KR19980086123A - Foshan Wastewater Treatment Method - Google Patents
Foshan Wastewater Treatment Method Download PDFInfo
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- KR19980086123A KR19980086123A KR1019970022389A KR19970022389A KR19980086123A KR 19980086123 A KR19980086123 A KR 19980086123A KR 1019970022389 A KR1019970022389 A KR 1019970022389A KR 19970022389 A KR19970022389 A KR 19970022389A KR 19980086123 A KR19980086123 A KR 19980086123A
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- hydrofluoric acid
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- containing wastewater
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- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 27
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 119
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000002351 wastewater Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- -1 fluorine ions Chemical class 0.000 claims abstract description 28
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 25
- 239000011737 fluorine Substances 0.000 claims abstract description 25
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 25
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 21
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000005189 flocculation Methods 0.000 claims abstract description 17
- 230000016615 flocculation Effects 0.000 claims abstract description 17
- 238000001556 precipitation Methods 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 150000001450 anions Chemical class 0.000 claims abstract description 15
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 14
- 238000001179 sorption measurement Methods 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 3
- 239000011521 glass Substances 0.000 claims description 10
- 230000015271 coagulation Effects 0.000 claims description 8
- 238000005345 coagulation Methods 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000011221 initial treatment Methods 0.000 claims description 2
- 238000011282 treatment Methods 0.000 abstract description 14
- 239000002244 precipitate Substances 0.000 abstract description 11
- 230000002776 aggregation Effects 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 239000011575 calcium Substances 0.000 description 10
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 9
- 229910001424 calcium ion Inorganic materials 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 7
- 238000004062 sedimentation Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 5
- 229910004261 CaF 2 Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 229920006318 anionic polymer Polymers 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 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
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
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Abstract
본 발명은 불산함유폐수 처리 방법을 제공한다.The present invention provides a method for treating hydrofluoric acid containing wastewater.
그 불산함유폐수 처리 방법은 칼라브라운관의 유리세정공정에서 발생되는 불산함유폐수의 불소이온(F-)을 제거하기 위한 불산함유폐수 처리 방법에 있어서: 불산함유폐수에 염화칼슘(CaCl2)과 염화 제2철(FeCl2·6H2O)과 음이온 폴리머(Anion-polymer)를 첨가하여 불화칼슘(CaF2)을 형성하는 응집반응 단계(S10); 상기 응집반응이 일어난 불산함유폐수를 침전조로 유입시켜 불화칼슘(CaF2)을 침전시키는 침전반응 단계(S20); 침전된 불화칼슘(CaF2)을 제거한 1차 처리수를 중화조로 유입시키고, 황산(H2SO4)과 수산화나트(NaOH)를 첨가하여 pH를 안정화시키는 중화반응 단계(S30); 및 상기 중화반응단계(S30)를 거친 2차 처리수를 음이온 교환 수지탑으로 유입시켜 잔류하고 있는 불소이온(F-)을 음이온 교환 수지에 흡착시키는 음이온 흡착반응 단계(S40)를 포함하는 것을 특징으로 한다.The hydrofluoric acid-containing wastewater treatment method is a hydrofluoric acid-containing wastewater treatment method for removing fluorine ions (F − ) from the hydrofluoric acid-containing wastewater generated in the glass-cleaning process of color-brown tubes: calcium chloride (CaCl 2 ) and chloride An agglomeration reaction step (S10) of forming calcium fluoride (CaF 2 ) by adding ferric iron (FeCl 2 · 6H 2 O) and an anion polymer; A precipitation reaction step (S20) of introducing the hydrofluoric acid-containing wastewater in which the flocculation reaction has occurred, to precipitate calcium fluoride (CaF 2 ); A neutralization step of introducing the first treated water from which precipitated calcium fluoride (CaF 2 ) is removed into a neutralization tank and stabilizing a pH by adding sulfuric acid (H 2 SO 4 ) and sodium hydroxide (NaOH); And an anion adsorption reaction step (S40) of adsorbing the remaining fluorine ions (F − ) to the anion exchange resin by introducing the secondary treated water having passed through the neutralization reaction step (S30) into an anion exchange resin tower. It is done.
이에 따라, 염화칼슘(CaCl2)에 의한 1차 불소이온(F-) 중화 응집·침전처리후, 음이온 교환수지에 의한 2차 불소이온(F-) 흡착처리를 함으로써, 중화처리를 위한 화학약품의 사용량을 줄일 수 있을 뿐 아니라, 불소이온(F-)의 제거 효율을 높이고, 침전물의 양을 감소시킬 수 있는 효과가 있다.As a result, calcium chloride (CaCl 2) 1 primary fluoride ion (F -) by neutralization flocculation, secondary fluoride ion (F -) by the precipitation process, the anion exchange resin chemicals for the neutralization treatment by the adsorption process of the In addition to reducing the amount of use, it is possible to increase the efficiency of removing fluorine ions (F − ) and to reduce the amount of precipitates.
Description
본 발명은 불산함유폐수처리방법에 관한 것으로서, 특히 CRT(Cathode-Ray Tube) 유리 세정공정에서 발생되는 불산(HF)이 함유된 폐수에 염화칼슘(CaCl2)과 음이온 교환수지를 첨가하여 불산(HF)의 불소이온(F-)을 제거하기 위한 불산함유폐수 처리 방법에 관한 것이다.The present invention relates to a hydrofluoric acid-containing wastewater treatment method, and more particularly, to hydrofluoric acid (HF) by adding calcium chloride (CaCl2) and an anion exchange resin to wastewater containing hydrofluoric acid (HF) generated in a CRT (Cathode-Ray Tube) glass cleaning process. It relates to a hydrofluoric acid-containing wastewater treatment method for removing fluorine ions (F − ).
일반적으로, CRT의 펀넬(Funnel)이나 패넬(Panel) 등의 유리(Grass) 표면에 부착되는 이물질은 Dog의 탈락이나 불균일 도포등 불량 발생의 원인이 된다. 따라서, CRT 제조 공정에서는 수차례의 유리(Grass) 자동 세정공정을 거쳐야 한다. 이 유리 세척공정에서는, 세정제로 약 50~80℃의 불산과 질산과 물이 함유된 혼합 산을 이용하며, 유리(Grass)를 세정한 후 Heat Dry 방식으로 건조를 한다.In general, foreign matter adhering to the surface of glass, such as funnel or panel of the CRT, may cause defects such as dog dropout or uneven coating. Therefore, CRT manufacturing process has to go through several glass automatic cleaning processes. In this glass cleaning process, a mixed acid containing hydrofluoric acid, nitric acid, and water at about 50 to 80 ° C. is used as a cleaner, and the glass is cleaned and dried by a heat dry method.
그러나, 이러한 유리 세정공정에서 사용되는 혼합 산의 성분 중 불산(HF)은 환경에 대단히 유해하므로 이 유해 요소를 제거하는 것이 대단히 중요하다.However, hydrofluoric acid (HF) among the components of the mixed acid used in this glass cleaning process is very harmful to the environment, so it is very important to remove this harmful element.
도 1은 종래의 불산함유폐수 처리 방법을 도시한 개략도이다.1 is a schematic view showing a conventional hydrofluoric acid-containing wastewater treatment method.
도 1에 도시된 바와 같이, 종래에는 1차 응집반응 단계(S1), 침전반응 단계(S2), 2차 응집반응 단계(S3), 2차 침전반응 단계(S4), 및 중화반응 단계(S5)를 거치면서 불산함유폐수를 처리하였다.As shown in FIG. 1, conventionally, the first aggregation reaction step (S1), the precipitation reaction step (S2), the second aggregation reaction step (S3), the second precipitation reaction step (S4), and the neutralization reaction step (S5) ) Was treated with hydrofluoric acid-containing wastewater.
일반적으로, 유리 세정용으로 사용된 불산함유폐수는, 약 150~200ppm의 불소이온(F-)을 함유하고 있다. 이러한 불소이온(F-)이 함유된 폐수는 모두 불산집수조로 모아진다.Generally, hydrofluoric acid containing wastewater used for glass cleaning contains about 150-200 ppm of fluorine ion (F <-> ). All wastewater containing fluorine ions (F − ) is collected in a hydrofluoric acid collection tank.
불산집수조에 모아진 불산함유폐수는 1차 응집 반응조로 유입된다. 이 1차 응집 반응조의 불산함유폐수에 약 3000ppm의 수산화칼슘(Ca(OH)2)과 약 200~300ppm의 황화제1철(FeSO4·7H2O)과 약 3ppm의 음이온 폴리머(Anion-polymer)를 첨가하면, 이온화된 수산화칼슘(CA(OH)2)의 칼슘이온(Ca2+)과 불산(HF)의 불소이온(F-)이 응집반응하여 불화칼슘(CaF2)을 형성되기 시작한다. 이 때, 상기 황화제1철(FeSO4·7H2O)과 음이온 폴리머(Anion-polymer)는 칼슘이온(Ca2+)과 불소이온(F-)의 응집반응이 용이하게 되도록 작용한다.(S1)The wastewater containing hydrofluoric acid collected in the hydrofluoric acid collection tank flows into the first flocculation reactor. About 3000 ppm of calcium hydroxide (Ca (OH) 2 ), about 200 to 300 ppm of ferrous sulfide (FeSO 4 · 7H 2 O), and about 3 ppm of anion-polymer were added to the hydrofluoric acid-containing wastewater of the primary coagulation reactor. When is added, calcium ion (Ca 2+ ) of ionized calcium hydroxide (CA (OH) 2 ) and fluorine ion (F − ) of hydrofluoric acid (HF) begin to aggregate to form calcium fluoride (CaF 2 ). At this time, the ferrous sulfide (FeSO 4 · 7H 2 O) and the anion polymer (Anion-polymer) acts to facilitate the aggregation reaction of calcium ions (Ca 2+ ) and fluorine ions (F − ). S1)
응집반응이 일어난 불산함유폐수는 1차 침전조로 유입된다. 이 1차 침전조에서 CaF2(불화칼슘)은 침전되어 가라앉는다. 이 칼슘이온(Ca2+)과 불소이온(F-)의 응집·침전 반응식은 다음과 같다.The hydrofluoric acid-containing wastewater from which flocculation occurs is introduced into the primary sedimentation tank. In this primary settling tank, CaF 2 (calcium fluoride) precipitates and sinks. The coagulation and precipitation equation of the calcium ion (Ca 2+ ) and the fluorine ion (F − ) is as follows.
2HF+Ca(OH)2=CaF2↓ + 2H2O2HF + Ca (OH) 2 = CaF 2 ↓ + 2H 2 O
상기 1차 침전조에서 불화칼슘(CaF2)의 침전물을 인출하여 탈수시켜 제거하면, 1차 침전조에는 1차 처리수가 남게된다.(S2)When the precipitate of calcium fluoride (CaF 2 ) is taken out and dehydrated in the primary sedimentation tank, the primary treated water remains in the primary sedimentation tank. (S2)
1차 처리수는 다시 2차 반응조로 유입된다. 이 2차 반응조에 유입된 1차 처리수에 다시 수산화칼슘(Ca(OH)2)과 황산제1철(FeSO4·7H2O)과 음이온 폴리머(Anion-polymer)를 첨가한다. 이 2차 반응조에서는 상술된 S1단계에서와 같이 칼슘이온(Ca2+)과 잔류하고 있는 불소이온(F-) 사이에 2차 응집반응이 일어나게 된다.(S3)The primary treated water is introduced back into the secondary reactor. Calcium hydroxide (Ca (OH) 2 ), ferrous sulfate (FeSO 4 · 7H 2 O), and anion polymer are added to the primary treated water introduced into the secondary reactor. In this secondary reactor, secondary agglomeration occurs between calcium ions (Ca 2+ ) and remaining fluorine ions (F − ) as in step S1 described above.
이 2차 응집반응이 일어난 폐수는 다시 2차 침전조로 유입되고, 응집된 불화 칼슘(CaF2)을 침전시킨다. 침전된 불화칼슘(CaF2)을 제거한 2차 처리수는, 불산(HF)이외의 다른 함유 물질에 의하여 pH 10~11의 염기 성질을 가지며, 불소이온(F-)의 잔류량은 약 8~10ppm이다.(S4)Wastewater from which the secondary flocculation reaction has occurred is introduced into the secondary sedimentation tank again to precipitate the aggregated calcium fluoride (CaF 2 ). Secondary treated water from which precipitated calcium fluoride (CaF 2 ) is removed has a basic property of pH 10 to 11 with a substance other than hydrofluoric acid (HF), and the residual amount of fluorine ions (F − ) is about 8 to 10 ppm. (S4)
상술된 바와 같이, 2차 응집·침전 반응에 의해 불소이온(F-)을 처리한 2차 처리수는 불소함유폐수의 기타 함유 물질에 의하여 염기 성질을 갖는다. 따라서, 이 2차 처리수에 강산인 황산(H2SO4)을 약 10% 첨가하여 중화시킨 후 방류하게 된다. 이 중화처리 후 방류되는 방류수의 pH 농도는 약 5.8~6.8이다.(S5)As described above, the secondary treated water treated with fluorine ions (F − ) by secondary flocculation and sedimentation reactions has a basic property by other substances containing fluorine-containing wastewater. Therefore, about 10% of sulfuric acid (H 2 SO 4 ), which is a strong acid, is added to the secondary treated water to neutralize and discharged. The pH concentration of the effluent discharged after this neutralization is about 5.8 to 6.8. (S5)
위와 같이, 종래의 불산함유폐수 처리 방법에서는, 두차례에 걸쳐 불산폐수에 수산화칼슘(Ca(OH)2)과 황화제1철(FeSO4·7H2O)과 음이온 폴리머(Anion-polymer)를 첨가하여 불소 성분을 응집·침전시켜 제거하고, 그 pH 농도가 10~11 정도인 처리수를 중화시켜 방류하였다.As described above, in the conventional hydrofluoric acid-containing wastewater treatment method, calcium hydroxide (Ca (OH) 2 ), ferrous sulfide (FeSO 4 · 7H 2 O), and anion-polymer are added to the hydrofluoric acid wastewater twice. The fluorine component was coagulated and precipitated to remove the precipitate, and the treated water having a pH concentration of about 10 to 11 was neutralized and discharged.
그러나, 그러한 종래의 불산함유폐수 처리 방법의 작용에 의하면, 불소이온을 제거한 처리수를 중화시키기 위해 황산등 과량의 화학약품처리를 하여야 하는 문제점이 있을 뿐 아니라, 불소이온의 제거효율이 낮고, 많은 양의 침전물이 발생하는 등의 문제점이 있다.However, according to the operation of the conventional hydrofluoric acid-containing wastewater treatment method, there is a problem in that an excessive amount of chemical treatment such as sulfuric acid is required to neutralize the treated water from which fluorine ions are removed. There is a problem that a positive precipitate is generated.
따라서, 본 발명은 상기와 같은 문제점을 해소하기 위하여 발명된 것으로, 중화처리를 위한 화학약품의 사용량을 줄일 수 있을 뿐 아니라, 불소이온의 제거 효율을 높이고, 침전물의 양을 감소시키기 위한 불산함유폐수 처리 방법을 제공하는데 그 목적이 있다.Therefore, the present invention was invented to solve the above problems, and can reduce the amount of chemicals used for the neutralization treatment, as well as increase the fluorine ion removal efficiency and reduce the amount of sediment. Its purpose is to provide a treatment method.
도 1은 종래의 불산함유폐수 처리 방법을 도시한 개략도.1 is a schematic view showing a conventional hydrofluoric acid-containing wastewater treatment method.
도 2는 본 발명의 일 실시예에 따른 불산함유폐수 처리 방법을 도시한 개략도.Figure 2 is a schematic diagram showing a hydrofluoric acid-containing wastewater treatment method according to an embodiment of the present invention.
* 도면의 주요부분에 대한 부호의 설명 *Explanation of symbols on the main parts of the drawings
S1~S5: 종래의 불산함유폐수 처리 방법S1 to S5: conventional hydrofluoric acid-containing wastewater treatment method
S10~S40:본 발명의 일 실시예에 따른 불산함유폐수 처리 방법S10 ~ S40: hydrofluoric acid-containing wastewater treatment method according to an embodiment of the present invention
ㄴN
이러한 목적을 달성하기 위해 본 발명에 따른 불산함유폐수처리 방법은, 칼라브라운관의 유리세정공정에서 발생되는 불산함유폐수의 불소이온(F-)을 제거하기 위한 불산함유폐수 처리 방법에 있어서, 불산함유폐수에 염화칼슘(CaCl2)과 염화제2철(FeCl2·6H2O)과 음이온 폴리머(Anion-polymer)를 첨가하여 불화칼슘(CaF2)을 형성하는 응집반응 단계, 상기 응집반응이 일어난 불산함유폐수를 침전조로 유입시켜 불화칼슘(CaF2)을 침전시키는 침전반응 단계, 침전된 불화칼슘(CaF2)을 제거한 1차 처리수를 중화조로 유입시키고, 황산(H2SO4)과 수산화나트륨(NaOH)를 첨가하여 pH를 안정화시키는 중합반응 단계 및, 상기 중화반응단계를 거친 2차 처리수를 음이온 교환 수지탑으로 유입시켜 잔류하고 있는 불소이온(F-)을 음이온 교환 수지에 흡착시키는 음이온 흡착반응 단계를 포함하는 것을 특징으로 한다.In order to achieve this object, the hydrofluoric acid-containing wastewater treatment method according to the present invention is a hydrofluoric acid-containing wastewater treatment method for removing fluorine ions (F − ) of the hydrofluoric acid-containing wastewater generated in the glass cleaning process of a color-brown tube. Coagulation reaction step of forming calcium fluoride (CaF 2 ) by adding calcium chloride (CaCl 2 ), ferric chloride (FeCl 2 · 6H 2 O), and anionic polymer (Anion-polymer) to the wastewater. Precipitation reaction step of precipitating calcium fluoride (CaF2) by introducing the wastewater into the settling tank, the first treatment water from which the precipitated calcium fluoride (CaF 2 ) was removed was introduced into the neutralization tank, and sulfuric acid (H 2 SO 4 ) and sodium hydroxide ( Anion adsorption that adsorbs the remaining fluorine ions (F − ) to the anion exchange resin by introducing the polymerization reaction step of stabilizing the pH by adding NaOH) and the second treated water that has undergone the neutralization reaction step into the anion exchange resin column. Characterized in that it comprises a complexing step.
상기 응집반응 단계는 염화제2철(FeCl2·6H2O)과 음이온 폴리머(Anion-polymer)가 응집반응을 용이하게 하기 위한 촉매로써 작용하는 것을 특징으로 한다.The coagulation step is characterized in that the ferric chloride (FeCl 2 · 6H 2 O) and the anion polymer (Anion-polymer) acts as a catalyst to facilitate the coagulation reaction.
상기 침전반응 단계는, 불산함유폐수의 염화칼슘(CaCl2)에 의한 응집·침전반응에 염산(HCl)이 부산물로 생성되며, 상기 염산(HCl)에 의하여 1차 처리수가 중화되어 pH 6~7이되며, 불화칼슘(CaF2) 이 침전된 후 1치처리수의 불소이온(F-)의 농도는 30~50ppm이 되는 것을 특징으로 한다.In the precipitation step, hydrochloric acid (HCl) is produced as a by-product in the flocculation and precipitation reaction of calcium chloride (CaCl 2 ) in hydrofluoric acid-containing wastewater, and the first treatment water is neutralized by hydrochloric acid (HCl) to pH 6-7. After the calcium fluoride (CaF 2 ) is precipitated, the concentration of fluorine ion (F − ) in the treated water is 30 to 50 ppm.
그리고, 상기 음이온 흡착반응 단계는, 잔류하고 있는 불송이온(F-)을 흡착하기 위한 음이온 교환 수지로 수산화질소화합물(R≡NOH)이 사용되며, 음이온 교환수지의 흡착반응 후, 수질의 불소이온(F-)의 함유농도가 2~3ppm이 되는 것을 특징으로 한다.In addition, in the anion adsorption reaction step, a nitrogen hydroxide compound (R≡NOH) is used as an anion exchange resin for adsorbing residual ions (F − ), and after the adsorption reaction of the anion exchange resin, It is characterized in that the concentration of ions (F − ) is 2-3 ppm.
이하, 첨부된 도면을 참조하여 본 발명의 바람직한 실시예를 상세히 설명하면 다음과 같다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.
도 2에 본 발명에 일 실시예에 따른 불산함유폐수 처리 방법의 개략도가 도시된다.2 is a schematic diagram of a hydrofluoric acid-containing wastewater treatment method according to an embodiment of the present invention.
도 2에 도시된 바와 같이, 본 발명의 일 실시에에 따른 불산함유폐수 처리 방법은, 염화칼슘(CaCl2)과 염화제2철(FeCl2·6H2O)과 음이온 폴리머(Anion-polymer)를 첨가하는 칼슘이온(Ca2+)과 불소이온(F-)을 응집시키는 응집반응 단계(S10), 상기 응집반응 단계(S10)를 거친 폐수를 침전조로 유입시켜 응집상태의 불화칼슘(CaF2)를 침전시키고 그 침전물을 인출하여 제거하는 침전반응 단계(S20), 침전물인 불화칼슘(CaF2)이 제거된 1차 처리수에를 중화조로 유입시키고 황산(H2SO4)과 수산화나트륨(NaOH)를 첨가하여 pH 헌팅을 안정화시키기 위한 중화반응 단계(S30) 그리고, 상기 중화반응 단계(S30)를 거친 2차 처리수를 음이온 교환 수지가 첨가된 음이온 교환 수지탑으로 유입시키고 불소이온(F-)을 흡착시키는 음이온 흡착반응 단계(S40)를 통해서 불산함유폐수를 처리한다.As shown in FIG. 2, the hydrofluoric acid-containing wastewater treatment method according to an embodiment of the present invention includes calcium chloride (CaCl 2 ), ferric chloride (FeCl 2 · 6H 2 O), and anion polymer (Anion-polymer). Agglomeration reaction step (S10) that aggregates the added calcium ions (Ca 2+ ) and fluorine ions (F − ), and the wastewater passed through the flocculation reaction step (S10) is introduced into the settling tank and the calcium fluoride in the aggregated state (CaF 2 ) Precipitate reaction step to precipitate and remove the precipitate by removing the precipitate (S20), the first treatment water in which the precipitate of calcium fluoride (CaF 2 ) is removed into a neutralization tank and sulfuric acid (H 2 SO 4 ) and sodium hydroxide (NaOH ) was added to neutralize the reaction steps to stabilize the pH hunting (S30) then, the neutralization reaction step (S30) the coarse second-order process can be a was introduced into the anion exchange resin column of an anion exchange resin was added fluoride ion (F - Wastewater containing hydrofluoric acid through the anion adsorption reaction step (S40) And Lee.
상술된 처리 단계들을 거쳐 불산함유폐수를 처리하는, 본 발명의 실시예에 따른 불산함유폐수 처리 방법의 상세한 작용은 설명하면 다음과 같다.The detailed operation of the hydrofluoric acid-containing wastewater treatment method according to the embodiment of the present invention for treating the hydrofluoric acid-containing wastewater through the above-described treatment steps is as follows.
칼라 브라운관 공정에서 유리 세정용으로 사용된 폐수는 약 150~200ppm의 불소이온(F-)을 함유하고 있다. 이러한, 불산함유폐수를 처리하기 위해서, 먼저 불산집수조에 모아진 불산함유폐수를 1차 응집 반응조로 유입시키고, 염화칼슘(CaCl2)과 염화제2철(FeCl2·6H2O)와 음이온 폴리머(Anion-polymer)를 첨가한다. 상기 1차 응집 반응조에서는 염화칼슘(CaCl2)의 칼슘이온(Ca+)과 불산함유폐수의 불소이온(F-) 사이에 응집반응이 일어나 불화칼슘(CaF2)이 형성되기 시작한다. 이 때, 염화제2철(FeCl2·6H2O)과 음이온 폴리머(Anion-polymer)는 칼슘이온(Ca+)과 불소이온(F-)의 응집반응을 용이하게 하기 위한 촉매로써 작용한다.(S10)Wastewater used for glass cleaning in the color CRT process contains about 150 to 200 ppm of fluoride ion (F − ). In order to treat the hydrofluoric acid-containing wastewater, first, the hydrofluoric acid-containing wastewater collected in the hydrofluoric acid collection tank is introduced into a first flocculation reactor, and calcium chloride (CaCl 2 ), ferric chloride (FeCl 2 · 6H 2 O), and anionic polymer (Anion) are introduced. -polymer). In the primary agglomeration reactor, agglomeration occurs between calcium ions (Ca + ) of calcium chloride (CaCl 2 ) and fluoride ions (F − ) of fluorine-containing wastewater, and calcium fluoride (CaF 2 ) begins to form. At this time, the iron (III) chloride (FeCl 2 · 6H 2 O) and anionic polymer (Anion-polymer) is the calcium ion (Ca +) and fluoride ions (F -) acts as a catalyst to facilitate the flocculation of. (S10)
불화칼슘(CaF2)이 형성된 폐수는 침전조로 유입된다. 이 침전조에서 불화칼슘(CaF2)이 침전되면 그 침전된 불화칼슘(CaF2)을 필터에 의해 걸러내어 인출한 후 탈수하여 제거한다.Wastewater in which calcium fluoride (CaF 2 ) is formed enters the settling tank. When calcium fluoride (CaF 2 ) is precipitated in this precipitation tank, the precipitated calcium fluoride (CaF 2 ) is filtered out by a filter, followed by dehydration and removal.
2HF+CaCl2=CaF2↓ + 2HCl2HF + CaCl 2 = CaF 2 ↓ + 2HCl
상술된 식은 불화칼슘(CaF2)의 침전 반응식이다. 상술된 반응식에서와 같이, 불산(HF)와 염화칼슘(CaCl2)의 반응 후, 그 부산물로써 염산(HCl)이 생성된다. 불소 이온(F-)의 응집·침전반응 후, 불화칼슘(CaF2)의 침전물을 인출한 1차 처리수는 불산함유폐수의 다른 함유 물질에 의하여 염기 성질을 가지고 있으나 응집반응의 부산물인 상기 염산(HCl)에 의해 중화된다.The above-mentioned formula is a precipitation scheme of calcium fluoride (CaF 2 ). As in the reaction scheme described above, after the reaction of hydrofluoric acid (HF) with calcium chloride (CaCl 2 ), hydrochloric acid (HCl) is produced as a by-product. After flocculation and sedimentation of fluorine ions (F − ), the primary treated water withdrawing the precipitate of calcium fluoride (CaF 2 ) has basic properties due to the other content of the wastewater containing hydrofluoric acid, but the hydrochloric acid is a byproduct of the flocculation reaction. Neutralized by (HCl).
위와 같이, 불화칼슘(CaF2) 침전물을 제거한 1차 처리수는, 불소이온(F-) 농도가 약 30~50ppm이고, 상기 염산(HCl)에 의해 그 pH 농도는 6~7로 중성의 성질을 갖는다. 즉, 불산(HF)이 함유 폐수는 염화칼슘(CaCl2)에 의해 중화 응집·침전반응을 하게 된다.(S20)As described above, the primary treated water from which the calcium fluoride (CaF 2 ) precipitate was removed has a fluorine ion (F − ) concentration of about 30 to 50 ppm and a pH of 6 to 7 due to hydrochloric acid (HCl). Has That is, the wastewater containing hydrofluoric acid (HF) undergoes neutralization flocculation and precipitation by calcium chloride (CaCl 2 ). (S20)
중화 응집·침전반응을 거친 1차 처리수는 중성의 성질을 갖게 되나 1차 처리수에 잔류하고 있는 칼슘이온(Ca2+)과 염화이온(Cl-)등 1차 처리수내에 잔류하고 있는 이온들에 의해 pH가 유동적으로 작용하는 pH헌팅이 발생한다.Neutralization flocculation treatment, can be subjected to the primary precipitation reaction is neutral, but have the property of calcium ions remaining in the treated primary (Ca 2+) and chloride ion (Cl -) ion, which remains in the primary treated water These results in pH hunting, in which the pH acts fluidly.
이러한 pH 농도를 안정화시키기 위해서 1차 처리수를 중화조로 유입시켜 황산(H2SO4)과 수산화나트륨(NaOH)를 첨가한다. 상기 황산(H2SO4)과 수산화나트륨(NaOH)은 이온화되고, 1차 처리수에 잔류하고 있는 칼슘이온(Ca2+)과 염화이온(Cl-)과 중화반응하여 황화칼슘(CaSO4) 염화나트륨(NaCl)을 형성한다. 이와 같이, 1차 처리수의 잔류 이온들이 제거됨으로 pH가 안정하게 유지된다.(S30)In order to stabilize the pH concentration, the first treatment water is introduced into a neutralization tank, and sulfuric acid (H 2 SO 4 ) and sodium hydroxide (NaOH) are added. The sulfuric acid (H 2 SO 4 ) and sodium hydroxide (NaOH) are ionized and neutralized with calcium ions (Ca 2+ ) and chloride ions (Cl − ) remaining in the primary treatment water to produce calcium sulfide (CaSO 4 ) Forms sodium chloride (NaCl). As such, the pH is kept stable by removing residual ions of the primary treated water.
중화조에서 그 pH가 안정되게 유지되도록 중화처리된 2차 처리수는 음이온 교환 수지가 첨가되어 있는 음이온 교환 수지탑으로 유입된다. 이 때, 음이온 교환수지로 수산화질소화합물(R≡NOH)이 첨가된다. 이 수산화질소화합물(R≡NOH)이 이온화되면서, 수산화기(OH-)가 떨어져 나간 R≡N+이온에 2차 처리수의 불소이온(F-)이 흡착된다. 음이온 교환수지의 흡착 반응식은 다음과 같다.In the neutralization tank, the secondary treated water neutralized to maintain its pH is introduced into the anion exchange resin tower to which an anion exchange resin is added. At this time, a nitrogen hydroxide compound (R≡NOH) is added to the anion exchange resin. As the nitrogen hydroxide compound (R≡NOH) is ionized, fluorine ions (F − ) of the secondary treated water are adsorbed to R≡N + ions from which the hydroxyl group (OH − ) is separated. The adsorption reaction of anion exchange resin is as follows.
H++F-+R≡NOH→R≡NF+H2O H + + F - + R≡NOH → R≡NF + H 2 O
즉, 상술된 반응식에 의해 2차 처리수에 잔류하고 있던 불소이온(F-)은 음이온 교환 수지에 흡착 처리된다.(S40)That is, the fluorine ions (F − ) remaining in the secondary treated water are adsorbed on the anion exchange resin by the reaction scheme described above (S40).
상술된 방법에 의한 염화칼슘(CaCl2)과 음이온 교환 수지를 이용한 불산함유 폐수 처리 후, 방류되는 방류수의 불소이온(F-)는 농도는 약 2~3ppm 이다. 종래의 불산함유폐수 처리 방법에서 폐수 처리된 방류수의 불소이온(F-)의 농도는 약 8~10ppm이므로, 종래의 불산함유폐수 처리 방법보다 불소이온(F-) 처리 효율이 약 65% 향상된다.After treatment with hydrofluoric acid-containing wastewater using calcium chloride (CaCl 2 ) and an anion exchange resin by the above-described method, the concentration of fluorine ions (F − ) in the effluent discharged is about 2-3 ppm. In the conventional hydrofluoric acid-containing wastewater treatment method, the concentration of fluorine ions (F − ) in the effluent treated with the wastewater is about 8 to 10 ppm, thereby improving the fluorine ion (F − ) treatment efficiency by about 65% compared to the conventional hydrofluoric acid-containing wastewater treatment method. .
이상과 같은 본 발명에 따른 불산함유폐수 처리 방법은, 염화칼슘(CaCl2)에 의한 1차 중화 응집·침전처리 후, 음이온 교환수지에 의한 2차 불소이온(F-) 흡착 처리를 함으로써, 중화처리를 위한 화학약품의 사용량을 줄일 수 있을 뿐 아니라, 불소 이온의 제거 효율을 높이고, 침전물의 양을 감소시킬 수 있는 효과가 있다.The hydrofluoric acid-containing wastewater treatment method according to the present invention as described above is neutralized by performing a secondary neutralization flocculation and sedimentation treatment with calcium chloride (CaCl 2 ) followed by a secondary fluorine ion (F − ) adsorption treatment with an anion exchange resin. In addition to reducing the amount of chemicals used for, there is an effect that can increase the removal efficiency of fluorine ions, and reduce the amount of sediment.
본 발명의 특정의 바람직한 실시예에 대해서 도시하고 설명하였지만, 이에 한정되지 않고 본 발명의 정신이나 이하 특허청구의 범위에서 이탈하지 않는 한도내에서 당업계의 통상의 지식을 가진자라면 여러가지 다양하게 응용과 변형이 가능할 것이다.While certain preferred embodiments of the present invention have been illustrated and described, those skilled in the art will appreciate that various modifications can be made without departing from the spirit of the present invention or the scope of the following claims. And variations will be possible.
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| KR100668012B1 (en) * | 2004-06-01 | 2007-01-15 | 산요덴키가부시키가이샤 | Treatment apparatus and treatment method of the water to be treated using the same |
| KR100841664B1 (en) * | 2006-05-30 | 2008-06-26 | 전치중 | Electrochemical Water Treatment System and Water Treatment Method |
| CN111747573A (en) * | 2020-07-13 | 2020-10-09 | 苏州苏净环保工程有限公司 | A treatment device and treatment process for coating electrophoresis wastewater |
| CN115072912A (en) * | 2022-06-22 | 2022-09-20 | 浙江巨化技术中心有限公司 | Combined treatment method of fluororesin production wastewater |
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| JPS5864181A (en) * | 1981-10-15 | 1983-04-16 | Hitachi Plant Eng & Constr Co Ltd | Treatment of fluorine-containing waste water |
| KR930010763A (en) * | 1991-11-22 | 1993-06-23 | 정용문 | How to process memo contents by voice |
| JPH06134471A (en) * | 1992-10-23 | 1994-05-17 | Kawasaki Steel Corp | Method for removing fluorine from waste water containing fluorine |
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| KR960034095A (en) * | 1995-03-30 | 1996-10-22 | 권석명 | Fluorine wastewater treatment method using calcium chloride and iron salt |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100668012B1 (en) * | 2004-06-01 | 2007-01-15 | 산요덴키가부시키가이샤 | Treatment apparatus and treatment method of the water to be treated using the same |
| KR100841664B1 (en) * | 2006-05-30 | 2008-06-26 | 전치중 | Electrochemical Water Treatment System and Water Treatment Method |
| US8323474B2 (en) | 2006-05-30 | 2012-12-04 | Chi-Jung Jeon | Electro-chemical water processing apparatus and method thereof |
| CN111747573A (en) * | 2020-07-13 | 2020-10-09 | 苏州苏净环保工程有限公司 | A treatment device and treatment process for coating electrophoresis wastewater |
| CN115072912A (en) * | 2022-06-22 | 2022-09-20 | 浙江巨化技术中心有限公司 | Combined treatment method of fluororesin production wastewater |
| CN115072912B (en) * | 2022-06-22 | 2024-03-19 | 浙江巨化技术中心有限公司 | Combined treatment method for fluororesin production wastewater |
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