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1 立論流理 Evaluation of drain water segregation system for etching tools and treatment performance for fluoride containing wastewater in semiconductor fabrication : : 年

2 流理 Evaluation of drain water segregation system for etching tools and treatment performance for fluoride containing wastewater in semiconductor fabrication Student Tingwen Chung Advisor Dr. Chihpin Huang 立論 A Thesis Master Degree Program of Environmental Technology for Sustainability College of Engineering National Chiao Tung University in Partial Fulfillment of the Requirements for the Degree of Master of Science In Engineering September 2008 Hsinchu, Taiwan, Republic of China 年

3 流理立理流行行度異理量硫離行流理狀理理若行不流若不不流流度度異了流離 P P 離 B B 離降數離硫離

4 Evaluation of drain water segregation system for etching tools and treatment performance for fluoride containing wastewater in semiconductor fabrication Student Tingwen Chung Advisor Dr. Chihpin Huang College of Engineering National Chiao Tung University Abstract This study goal is appraised the semiconductor fabrication the fluoride containing wastewater to process the facility and potency of the etching tools draining water divergence, and designated the science park some semiconductor fabrication carries on the appraisal, carries on the improvement suggestion according to the appraisal content. This study Effluents from production lines representing semiconductor manufacture, and investigates causes for effluent fluoride concentration differences between values detected by fluoride electrode and values monitored by Science Industrial Park Administration (SIPA). as well as effluents from intermediate units, were analyzed on-site by instrumental methods. The impact of sulfate concentration needs to be taken into consideration, with less impact of phosphates. Based on water quality monitoring, effluents could be diverted to acid-alkaline wastewater treatment trains, to fluidized bed or to remain being directed into fluorine intermediate units. Alkaline treatments lead to better removal based on experiments. Increasing ph from the first unit can maintain system ph as alkaline. Hence, sole ph adjustment is recommended for first fluorine unit, without calcium fluoride addition. Insignificant removals by adding calcium fluoride occurred with low influent ph, while ph adjustments couldn t complete in the first unit. Calcium fluoride addition is recommended starting at the second unit. Effluent fluoride concentration differences between values detected by online fluoride electrode and values monitored by Science Industrial Park Administration (SIPA) were investigated. Calibration is required. In addition to calibration, hydroxyl

5 P P ions in effluents were found to gradually consume LaFB3B in online fluoride electrodes and to damage efficiency and service life of electrodes. Values monitored by electrodes needed to be checked regularly, and fluoride electrodes needed to be routinely replaced. Keywords fluoride-containing wastewater phosphates sulfate fluoride electrode

6 論老論漏見益行羚勵行兩

7 錄.. I..... II..... IV 錄.. V 錄 VI 錄 VII 理說來來理流..15 料料論理理粒粒量度異 ph 46 論論參.51

8 錄異 ph 來理路理流理粒不 ph 粒粒 (Ca/F=1) 不 ph 粒粒 (Ca/F=2) 理粒不 ph 粒不 ph 離度沈離度..48

9 錄類流度

10 1.1 不類若類離離見量 30~50% 來爐 Local scrubber 來若行流易理理理來行流良理流行 (1) (2) 理度異 1

11 連 17 行 ph 度離度 SOB4PB P POB4PB 2- 流理 3- P 兩離度料理 ( ) 度異離 ( NIEA W413.52A) 兩離度異離度行兩不 P ( ) 理理理行不 ph 離離離度數理理理行 ph 離離離度 2

12 1.2.4 理流離 15 mg/l 量量理論度度流理率度數 mg/l 度數 mg/l ph 2~5 離硫硫離離硫理率理流兩理若良流理流離度硫度度料流流兩理理理理論理量降理 3

13 說來 (F, Fluorine) (Fluorspar) (NaB2BAlFB6,Bcryolite) (CaB10BFB2B(PO4)B6B, Fluorapatite) 度 1.4 mg/l 度 9~10 mg/l NHB4BF NaF CaFB2B KF PbFB2B Ca Ba Pb 料殺零量年量 2000 P P 例量都 (SiFB4 BSilicon tetra fluoride) 煉 Bauxite ore HF - 離 FP P 利 CaFB2 BFluorspar 煉硫 P 阮 P 4

14 2.1.2 Hydrofluoric acid, HF 1931 年精煉來量更離離力離度離離不立不立刺易露立狀易療良離離 P 更益露量葉累若女年 P 行行若不良量度落 P P P P 5

15 P 利度 mg/l 省來量 0.8 mg/l 料茶年來更量來若量來易 Fluorosis 8 mg/l 量 3 mg/l 不洞更阮 P 6

16 2.2 來來爐 Local scrubber 粒金離來金粒 P 離硫量 CMP 理 HB2BOB2B NHB4BOH 粒理率不 ph 9 逸列 (1) ABS (2) HB2BSOB4B HB2BOB2B HF NHB4BOH HCl (3) HF NHB4BF HNOB3B HB2BOB2B HCl HB2BSOB4B HAC HB3BPOB4B HBr Al Si (4) 爐 HF P (5) NaOH HCl HB2BOB2B (6) ( )Si Si+ HNOB3B + 6HF HB2BSiFB6B + HNOB3B + HB2BO (2-1) 7

17 + SiOB2B HF SiOB2B ( )SiOB2B SiOB2B + 6HF HB2B SiFB6B + HB2BO (2-2) NHB4BF 離 8

18 P + P 2.3 理理流理度離陸流來理離流理理 (1) 利離不理利離離 CaP 2+ 2FP - CaFB2(s)B Ksp = P -11 P(2-3) 例來了離 ph 離度離離離 (SiP P AlP P FeP 3+ P ) 硫離率 P ( 2001) 度省 ( 不 ) 率泥量流離流度理粒不易理 P 9

19 理離不度塞路羽易降兩 P P 理 ph 6~9 離 15 mg/l 理 ph ph % 率降量 P 麟 P ph ph 量粒降粒更粒率羽理理來理了硫了硫理沈硫了流量量泥論量 2 理論量便流量量離益 ph 5 ph 量泥 P P 10

20 來理離來離不量理令羽粒度 P P 行 P 靖 P 兩不量行離粒 P 李 P 行理粒沈降 - 降利 CMP Silica 粒粒 0.5 µm MF 行離 P 林隆 P (2) 流度 ( 100 mg/l) 不若度理粒流度量理離度降 P (Yang et al.,2001) P 度更度流泥流不粒理量離 P P 11

21 (3) 離離行離離離理理來理流連離離度理度理度不離來理度離理度料離行理 P Hichour 1999 P 離離硫更離流流量離 (4) 流流 P 李 P 數理蘭 DHV PERMUTIT 50 理理易量泥泥理量浪流理利不泥流理流 12

22 度 ph 流流量 P P 流 2000 年數流流兩利度度率粒利利 P 李利流度率降 P (Aldaco 2006) P P 粒若流離度降率流流 ph 6~8 度 400~800 mg/l 離若 10 mg/l 理率 P P 離度 800 mg/l 率降度 10 mg/l 離理度連連 P (5) 理理理栗立 PLANT 行 P 13 (Miki et al 1996) P 流

23 流流度 ph 理度 100 % 更料率 (2-4) 行 CaCOB3B 2HF CaFB2B COB2B HB2BO (2-4) 利泥泥離料 P P 泥離泥良 (6) 沈理兩離粒離度流利粒行離 P Huang and Liu,1999 P 理 Sodium oleate NaOl:CB18BHB33BCOOP PNaP P P P (7) 理 - 理量行離 MPa 離利行 P 劉 P + 14

24 2.4 流 P 年率 50 率 30% 率 80% 年 85 年率 70 率 50% 率 80% 年率 85 率 60% 率 70%P 若率了來率流流狀流不良異降率立不量流例 PWR Pure Water Reclaim 2. WWR Waste Water Reclaim 3. AWR Acid Waste Water Reclaim 4. Oxide-CMP Reclaim 5. 金 Metal-CMP Reclaim 6. 度 AWL Acid Waste Water Low P 15

25 7. 度 AWH Acid Waster Water High 8. 度 FWL Hydrofluoric Acid Low 9. 度 FWH Hydrofluoric Acid High 10. 度 IPA IPAL IPA Low 11. 度 IPA IPAL IPA High 12. 度 HB2BSOB4B HB2BSOB4 B-R 不流不理度類行不異切不量 P 林 P 16

26 料理流行 (1) (2) 理度異 ph 3-1 料理 1. ph 2. 離 3. 度硫理度異 1. 量 IC 量 1. ph 2. 離 3. 粒 4. 量 1. ph 2. 離 3. 離

27 3.1 料 (1) 35 % 度 35 % 離來 Panreac (2) 離度 100 mg/l Merck 99% (3) 離度 (Total ion strength adjustmen buffer TISAB ) 500ml 57 ml 58 g 4 g 1,2- (1,2-Cyclohexyl enediaminetetracetic acid CDTA) 6N ph 3.5~5.5 1L 量量 1L (4) ph 0.1 N 3 N HCl 0.1 N 3 N NaOH 來 ph (5) 離 1000 mg/l 量 Merck 99% (6) ISAB 離 18

28 3.2 (1) 度 HACH RATIO/XR channel 0.2 NTU~2000 NTU 度 (2) 度 (conductivity meter) WTW Multi Level 1 度 ph (3) (Jar tester) Phipps Bird PB rpm 20 rpm 7.6 cm 1.7 cm 六 1L (4) 雷奈粒 / 量量 Malvern Zetasizer nano ZS 粒粒 / 量量來量粒粒量粒度粒 0.6 nm~6 µm 粒 3 nm~10 µm (5) 度 (UV-VIS spectrophotometer) HITACHI U-3010 UV-VIS 度 420 nm 來 SOB4PB (6) 離 2- P 度 HACH/U.S.A SENSION 4 離 (model 51928) 量 ph 離 crystal membrane 度 19

29 19900 mg/l 度 0.02 mg/l 離 ph 5~9 行量 (7) 粒粒 Mastersizer 2000 Malvern 理利雷藍雷立葉粒度量粒利量 0.02 µm 2000 µm (8) IC (DIO NEX-DX-120) 離離離離來離 (9) ph meter HACH/U.S.A ph (10) 離 SENTEK/England (11) 24 連 ICW 6712 率 (12) 離 E-CHEM F 離 ph 5.5 離度量 0.02mg/L-1000mg/L (13) 離 E-CHEM 9110-Ca 理離量 ,000mg/L 20

30 3.3 ph 離度硫 (1) ph (NIEA W424.50A) 利參離離度數 ph 25 理離 10 ph mv (2) 離 (NIEA W413.52A) 離離 ph 利參離離度 (3) 離離 (NIEA W415.52B) POB4PB 離離 FP P BrP 3 2 P SOB4PB P NOB2PB P NOB3PB P ClP P 了離離流流列離離力不離離流量離度度離流度留度度量 P (4) 度度 (NIEA W203.51B) 21

31 P P mmho P 度 Conductivity 流 1 cmp 2 1 cm Resistance 數 mho / cm 度 10P -3 10P -6 / cm µmho / cm 度度行度度 (5) 硫度 (NIEA W430.51C) 硫硫度 420 nm 度量量 (6) 度 / (NIEA W427.52B) 硫硫理 (phosphomolybdic acid) 藍藍 (molybdenum blue) 度 880 nm 度量理量 22

32 3.4 (1) 24 連 17 行了 ph 度離度 SOB4PB 2- P POB4PB 3- P 離料度 (FWH) FWH 路行連 24 不連流量 24 不路利路留流見 3-2 度料行行路行 1. ph 2. 離 3. 度硫

33 (2) 理理行不 ph 離離數理理流量 ph 離度粒 Ca/F=1 Ca/F=2 量不 ph 粒流見 3-3 行理 (1) ph (2) 不 (3) 行 rpm (4) 20 粒粒 (5) 10 離度粒粒 ph 硫度 24

34 行理流行流不離粒

35 (3) 度異流度度異了度異 : 連流錄離 ( ) NIEA W413.52A 離度 ph 5.5 離度離量離度流見 3-4 連流錄離量離量離數行數離量離 3.4 異 26

36 4 ph 離離流見 3-5 理理理量離離理 3.5 ph 27

37 論 4.1 ( 4.1) 流度 local scrubber 流參 4.1 度度烈不度度路 ( 4.2) 連 24 ( 4.3) 不連流量 24 更來流度異度數 mg/l 度數 mg/l 硫度 mg/l 硫數離度度離易來量度離度離度度度流 28

38 不 2 數不度硫度來度 750 mg/l 硫度 475 mg/l 度 3 mg/l 理量硫離硫度離 ph 量泥 P P 流不 ph 來泥離率 WVZ51 列硫量行流流度 AWH 度 (AWL) 度 FWH 度 FWL 度 FWH 行流行論理理流兩理流行料理流硫不流理 5 mg/l 離度離理率量 P P 離度沈 29

39 理 1. 量理 WFT51 WHZ51 WID51 WRM51 WDS51 WRO51 WRP51 2. 量流理 WBT52 WED52 WKZ51 WKZ71 WMS71 WMT54 WDO51 WOT51 WWT54 3. 硫理 WVZ51 類見 4.3 Fw L/S 4.1 來理 4.2 路

40 FP FP P P POB4PB PP P POB4PB P P P P ph conductivity 3-2- SOB4B P (mg/l) (µs/cm) (mg/l) (mg/l) FW ,454 7, FW ,429 7, L/S L/S , FW , FW , ph 4.2 P - conductivity 3-2- SOB4B P (mg/l) (µs/cm) (mg/l) (mg/l) WBT WDS ,322 10, WED WFT ,260 37, WHZ , ,550 WID , WKZ WKZ WMS WMT , WOD WOT WRM , , WRO WRP ,921 10, WVZ , ,200 WWT

41 4.3 類理流 WFT51 WHZ51 WID51 WRM51 WDS51 WRO51 WRP51 WBT52 WED52 WKZ51 WKZ71 WMS71 WMT54 WDO51 WOT51 WWT54 WVZ51 32

42 P 4.2 理理理流見 4.4 NaOH HCl CaClB2B ph NaOH HCl CaClB2B ph NaOH HCl PACl ph 離 Polymer HCl NaOH CaClB2B ph HCl NaOH CaClB2B ph HCl NaOH PACl Polymer ph, FP 理流 33

43 4.2.1 理理 ph 離行理 ( 4.4) 95 年 11 行理度 10 mg/l ph 落 6~7 量都粒粒粒 PACl 行兩零沈不 P 1980 P 度 ph ph ph 粒 96 年 1 行 4.5 理度 85 mg/l 降 6 mg/l 流 15 mg/l 流不流離度流 15 mg/l 流流不流 ph 落 6~7 Zeta Potential 量量 34

44 4.4 [ FP - 95 年流 P] (mg/l) ph ZP (mv) [ FP - 96 年流 P] (mg/l) ph ZP (mv)

45 4.2.2 粒粒粒量理流流 4.5 理粒 2 例粒粒 1~100 µm 落粒不易降例粒粒 1000 µm 粒數粒易粒 2 粒 5 理來粒粒行粒粒 polymer 流粒數量理粒 36

46 25 raw water analysis volume (%) ÏÀ³¼Ñ1 ÏÀ³¼Ñ2 Ö²V¼Ñ ºC²V¼Ñ X y¼ñ 流 pt size(10-6 m) 4.5 理粒了粒粒 ph 粒粒 Ca/F=1 Ca/F=2 不 ph 粒粒 4.6 Ca/F=1 ph 粒粒 ph 都兩例來 Ca/F=1 ph7~8 粒率 ph 粒狀不粒率不 4.7 Ca/F=2 不 ph 粒粒 ph 兩 Ca/F 2 降粒率粒來粒度粒粒論粒粒落 0.1~1 µmp 隆 2003 P 粒林 37

47 ph 10.0 ph 9.08 ph 7.95 ph 6.82 ph 5.83 ph 4.5 ph 3.0 Ca/F=1 mixing=20 min [F - ] 0 =712 ppm volume (%) pt size (10-6 m) 4.6 不 ph 粒粒 (Ca/F=1) volume % ph 10 ph 9.15 ph 7.8 ph 6.83 ph 5.9 ph 4.85 ph 3.88 ph 2.89 Ca/F=2 mixing 20 min [F - ] 0 =712 ppm pt size (10-6 m) 4.7 不 ph 粒粒 (Ca/F=2) 38

48 流粒 4.8 粒粒粒流度粒流量粒沈留留不量粒粒 0.1~1 µm 4.8 流粒落 4.7 Ca/F=2 ph 6.8 粒 raw water analysis(1/26) pt vs ½ pt vs 流 X 8 volume % pt size (10-6 m) 4.8 理粒 39

49 4.2.3 粒量了粒粒粒更了更粒量粒 4.9 不 ph 不 ph 粒粒數量粒 3 nm~10 µm 零粒量不利沈降 40

50 35 30 Zeta Potential (mv) Ca/F=0.5 Ca/F=0.5 Ca/F=1.0 Ca/F=1.0 Ca/F=2.0 Ca/F=2.0 Ca/F=0.5,mean Ca/F=1.0,mean Ca/F=2.0,mean ph 4.9 不 ph 粒 41

51 P 4.3 度異離度異兩不 P 離度 (NIEA W413.52A) 離度流粒不離度量離離度 ( ) 離離 ph ph 5~9 行量流離流度離理說離離 LaFB3B CaP 參 Ag-AgCl 0.1mole/L NaCl 10P, 100KP 離 P -3 Pmole/L NaF PM 量參離 E = 數 RT /nf log[fp P] 4-1 離 mol/l. LaF 3 度, 10-7 mol/l 離離 OH - 離, OH - 離列 4-2 LaF 3 +3OH - La(OH) 3 +3F

52 HP HP P + P + P P 離, La(OH)B3B 若 ph, 離了 HF HFP HFB3PB 2- P 量 ph HAc-NaAc 來量離, 了離 AlP 3+ P FeP 3+ P 離度離度 NaCl 離 CB3BHB4B(OH)(COB2BNa)B3B ph 離度離離度 (Total ionic strength adjustment buffer, TISAB) 離離度 (1) ph 離 (HP - 離 (FP P) 行列 + P) F HF - 2F HFB2PB 4-3 P 4-4 離 (free Fluoride) 度降 (2) ph 離 (OHP P) 離列 - LaFB3B +3OHP - La(OH)B3B + 3FP - P 4-5 離來 FP - - P 離 (OHP P) 離 LaFB3B 離降數離流流度 43

53 度異利離流度離離 ph 5~9 95 年流 4.5 數 ( ) 數異不流離數不離流粒離離 ph IC ( 離 ) 量數不流離數不流量數離數 3.2 流若離 (OHP P) 離 LaFB3B 離降數異流量數數 3.34 mg/l 量 ( ) mg/l 離了度 IC( 離 ) 量數行更降行數離離理 ph 5.5 流離 - 44

54 4.5 流度流度 (mg/l) ( ) ( ) IC

55 4.4 ph 量量 ph 行理 ph 理 ph ph 6.5 ph 8 ph 利 ph 8 量若 ph ph ph 4.2 離度 57 mg/l 4.6 ph 5 離度 20 mg/l ph 6 離度 8.8 mg/l ph 7 離度 8 mg/l ph 6 離降 9 mg/l 量量度來說 ph 6 林隆 2003 論行 ph6 ph8 度 ph6 度 ph8 行 ph 不流若 ph ph 不不 ph 離 CaClB2B CaFB2B(S) CaFB2B (S) ph ph ph P 麟 ph ph P 46

56 FP FP FP FP P (mg/l) P (mg/l) P (mg/l) P (mg/l) P (mg/l) P (mg/l) P (mg/l) P (mg/l) ph 率 4.10 離降 96/4/16 行 4.11 沈離數離度降 4.6 CaP CaP - 1 ph 量 ph CaP CaP ph 5 量 ph ph 6 量 ph ph 7 量 ph

57 4.10 不 ph 離度 4.11 沈離度 48

58 論 5.1 論 1. 度不理流 2. 理理流離度量行粒 Ca/F=1 ph7~8 粒率 Ca/F 2 降粒率粒不量 3. 度異流離數不流量數度異流離 (OHP P) 離 LaFB3B 離降數異 - 4. 理 ph 8 ph 利 49

59 WVZ51 列硫量行量 WFT51 WHZ51 WID51 WRM51 WDS51 WRO51 WRP51 理量 WBT52 WED52 WKZ51 WKZ71 WMS71 WMT54 WDO51 WOT51 WWT54 流理 2. 流離度離度異數離離流離 3. 理 ph7~8 粒率利沈降行 ph 不 ph 理 50

60 參 (1980) 理立館行阮 (1989) 理 ( ) 阮 (1989) 理 29 念阮 (1996) 理理略 30 行 1995 (1998) 理立論李 (1999) 理 7 12 路理 (2000) 理 (2000) 理立論李蘭理立 (2001) 流理論劉 (2001) 離理論 - (2002) (2002) VLSI 立 51 理 (2002) 理立論林隆 (2003) 理 MF 濾率略立論林 2003 力林流理 2003 年論麟林劉 2003 降理例 2003 年論 2003 理降 SS 例

61 2003 年論 2005 力 37 李 2005 理例 2005 年論 (2006) 立論靖 2007 立論林 2007 流理益 2007 年論 Aldaco, R., Garea, A. and Irabien, A., Fluoride recovery in a fluidized bed: Crystallization of calcium fluoride on silica sand,indsustrial and Engineering Chemistry Research,45(2), (2006) Hichour, M., Persin, F., Molenat, J., Sandeaux, J. and Gavach, C., Fluoride removal from diluted solution by donnan dialysis with anion-exchange membranes, Desalination, 122(1),53-62(1999) Huang, C. J. and Liu, J. C., Precipitate flotation of fluoride-containing wastewater from a semiconductor manufacturer, Water Research,33(16), (1999) Kang, W. H., Kim, E. I. And Park, J. Y., Fluoride removal capacity of cement past Desalination,202(1-3),38-44(2007) Miki, N., Maeno, M., Fukudome, T. and Ohmi, T., Advanced fluorite regeneration technology to recover spent fluoride chemicals drained from semiconductor manufacturing process, IEICE Transactions on Electronics,E79-C(3), (1996) Yang, M., Zhang, Y., Shao, B., Qi, R. and Myga, H. Precipitative removal of fluorid from electronics wastewater, Journal of Environmental Engineering, 127(10), (2001) 52

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