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© 2014 Evoqua Water Technologies LLC
AN ADVANCED OXIDATION PROCESS UPDATE
FOR REMOVAL OF LOW ORGANIC LEVELS
Ultrapure Water Micro – Phoenix, AZ
By Bruce Coulter, Glen Sundstrom, Chris Hall, Sevang Doung
Evoqua Water TechnologiesDecember 2-3, 2014
Page 2
EVOQUA?
Previously Siemens , Veolia, USFilter
Key Market Focus
• Municipal
• Food and Beverage
• Pharmaceutical
• Health Care and Education
• Light Industry
• Power
•Microelectronics (Semiconductor, Support Companies, Labs,
Universities, Solar)
Key Offerings
• Capital Equipment (Pure Water & Waste Water)
• After Market
• Service
• Mobile assets
e – vo - kwa
Page 3
PURPOSE OF PRESENTATION
• Provide an update of Vanox™ AOP from the perspective of reduction of a wider range of TOC species other than just urea and IPA.
• Background behind this work
• The organics selected and why
– Understanding the removal effectiveness of Vanox™ AOP allows for:
» Greater confidence in overall TOC reduction from a customer perspective
» Allows for optimization (ie if an easier organic, can reduce capital & COO)
• The test apparatus used
• Results
• Provide list of future and ongoing developments
Page 4
WHAT IS VANOX™ AOP?
TOC
Oxidant
Feed
AOPR
Residual
Oxidant
TOC/Oxidant
Control
AOPR – Advanced Oxidation Process Reactor
TOC
Instruments
Process flow
Control logic path
PROCESS OVER VIEW
FIT
• Oxidant used
• UV Lamp wavelength
• AOPR Design
• Controls / Instruments
Page 5
POU System initially supplied to address several critical parameters (TOC, Particles, Temperature, Oxygen) of which a primary requirement was to reduce urea from 15 ppb as C to < 1 ppb as C
BACKGROUND – POU INSTALLATIONS STARTING 2006
AOP part of the
POU system
Page 6
AOP INITIALLY APPLIED TO POU APPLICATIONS FOR DIFFICULT TO REMOVE TOC’S – ACTUAL SITE OPERATING DATA
This illustrates Urea removal from the bulk UPW Loop Supply (Red)
prior to feeding to the Critical Tools from the POU Equipment Supply (Green)
Preference for more
stable levels to the Tools
vs just meeting spec
0
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4/19/2007 0:00 4/23/2007 0:00 4/27/2007 0:00 5/1/2007 0:00
TO
C (
pp
b a
s C
)
POU Feed (UPW Loop)
POU Effluent
Page 7
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
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4/19/2007 0:00 4/23/2007 0:00 4/27/2007 0:00 5/1/2007 0:00
Pe
rce
nt
TOC
Re
du
ctio
n
TOC
(p
pb
as
C)
POU Feed (UPW Loop)
POU Effluent
Percent TOC Reduction
AOP INITIALLY APPLIED TO POU APPLICATIONS FOR DIFFICULT TO REMOVE TOC’S – ACTUAL SITE OPERATING DATA
This illustrates Urea removal from the bulk UPW Loop Supply (Red)
prior to feeding to the Critical Tools from the POU Equipment Supply (Green)
along with illustrating the AOP process automatically maintaining near flat line
effluent to TOC below 1 ppb by adjusting % TOC Reduction (Blue)
Page 8
ACTUAL RESPONSE IN 2008 OF AOP IN POU SYSTEM DURING AN IPA EVENT
0
5
10
15
20
25
30
35
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Days Running
TO
C (
pp
b a
s C
)
34.43 ppb
3.06 ppb1 ppb spec.
9 hour “event”
AOP Inlet
AOP Effluent
Legend:
This system was designed
for a maximum of 18 ppb
Preference for more stable
levels to the Tools vs just
meeting spec
Because of effectiveness
of IPA reduction, AOP can
be effectively used as a
Reclaim TOC polishing
unit operation & in a
Makeup position, can
serve as additional
protection from a Reclaim
excursion
This illustrates IPA removal from the bulk UPW Loop Supply (Red)
prior to feeding to the Critical Tools from POU Supply (Green)
Page 9
WHERE AOP IS USED IN A UPW SYSTEM
Pretreatment/Makeup
(Filters, RO)
Primary System(UV, Degas, MB, CF)
Polishing Equipment
(UV, MB, Degas, CF, UF)
POU
UPW POU(critical tools)
POU
UPW AOP
Reclaim AOP
Page 10
This lead to the supply of a full size AOP for treating all of UPW water just downstream of the Makeup RO’s to consistently reduce TOC to less than 1 ppb as C at this location in the UPW System.
BACKGROUND –FULL SIZE AOP STARTING 2010
This far upstream lead to certain technical challenges• Stable/accurate analytical readings of TOC for control
• Unknown TOC’s that could exist in the background TOC readings that
AOP may or may not be removing and/or the TOC analyzer may or may
not be detecting
• Huber analysis to speciate / categorize the TOC’s present
TOC
Oxidant
Feed
Residual
Oxidant
TOC/Oxidant Control
TOCFIT
2 Pass RO
Effluent
AOPR
UPW
Primary System
Page 11
AOP SYSTEM PERFORMANCE VIA “HUBER ANALYSIS“
Organic ClassIn
ppt (C)
Out
ppt (C)% Red
DOC 2,581 1,296 49.8
HOC 595 420 29.4
CDOC 1,986 876 55.9
Urea (LMW Neutral) 483 143 70.4
LMW Neutrals 245 79 67.8
Bio-polymers 281 126 55.2
X1 (SOM) 575 285 50.4
HS+ Building Blocks 153 79 48.4
X3 (SOM) 68 37 45.6
X2 (SOM) 63 40 36.5
LMW Acids 118 87 26.3
• At a single point in time,
the AOP system removed
these organic species.
• With a higher TOC load,
the removal will be greater
to achieve the same
effluent quality.
On-line TOC 900 1,752 675 61.5%
2 Pass Reverse
Osmosis
AOP
Reactor
Oxidant injection
Sample
Point 1
Sample
Point 2
Page 12
TARGETED ORGANIC SPECIES
Organic Uses
Atrazine Herbicide
Carbaryl Insecticide
Chloroform Chlorine disinfection byproduct from contact with NOM
Formic AcidNaturally occurring due to forest emissions, used in the food
chain as a preservative, dye industry, cleaning products, etc.
Humic Acid NOM (decaying plant debris)
IPACommon organic used in Semiconductor fabs that periodically
and accidentally gets introduced into the UPW Supply, Reclaim
Starch Bacterial byproduct found in feed water
Tryptophan Amino acid, food supplement
UreaFound in most surface waters to varying degrees depending on
geographical locations and agricultural activity
Being a member of ITRS, an informal ITRS TOC survey was performed with a
few select members
Page 13
UREA – CH4N2O
DIFFICULT TO REMOVE TOC COMMONLY FOUND IN SURFACE WATER SUPPLIES TO VARYING LEVELS
• Properties
•60.06 g/mol
•Melting point 132-135 ºC
•Boiling point: Decomposes before boiling
• Uses
•Nitrogen fertilizer and feed supplement
• Reasons for interest
•Common existing UPW unit operations do not effectively remove this TOC specie and therefore locations with urea present in the feed water will have urea in the UPW water. Since urea is not effectively removed with conventional UPW equipment, the TOC fluctuation in the feed water will pass into the UPW Supply to a high degree.
Page 14
CHLOROFORM – CHCl3
MOST COMMONLY SEEN IN UPW LOOP SUPPLY WATERS
• Properties
•119.38 g/mol
•Melting point -63ºC
•Boiling point 60.5-61.5ºC
• Uses
•Used as a solvent for fats, oils, rubber, resin and adhesives
•Also used in building, paper and board industries and pesticide production
• Reasons for interest
•Most commonly seen residual organic found in UPW waters.
•Primary source of chloroform is its creation as a disinfection byproduct when chlorine is used.
•Can fluctuate noticeably depending on treatment of the raw water supply.
Page 15
ATRAZINE - C8H14Cl N5
EXAMPLE OF ANOTHER TOC SPECIE INVESTIGATED
• Properties
•215.68 g/mol
•Melting point 175ºC
•Boiling point 200ºC
• Uses
•Herbicide (weed killer)
• Reasons for interest
•Most commonly detected pesticide contaminating US drinking water and therefore suspected as a background organic not normally tracked in UPW applications
•Nitrogen bonds leads to interest in effectiveness of AOP to reduce it although it should be readily rejected by a healthy RO unit due to MW.
Page 16
PROPERTIES OF TESTED ORGANIC COMPOUNDS
Organic MW, g/mol BP, °C Formula H V P
Atrazine 215.68 200 C8H14Cl N5 – – +
Carbaryl 201.22 315 C12H11NO2 – – +
Chloroform 119.38 61 CHCl3 – + –
Formic Acid 46.03 101 CH2O2 + – +
Humic Acid 4,000* -- C187H186O89N9S1 + – –
IPA 60.1 83 C3H8O + + +
Potato Starch 162.07 -- (C6H10O5)N + – –
Tryptophan 204.23 -- C11H12N2O2 + – +
Urea 60.06 -- CH4N2O + – +
* AverageH = Hydrophilic V = Volatile P = Polar
Page 17
AOP SYSTEM PERFORMANCE VIA “HUBER ANALYSIS“
Organic ClassIn
ppt (C)
Out
ppt (C)% Red
Organics Investigated(italics – example but not tested)
DOC 2,581 1,296 49.8
HOC 595 420 29.4 Carbaryl(?)
CDOC 1,986 876 55.9
Urea (LMW Neutral) 483 143 70.4 Urea
LMW Neutrals 245 79 67.8Atrazine, Carbaryl(?), IPA,
Urea (not in total)
Bio-polymers 281 126 55.2 Polysaccharides
X1 (SOM) 575 285 50.4 Ethanol
HS+ Building Blocks 153 79 48.4 Humic acid, Starch
X3 (SOM) 68 37 45.6 TMA
X2 (SOM) 63 40 36.5
LMW Acids 118 87 26.3 Formic acid, Tryptophan
On-line TOC 900 1,752 675 61.5%
Chloroform is volatile and not detected with the Huber analysis
Page 18
TEST APPARATUS – PROCESS FLOW DIAGRAM
Callout text goes here
Sievers 900
Page 19
TEST APPARATUS
1. Calibrate/validate TOC analyzer
for urea measurement
2. Establish baseline TOC via
recirculation through UV
3. Add specific organic while
recirculating with UV off to
establish baseline with target
TOC at a target level
4. Establish /maintain target flow
5. Turn on UV only for impact
6. Dose (increase as necessary) to
determine % TOC reduction until
99-100% TOC reduction
obtained.
Page 20
0
5
10
15
20
25
30
9:36 AM 3:36 PM 9:36 PM 3:36 AM 9:36 AM 3:36 PM 9:36 PM
TO
C (
pp
b)
Time
20 ppb Urea
DIW Baseline
2.1 ppb TOC
With Urea
23.3 ppb TOC
UV on, to drain
UV only
21.5 ppb TOC
UV + persulfate
1.4 ppb TOC
1 ppb
Urea added as C
= 23.3 - 2.1 = 21.2 ppb
Urea reduction by UV alone
= (23.3 - 21.5)/21.2 = 8.5%
Urea reduction by UV + persulfate
= (23.3 - 1.4)/21.2 = 103.3%
Page 21
0
5
10
15
20
25
30
35
12:00 AM 12:57 AM 1:55 AM 2:52 AM 3:50 AM 4:48 AM 5:45 AM
TO
C (
pp
b)
Time
30 ppb Chloroform
DIW Baseline
2.8 ppb TOC
With Chloroform
31.4 ppb TOC
UV only
3.6 ppb TOC
UV+ persulfate
1.6 ppb TOC
Chloroform added as C
= 31.4 - 2.8 = 28.6 ppb
Chloroform reduction by UV alone
= (31.4 - 3.6)/28.6 = 97.2%
Chloroform reduction by UV persulfate
= (31.4 - 1.6)/28.6 = 104.2%
UV on
to drain
1ppb
Page 22
0
5
10
15
20
25
30
35
40
45
9:36 AM 2:24 PM 7:12 PM 12:00 AM 4:48 AM 9:36 AM 2:24 PM
TO
C (
pp
b)
Time
25 ppb Atrazine
DIW Baseline
2.30 ppb TOC
With Atrazine
27.2 ppb TOC
UV only
9.76 ppb TOC
UV + persulfate
2.6 ppb TOC
Atrazine added as C= 27.2 - 2.30 = 24.9 ppb
Atrazine reduction by UV alone= (27.2 - 9.76)/24.9= 70%
Atrazine reduction by UV + persulfate= (27.2 - 2.6)/24.9= 98.8%
UV on
to drain
1 ppb
Page 23
SUMMARY OF AOP EFFECTIVENESS FOR DIFFERENT TRACE ORGANIC COMPOUNDS
% TOC Destruction
Organic Feed ppbVanox™ UV
only
Vanox™ UV +
Persulfate
Atrazine 25 70 99
Carbaryl 29 95 100
Chloroform 29 97 100
Formic Acid 30 100 --
Humic Acid 33 90 99
IPA 30 77 100
Starch 33 94 100
Tryptophan 29 94 100
Urea 21 9 100
Page 24
TOC DESTRUCTION OF IPA AT TYPICAL RECLAIMWATER CONCENTRATIONS
% TOC Destruction
ppb IPA as C Vanox™ UV onlyVanox™ UV +
Persulfate
100 84.4 101.6
250 60.9 100.9
500 33.6 100.3
1000 15.1 100.3
Page 25
DEVELOPMENTS WITH EVOQUA’S INVESTMENTS-AOP DEMO, POU DEMO, TECHNOLOGY SUITE
Technology Suite-Rockford - 2014• Installation complete Dec 2014
• Commissioning POU Demo Jan-Feb 2015
• Objectives starting March 2015
Vanox™ POU Demo - 2013Vanox™ AOP Demo - 2009
Tech Suite Areas
• POU Demo
• Instrument calibration/ validation
• Resin development/validation
• Developmental
Page 26
AOP TECHNOLOGY SUITE OBJECTIVES
TOC’s consistently below 0.5 ppb as C
• Analytical issues (collaboration)
– Reliability and repeatability at sub 0.5 ppb levels
• Determine how low the TOC level can be driven
• Investigate other TOC’s (collaboration)
– UPW degradation products such as TMA from IX resins
– TOC’s in Reclaim sources
– Other organics of interest
Reduce / eliminate oxidant dosing
• Organic dependent (collaboration)
Reduce capital cost and COO
• CFD modeling / validations
• Component selection / validations
• Reduced footprint
Page 27
TECHNOLOGY SUITE OTHER OBJECTIVES
Particles to support sub 10 nm geometries
• Filtration (collaboration)
• Component selection (collaboration)
• Analyzer validation / correlation (collaboration)
Resin improvements
• Particles, Metals, TOC, Stability, Rinse up (collaboration)
Training
Technology Demonstration & Validation
EDI enhancements
for microelectronics applications
LiquiTrak®
Scanning TPC 100010 nm particle counter
PVDF IX Columns
VNX-EX EDI Module
Page 28
SUMMARY
• Of all organics tested to date, urea remains the most difficult to remove TOC.
• The Huber Analysis consistently indicates higher TOC’s than what on-line analyzers show which is an ongoing point of discussion. Vanox ™ shows reduction of organics in the various Huber categories.
• Continuing alliance with ITRS for organics of interest to provide a process solution.
• Continued work needs to be done on TOC metrology to support the lower TOC levels now consistently obtainable.
• The above developments requires continued collaboration.
Page 29
CONTACTS
Bruce L. Coulter
Technical Director - Semiconductor
Rockford, IL
+1 815.921.8270
Sevang Doung
Lab Technician – R&D
Lowell, MA
+1 978.614.7469
Christopher Hall
Product Manager – Vanox™
Colorado Springs, CO
+1 719.550.2202
Glen Sundstrom
Process Engineer – Ultrapure Water
Rockford, IL
+1 815.921.8282
