離子的莫耳比值為1.2。The pH value of the wastewater containing zinc ions at a concentration of 300 mg/L (as the solution to be treated) is adjusted with sodium hydroxide to obtain a first solution containing zinc ions and having a pH value of 5 to 7 (i.e., the solution to be treated after adjusting the pH value), and the first solution is mixed with a crystallizing agent solution containing sodium carbonate and water at a concentration of 330 mg/L and having a pH value of 9 to 11. The wastewater is transported to a fluidized bed crystallization device that does not contain a heterogeneous carrier for mixing, and the pH value after mixing is 7.2, so that the zinc ions in the first solution react with the sodium carbonate in the crystallizer solution at a pH value of 7.2 to obtain zinc carbonate crystal precipitated particles and a mixed solution, wherein the mixed solution contains zinc ions that have not reacted with the sodium carbonate and zinc carbonate crystal suspended particles. The molar ratio of carbonate ions in the crystallizer to zinc ions in the wastewater is 1.2.
將該混合溶液進行過濾處理，獲得包含該碳酸鋅結晶懸浮顆粒的殘留物及包含未與該碳酸鈉反應且濃度為6mg/L的鋅離子的濾液。其中，該殘留物中的碳酸鋅結晶懸浮顆粒與該混合溶液中的碳酸鋅結晶懸浮顆粒的濃度比值為50至100。The mixed solution is filtered to obtain a residue containing the zinc carbonate crystal suspended particles and a filtrate containing zinc ions that have not reacted with the sodium carbonate and have a concentration of 6 mg/L. The concentration ratio of the zinc carbonate crystal suspended particles in the residue to the zinc carbonate crystal suspended particles in the mixed solution is 50 to 100.
將該殘留物輸送回該流體化床結晶裝置中，並使該殘留物中的碳酸鋅結晶懸浮顆粒與該結晶劑溶液中的碳酸鈉反應，獲得碳酸鋅結晶沉澱顆粒。The residue is transported back to the fluidized bed crystallization device, and the zinc carbonate crystal suspended particles in the residue are reacted with sodium carbonate in the crystallization agent solution to obtain zinc carbonate crystal precipitated particles.
採用離子交換法並利用離子交換樹脂對該濾液進行分離處理，獲得淨化水及包含未與該碳酸鈉反應且濃度為300mg/L的鋅離子的處理液。其中，該處理液中的未與該碳酸鈉反應的鋅離子與該濾液中的未與該碳酸鈉反應的鋅離子的濃度比值為50至100。The filtrate is separated by using an ion exchange method and an ion exchange resin to obtain purified water and a treatment solution containing zinc ions that have not reacted with the sodium carbonate and have a concentration of 300 mg/L. The concentration ratio of the zinc ions that have not reacted with the sodium carbonate in the treatment solution to the zinc ions that have not reacted with the sodium carbonate in the filtrate is 50 to 100.
將該處理液與下一批次的廢水進行混合，而成為下一次處理程序的待處理溶液，並利用氫氧化鈉調整該下一次處理程序的待處理溶液的pH值，獲得包含汙染物離子的第二溶液，並將該第二溶液輸送回該流體化床結晶裝置中與該結晶劑溶液混合且混合後的pH值為7.2，以使該第二溶液中的鋅離子與該結晶劑溶液中的碳酸鈉在pH值為7.2下反應，獲得碳酸鋅結晶沉澱顆粒。The treated solution is mixed with the next batch of wastewater to form a solution to be treated in the next treatment process, and the pH value of the solution to be treated in the next treatment process is adjusted by sodium hydroxide to obtain a second solution containing pollutant ions, and the second solution is transported back to the fluidized bed crystallization device to be mixed with the crystallizer solution and the pH value after mixing is 7.2, so that the zinc ions in the second solution react with the sodium carbonate in the crystallizer solution at a pH value of 7.2 to obtain zinc carbonate crystal precipitation particles.
[實施例2至6][Examples 2 to 6]
實施例2至6是以與實施例1類似的方式進行，差別在於改變廢水中的汙染物離子、pH值範圍及結晶劑，如表1所示。Examples 2 to 6 were carried out in a similar manner to Example 1, except that the pollutant ions in the wastewater, the pH range and the crystallizing agent were changed, as shown in Table 1.
[比較例1][Comparison Example 1]
將包含濃度為300mg/L的鋅離子的廢水與一包含濃度為330mg/L的碳酸鈉及水的結晶劑溶液輸送至一不包含異質擔體的流體化床結晶裝置中進行混合，以使該廢水中的鋅離子與該結晶劑溶液中的碳酸鈉反應，獲得碳酸鋅結晶沉澱顆粒及混合溶液，該混合溶液包含未與該碳酸鈉反應的鋅離子及碳酸鋅結晶懸浮顆粒。其中，該結晶劑中的碳酸根離子與該廢水中的鋅離子的莫耳比值為1.2。Wastewater containing zinc ions at a concentration of 300 mg/L and a crystallizer solution containing sodium carbonate and water at a concentration of 330 mg/L are transported to a fluidized bed crystallization device without a heterogeneous carrier for mixing, so that the zinc ions in the wastewater react with the sodium carbonate in the crystallizer solution to obtain zinc carbonate crystal precipitated particles and a mixed solution, wherein the mixed solution contains zinc ions that have not reacted with the sodium carbonate and zinc carbonate crystal suspended particles. The molar ratio of carbonate ions in the crystallizer to zinc ions in the wastewater is 1.2.
[比較例2至6][Comparison Examples 2 to 6]
比較例2至6是以與比較例1類似的方式進行，差別在於改變廢水中的汙染物離子及結晶劑，如表2所示。Comparative Examples 2 to 6 were conducted in a similar manner to Comparative Example 1, except that the pollutant ions and crystallizing agents in the wastewater were changed, as shown in Table 2.
[評價項目][Evaluation Items]
汙染物離子的去除率：以下以實施例1為例進行說明，其餘實施例2至6及比較例1至6是以相同的方式進行量測。利用一台原子吸收光譜儀(廠牌：Perkin Elmer；型號：PinAAcle 500)對實施例1的混合溶液進行量測，獲得該混合溶液中未與該碳酸鈉反應的鋅離子濃度，並依據下述的公式(1)計算出實施例1的汙染物離子去除率。要說明的是，由於實施例5至6及比較例5至6的草酸根離子與磷酸根離子屬於陰離子，因此是利用一台離子層析儀(廠牌：Dionex；型號：22176-60004)進行量測。 公式(1)：汙染物離子去除率(單位：%)={1－[(混合溶液中未與結晶劑反應的汙染物離子濃度×廢水的進流流量與結晶劑溶液的進流流量的總和)/(廢水中的汙染物離子濃度×廢水的進流流量)]}×100% Pollutant ion removal rate: Example 1 is used as an example for explanation. The remaining Examples 2 to 6 and Comparative Examples 1 to 6 are measured in the same manner. An atomic absorption spectrometer (brand: Perkin Elmer; model: PinAAcle 500) is used to measure the mixed solution of Example 1 to obtain the concentration of zinc ions that have not reacted with the sodium carbonate in the mixed solution, and the pollutant ion removal rate of Example 1 is calculated according to the following formula (1). It should be noted that since the oxalate ions and phosphate ions in Examples 5 to 6 and Comparative Examples 5 to 6 are anions, an ion chromatograph (brand: Dionex; model: 22176-60004) is used for measurement. Formula (1): Pollutant ion removal rate (unit: %) = {1-[(Concentration of pollutant ions in the mixed solution that have not reacted with the crystallizer × the sum of the inflow flow rate of wastewater and the inflow flow rate of the crystallizer solution)/(Concentration of pollutant ions in the wastewater × inflow flow rate of wastewater)]}×100%
結晶沉澱顆粒的結晶率：以下以實施例1為例進行說明，其餘實施例2至6及比較例1至6是以相同的方式進行量測。將實施例1的混合溶液與硝酸進行混合，以使該混合溶液中的碳酸鋅結晶懸浮顆粒溶解，獲得一待測溶液。利用一台原子吸收光譜儀(廠牌：Perkin Elmer；型號：PinAAcle 500)對該待測溶液進行量測，獲得該待測溶液中的鋅離子濃度，並依據下述的公式(2)計算出實施例1的結晶沉澱顆粒的結晶率。要說明的是，由於實施例5至6及比較例5至6的草酸根離子與磷酸根離子屬於陰離子，因此是利用一台離子層析儀(廠牌：Dionex；型號：22176-60004)進行量測。 公式(2)：結晶沉澱顆粒的結晶率(單位：%)={1－[(待測溶液中的汙染物離子濃度×廢水的進流流量與結晶劑溶液的進流流量的總和)/(廢水中的汙染物離子濃度×廢水的進流流量)]}×100% Crystallization rate of crystallized precipitated particles: Example 1 is used as an example for explanation below, and the remaining Examples 2 to 6 and Comparative Examples 1 to 6 are measured in the same manner. The mixed solution of Example 1 is mixed with nitric acid to dissolve the zinc carbonate crystal suspended particles in the mixed solution to obtain a test solution. The test solution is measured using an atomic absorption spectrometer (brand: Perkin Elmer; model: PinAAcle 500) to obtain the zinc ion concentration in the test solution, and the crystallization rate of the crystallized precipitated particles of Example 1 is calculated according to the following formula (2). It should be noted that since the oxalate ions and phosphate ions in Examples 5 to 6 and Comparative Examples 5 to 6 are anions, an ion chromatograph (brand: Dionex; model: 22176-60004) was used for measurement. Formula (2): Crystallization rate of crystallized precipitate particles (unit: %) = {1-[(pollutant ion concentration in the solution to be tested × the sum of the inflow flow rate of wastewater and the inflow flow rate of crystallizer solution)/(pollutant ion concentration in wastewater × inflow flow rate of wastewater)]} × 100%
表1
表2
參閱表1及表2，實施例1至6透過對包含結晶懸浮顆粒及未與該結晶劑反應的汙染物離子的混合溶液進行過濾處理，獲得殘留物及濾液，繼而將該殘留物輸送回流體化床結晶裝置中，以及將該濾液進行分離處理後輸送回流體化床結晶裝置，因此，實施例1至6具有99.9%的汙染物離子去除率，此表示實施例1至6的方法確實能夠有效地去除廢水中的汙染物離子，從而使排放出的淨化水中幾乎不存在有汙染物離子。此外，實施例1至6還具有99.9%的結晶沉澱顆粒結晶率，此表示實施例1至6的方法除了能夠有效地去除廢水中的汙染物離子外，還能夠有效地將該汙染物離子轉變成結晶沉澱顆粒。Referring to Table 1 and Table 2, Examples 1 to 6 filter a mixed solution containing crystallized suspended particles and pollutant ions that have not reacted with the crystallizer to obtain a residue and a filtrate, and then transport the residue back to the fluidized bed crystallization device, and transport the filtrate back to the fluidized bed crystallization device after separation treatment. Therefore, Examples 1 to 6 have a pollutant ion removal rate of 99.9%, which means that the methods of Examples 1 to 6 can indeed effectively remove pollutant ions in wastewater, so that there are almost no pollutant ions in the discharged purified water. In addition, Examples 1 to 6 also have a crystallization rate of 99.9% of the crystallized precipitate particles, which means that the methods of Examples 1 to 6 can not only effectively remove pollutant ions in wastewater, but also effectively convert the pollutant ions into crystallized precipitate particles.
反觀比較例1至6，比較例1至6並未對包含未與該結晶劑反應的汙染物離子及結晶懸浮顆粒的混合溶液進行過濾處理及其他後續處理步驟，因此，比較例1至6僅有98%至99%的汙染物離子去除率，此表示比較例1至6的方法所排放出的淨化水中仍存在有約1%至2%的汙染物離子。此外，比較例1至6僅有95%至98%的結晶沉澱顆粒結晶率，此表示比較例1至6的方法所排放出的淨化水中仍存在有約2%至5%的結晶懸浮顆粒。In contrast, in Comparative Examples 1 to 6, the mixed solution containing pollutant ions and crystallized suspended particles that have not reacted with the crystallization agent is not subjected to filtration treatment and other subsequent treatment steps. Therefore, Comparative Examples 1 to 6 have only a pollutant ion removal rate of 98% to 99%, which means that about 1% to 2% of pollutant ions are still present in the purified water discharged by the methods of Comparative Examples 1 to 6. In addition, Comparative Examples 1 to 6 have only a crystallization rate of precipitated particles of 95% to 98%, which means that about 2% to 5% of crystallized suspended particles are still present in the purified water discharged by the methods of Comparative Examples 1 to 6.
基於上述，相較於比較例1至6的汙染物離子去除率及結晶沉澱顆粒結晶率，實施例1至6具有高的汙染物離子去除率及結晶沉澱顆粒結晶率，此表示實施例1至6能更有效地去除廢水中的汙染物離子，而具有優異的汙染物離子去除效果。此外，由於實施例1至6能夠在幾乎不排放結晶懸浮顆粒及未與該結晶劑反應的汙染物離子的情況下，反覆地將汙染物離子及結晶懸浮顆粒回收並使其與結晶劑反應而形成結晶沉澱顆粒，因此，實施例1至6還具有近乎零汙染物排放的優點。Based on the above, compared with the pollutant ion removal rate and the crystallization rate of the crystallized precipitate particles of Comparative Examples 1 to 6, Examples 1 to 6 have high pollutant ion removal rates and crystallization rates of the crystallized precipitate particles, which means that Examples 1 to 6 can more effectively remove pollutant ions in wastewater and have excellent pollutant ion removal effects. In addition, since Examples 1 to 6 can repeatedly recover pollutant ions and crystallized suspended particles and react them with the crystallization agent to form crystallized precipitated particles without almost discharging crystallized suspended particles and pollutant ions that have not reacted with the crystallization agent, Examples 1 to 6 also have the advantage of almost zero pollutant discharge.
綜上所述，本發明處理廢水中汙染物離子的流體化床均質結晶方法，透過將汙染物離子與結晶劑反應後所獲得的包含結晶懸浮顆粒及未與該結晶劑反應的汙染物離子的混合溶液進行過濾處理，獲得包含結晶懸浮顆粒的殘留物及包含未與該結晶劑反應的汙染物離子的濾液，以及將該殘留物輸送回流體化床結晶裝置，及將該濾液進行分離處理後輸送回流體化床結晶裝置，以使結晶懸浮顆粒及汙染物離子能夠回到該流體化床結晶裝置與結晶劑及下一批次的廢水反應而生成結晶沉澱顆粒，從而使所排放出的淨化水中幾乎不含有汙染物離子及結晶懸浮顆粒，而具有高的汙染物離子去除率及高的結晶沉澱顆粒結晶率。此外，本發明處理廢水中汙染物離子的流體化床均質結晶方法還具有近乎零汙染物排放的優點。另外，本發明流體化床均質結晶設備透過該結晶劑供應裝置1、該流體化床結晶裝置2、該過濾裝置3、該迴流裝置4及該分離裝置5的相互配合，尤其是該過濾裝置3、該迴流裝置4及該分離裝置5，從而能夠有效地去除廢水中的汙染物離子，且達到近乎零汙染物排放的功效，故確實能達成本發明的目的。In summary, the fluidized bed homogeneous crystallization method for treating pollutant ions in wastewater of the present invention comprises filtering a mixed solution containing crystallized suspended particles and pollutant ions that have not reacted with the crystallizer, obtained after the pollutant ions react with the crystallizer, to obtain a residue containing crystallized suspended particles and a filtered solution containing pollutant ions that have not reacted with the crystallizer, and then transporting the residue back to the fluidized bed homogeneous crystallization system. The filter liquid is separated and then transported back to the fluidized bed crystallization device, so that the crystallized suspended particles and pollutant ions can return to the fluidized bed crystallization device to react with the crystallizer and the next batch of waste water to generate crystallized precipitated particles, so that the discharged purified water contains almost no pollutant ions and crystallized suspended particles, and has a high pollutant ion removal rate and a high crystallization rate of crystallized precipitated particles. In addition, the fluidized bed homogeneous crystallization method for treating pollutant ions in waste water of the present invention also has the advantage of almost zero pollutant discharge. In addition, the fluidized bed homogenization crystallization device of the present invention can effectively remove pollutant ions in wastewater and achieve the effect of nearly zero pollutant discharge through the mutual cooperation of the
惟以上所述者，僅為本發明的實施例而已，當不能以此限定本發明實施的範圍，凡是依本發明申請專利範圍及專利說明書內容所作的簡單的等效變化與修飾，皆仍屬本發明專利涵蓋的範圍內。However, the above is only an embodiment of the present invention and should not be used to limit the scope of implementation of the present invention. All simple equivalent changes and modifications made according to the scope of the patent application of the present invention and the content of the patent specification are still within the scope of the present patent.
1:結晶劑供應裝置 2:流體化床結晶裝置 21:反應空間 3:過濾裝置 4:迴流裝置 5:分離裝置 6:酸鹼值調整裝置 1: Crystallizer supply device 2: Fluidized bed crystallization device 21: Reaction space 3: Filter device 4: Circulation device 5: Separation device 6: pH value adjustment device
本發明的其他的特徵及功效，將於參照圖式的實施方式中清楚地呈現，其中： 圖1是一示意圖，說明本發明流體化床均質結晶設備的第一實施例； 圖2是一示意圖，說明本發明流體化床均質結晶設備的第二實施例； 圖3是一示意圖，說明本發明流體化床均質結晶設備的第三實施例；及 圖4是一示意圖，說明本發明流體化床均質結晶設備的第四實施例。 Other features and effects of the present invention will be clearly presented in the embodiments with reference to the drawings, wherein: FIG. 1 is a schematic diagram illustrating a first embodiment of the fluidized bed homogeneous crystallization apparatus of the present invention; FIG. 2 is a schematic diagram illustrating a second embodiment of the fluidized bed homogeneous crystallization apparatus of the present invention; FIG. 3 is a schematic diagram illustrating a third embodiment of the fluidized bed homogeneous crystallization apparatus of the present invention; and FIG. 4 is a schematic diagram illustrating a fourth embodiment of the fluidized bed homogeneous crystallization apparatus of the present invention.
1:結晶劑供應裝置 1: Crystallization agent supply device
2:流體化床結晶裝置 2: Fluidized bed crystallization device
21:反應空間 21: Reaction space
3:過濾裝置 3: Filter device
4:迴流裝置 4: Circulation device
5:分離裝置 5: Separation device
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