A Solution for Microelectronics Manufacturing Wastewater Treatment Nabin Chowdhury 1, Denise Horner 1, Temple Ballard 2, Barbara Schilling 3 1 SUEZ/Degremont North American Research and Development Center; 2 SUEZ Treatment Solutions, Richmond, VA; 3 SUEZ treatment Solutions, Leonia, NJ. VWEA, Charlottesville, VA March 8, 2016
Outline Context Drivers Objectives Process Development Waste Characteristics Biodegradability Test Processes Selection Experimental Results Biodegradability Test Waste Stream #1 Waste Stream #2 Findings 2 I March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment
Context Microelectronics manufacturing is one of the fastest growing industries A typical semiconductor manufacturing facility consumes 6.7 MGD water Manufacturing process uses toxic and recalcitrant chemicals Industries are looking for water reuse technologies. (American Water Intelligence, 2012). 3 I March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment
Chemicals/Contaminants Parameter Concentration (mg/l) Tetra-methyl ammonium hydroxide (TMAH) 5,000-60,000 Di-methyl sulfoxide <2000 Glycerol 5,000-66,000 Pyrazole 50-2,000 N-methyl pyrrolidone (NMP) 0-23,000 Triethanolamine (TEA) 0-10,000 Ethylene glycol (EG) 0-10,000 Morpholinopropylamine 0-3,000 Formaldehyde 60-700 Acetone 100-200 Methanol 300-400 Methyl methacrylate 600-700 Calcium fluoride 700-800 Potassium hydroxide 50-1000 4 I March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment
Drivers Increased pollutants loading limits POTWs ability to treat industrial discharges Difficult to treat complex water matrix Corrosive, alkaline wastewater (ph ~12) Toxic and persistent organic compounds Inhibitory to biological processes (e.g. TMAH). Limited information on pilot/full scale demonstration of >95% TOC and TN removal from high strength microelectronics WW. 5 I March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment
Objectives Develop a sustainable solution for microelectronics WW treatment Investigate biodegradability of toxic substances (e.g. TMAH) Evaluate nitrification and denitrification options Achieve >98% TMAH degradation, >95% TOC and TN removal Develop design, operational and kinetic parameters. 6 I March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment
Waste Characteristics Waste stream #1: Organic rich combined waste Waste stream #2: Segregated waste (TMAH only) Parameter Waste Stream #1 Waste Stream #2 ph >12 >12 TMAH (mg/l) 49,762 23,000 TOC (mg/l) 79,528 17,561 TN (mg/l) 9,311 4,675 COD (mg/l) 174,024 n/a 7 I March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment
Analytical (mg/l) TMAH (mg/l) TOC, TKN Correlation with TMAH 600 500 400 300 R² = 0.990 R² = 0.999 Analytical correlations: TOC/TMAH = 0.527 TKN/TMAH = 0.154 200 100 0 TOC 300 TKN R² = 0.9992 250 0 50 100 150 200 250 200300 TKN, TOC (mg/l) 150 100 50 0 R² = 0.9903 0 50 100 150 200 250 300 Theoretical (mg/l) TOC TKN COD 8 I March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment
Concentration, mg/l Oxygen Uptake, mg TMAH Biodegradation 200 160 120 Oxygen Uptake Activated Sludge Acativated sludge TMAH 35 mg/l Respirometer testing: biodegradation of TMAH using AS and acclimated biomass OU for degradation of TOC/TMAH and formation of ammonia-nitrogen 80 Acclimated sludge 40 0 0 20 40 60 80 Time (hour) Acclimated sludge TMAH 35 mg/l 50 Acclimated sludge TMAH 70 mg/l 40 30 TOC Degradation Activated sludge TMAH 35 mg/l Acclimated sludge TMAH 35 mg/l Acclimated sludge TMAH 70 mg/l 20 10 0 0 20 40 60 80 Time (hour) 9 I March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment
Waste Stream #1 Pre-Anoxic + Aerobic + Clarifier + Aerobic + Clarifier or Pre-Anoxic + Aerobic + Clarifier + AOP + Post-Anoxic + Clarifier C source Q inf Pre Anoxic Aerobic Reactor Clarifier AOP Post Anoxic Clarifier Q eff 10 I March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment
Waste Stream #1: Lab-scale Test Data Influent Anoxic Aerobic AOP Post Anoxic Effluent Removal COD (mg/l) 2,600 925 85 <30 n/a n/a >98% TOC (mg/l) 1,350 450 60 <30 n/a n/a >98% NH 4 -N (mg/l) 14 56 106 <1.0 n/a 3 >98% NO 3 -N (mg/l) <0.4 <0.4 <0.4 97 <0.4 <0.4 n/a TKN (mg/l) 165 141 118 33 n/a 27 >80% 11 I March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment
Waste Stream #2 Aerobic + Clarifier + AOP + Post-Anoxic + Clarifier C source Q eff Q inf Aerobic Reactor Clarifier AOP Post Anoxic Clarifier 12 I March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment
TOC Concentration, mg/l TOC Removed, % West Stream #2: Bench-scale Test Results 4,000 100% 3,000 80% 2,000 1,000 Inf TOC Eff TOC % TOC Removal 60% 40% 20% 0 0 7 14 21 28 35 42 49 56 63 70 77 84 91 0% Days 13 I March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment
TKN, NH4-N Concentration, mg/l TMAH Conversion, % West Stream #2: Bench-scale Test Results Influent TN 750 mg/l Aerobic effluent NH 4 -N 670 mg/l Effluent TN <30 mg/l 1000 900 800 700 600 500 400 300 200 100 0 Sample Influent Effluent % TMAH TMAH Removal (mg/l) (mg/l) 1 4,000 39 99% 2 4,100 <0.5 99% TMAH Biodegradation 3 3,700 <0.5 99% 0 7 14 21 28 35 42 49 56 63 70 77 84 91 Days Inf TKN Aero Eff TKN Aero Eff NH4-N % TMAH Conversion Inf NH4-N 100 90 80 70 60 50 40 30 20 10 0 14 I March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment
West Stream #2: Bench-scale Test Results AOP: Ozonation NH 4 -N NO 3 -N 15 I March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment
TN, NH4-N Concentration, mg/l TN Removed, % West Stream #2: Bench-scale Test Results Aerobic degradation AOP (nitrification) Anoxic (biological de-nitrification) 1000 TN Performance 100 800 80 600 60 400 200 Inf TN NH4-N in Bio-Effluent % TN Removal Final Eff TN Bio Eff TKNs 40 20 0 0 7 14 21 28 35 42 Days 0 16 I March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment
West Stream #2: Bench-scale Test Results Aerobic-AOP-Anoxic for TMAH treatment Influent Aerobic AOP Anoxic Effluent Removal COD (mg/l) <30 201 67 n/a n/a n/a TOC (mg/l) 2,800 80 n/a n/a n/a >98% NH 4 -N (mg/l) 7 690 8 n/a 6.4 n/a NO 3 -N (mg/l) <0.4 <0.4 610 <0.4 <0.4 n/a NO 2 -N (mg/l) <0.5 <0.5 <0.5 <0.5 <0.5 n/a TKN (mg/l) 750 715 30 n/a 26 >95% TMAH (mg/l) 4,000 n/a n/a n/a BDL >99% 17 I March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment
Findings Combination of AOP and Biological treatment provides a complete treatment solution for microelectronics wastewater Aerobic biodegradation of TMAH generated ammonia-nitrogen even at TMAH of 4000 mg/l. Biological nitrification was not observed throughout the study Ozonation (AOP) completely nitrify ammonia-nitrogen generated from the aerobic biodegradation of TMAH >98% TMAH degradation, and >95% TOC and TN were achieved. 18 I March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment
Acknowledgement SUEZ / Degremont North American Research and Development Center (DENARD), Ashland, VA John Williamson Keith Newton SUEZ Treatment Solutions, Richmond, VA Temple Ballard Rich Ubaldi Amit Kaldate SUEZ Treatment Solutions, Leonia, NJ Bruno Heiniger 19 I March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment
Thank You! Questions & Answers Nabin Chowdhury, PhD Sr. R&D Engineer SUEZ / Degremont North American Research & Development Center nabin.chowdhury@suez-na.com 804-521-7478 20 I March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment