A Solution for Microelectronics Manufacturing Wastewater Treatment
Nabin Chowdhury1, Denise Horner1, Temple Ballard2, Barbara
Schilling3
1 SUEZ/Degremont North American Research and Development Center;2SUEZ Treatment Solutions, Richmond, VA;
3SUEZ treatment Solutions, Leonia, NJ.
VWEA, Charlottesville, VA – March 8, 2016
2 I
Outline
Context
Drivers
Objectives
Process Development
Waste Characteristics
Biodegradability Test
Processes Selection
Experimental Results
Biodegradability Test
Waste Stream #1
Waste Stream #2
Findings
March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment
March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment3 I
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).
March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment4 I
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
March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment5 I
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
Limited information on pilot/full scale demonstration of >95% TOC and
TN removal from high strength microelectronics WW.
(e.g. TMAH).
March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment6 I
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.
March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment7 I
Waste Characteristics
Waste stream #1: Organic rich combined waste
Waste stream #2: Segregated waste (TMAH only)
ParameterWaste 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
March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment8 I
TOC, TKN Correlation with TMAH
R² = 0.999R² = 0.990
0
100
200
300
400
500
600
0 50 100 150 200 250 300
TMA
H (m
g/L)
TKN, TOC (mg/L)
TOC
TKN R² = 0.9992
R² = 0.9903
0
50
100
150
200
250
300
0 50 100 150 200 250 300
Ana
lyti
cal (
mg/
L)
Theoretical (mg/L)
TOC TKN COD
Analytical correlations:
TOC/TMAH = 0.527
TKN/TMAH = 0.154
March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment9 I
TMAH Biodegradation
0
40
80
120
160
200
0 20 40 60 80
Ox
yg
en
Up
tak
e,
mg
Time (hour)
Oxygen Uptake
Activated Sludge
Acativated sludgeTMAH 35 mg/L
Acclimated sludge
Acclimated sludgeTMAH 35 mg/L
Acclimated sludgeTMAH 70 mg/L
Respirometer testing: biodegradation of
TMAH using AS and acclimated biomass
OU for degradation of TOC/TMAH and
formation of ammonia-nitrogen
0
10
20
30
40
50
0 20 40 60 80
Con
cen
trat
ion,
mg/
L
Time (hour)
TOC Degradation
Activated sludge TMAH 35 mg/L
Acclimated sludge TMAH 35 mg/L
Acclimated sludge TMAH 70 mg/L
March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment10 I
Waste Stream #1
Pre-Anoxic + Aerobic + Clarifier + Aerobic + Clarifier
or
Pre-Anoxic + Aerobic + Clarifier + AOP + Post-Anoxic + Clarifier
Qinf
Aerobic
Reactor
Pre
AnoxicClarifier
QeffClarifierPost
Anoxic
AOP
C source
March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment11 I
Waste Stream #1: Lab-scale Test Data
Influent Anoxic Aerobic AOPPost
AnoxicEffluent 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%
NH4-N (mg/L) 14 56 106 <1.0 n/a 3 >98%
NO3-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%
March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment12 I
Waste Stream #2
Aerobic + Clarifier + AOP + Post-Anoxic + Clarifier
Qeff
Aerobic ReactorClarifier Clarifier
Post
Anoxic
AOP
C source
Qinf
March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment13 I
West Stream #2: Bench-scale Test Results
0%
20%
40%
60%
80%
100%
0
1,000
2,000
3,000
4,000
0 7 14 21 28 35 42 49 56 63 70 77 84 91
Inf TOC
Eff TOC
% TOC Removal
TOC
Co
nce
ntr
atio
n, m
g/L
TOC
Re
mo
ved
,%
Days
March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment14 I
West Stream #2: Bench-scale Test Results
Influent TN 750 mg/L
Aerobic effluent NH4-N 670 mg/L
Effluent TN <30 mg/L
0
10
20
30
40
50
60
70
80
90
100
0
100
200
300
400
500
600
700
800
900
1000
0 7 14 21 28 35 42 49 56 63 70 77 84 91
Inf TKN
Aero Eff TKN
Aero Eff NH4-N
% TMAH Conversion
Inf NH4-N
TKN
, NH
4-N
Con
cent
rati
on, m
g/L
TMA
H C
onve
rsio
n,%
TMAH Biodegradation
Days
SampleInfluent TMAH (mg/L)
Effluent TMAH (mg/L)
% Removal
1 4,000 39 ≥99%
2 4,100 <0.5 ≥99%
3 3,700 <0.5 ≥99%
March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment15 I
West Stream #2: Bench-scale Test Results
AOP: Ozonation
NH4-N NO3-N
March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment16 I
West Stream #2: Bench-scale Test Results
Aerobic degradation – AOP (nitrification) – Anoxic (biological de-nitrification)
0
20
40
60
80
100
0
200
400
600
800
1000
0 7 14 21 28 35 42
Inf TN Final Eff TN
NH4-N in Bio-Effluent Bio Eff TKNs
% TN Removal
TN, N
H4-
N C
once
ntra
tion
, mg/
L
TN R
emov
ed,%
TN Performance
Days
March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment17 I
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%
NH4-N (mg/L) 7 690 8 n/a 6.4 n/a
NO3-N (mg/L) <0.4 <0.4 610 <0.4 <0.4 n/a
NO2-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%
March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment18 I
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.
March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment19 I
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
March 8, 2016; A solution for Microelctronics Manufacturing WW Treatment20 I
Thank You!
Questions & Answers
Nabin Chowdhury, PhD
Sr. R&D Engineer
SUEZ / Degremont North American Research & Development Center
804-521-7478
