combined ion exchange for removal of dissolved … · · 2017-01-13combined ion exchange for...
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Combined Ion Exchange for Removal of Dissolved
Organic Carbon and Hardness Treavor Boyer
30 August 2016
EPA's Small Drinking Water Systems Webinar Series
Removal of Multiple Contaminants: Biological Treatment and Ion Exchange
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AcknowledgementsSmall, Safe, Sustainable (S3) Public Water
Systems through Innovative Ion Exchange
(R835334)
EPA Center: Water Innovation Network
for Sustainable Small Systems (WINSSS)
(R835602)
R835334
Many great students – Jennifer Apell, Katie Indarawis, Sarah
Comstock, Gabe Maul, Jerrine Foster, Yue Hu, Alysse Ness
Dr. Qiong (Jane) Zhang
Cedar Key Water
& Sewer District
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Challenges faced by small water systems
Oxenford & Barrett, 2016. Understanding Small Water System
Violations and Deficiencies. Journal AWWA, 108(3), 31–37.
• Management and operations
• Source water
• Security
• Pumps
• Compliance
• Data verification
• Treatment
• Finished water storage
• Distribution
• Financial
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Challenges faced by small water systems
Fe
oxidationDOC
removal
Hardness
removal
Turbidity
removal
Disinfection
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Challenges faced by small water systems
Fe
oxidationDOC
removal
Hardness
removal
Turbidity
removal
Disinfection
Fe
oxidationDOC
removal
Hardness
removal
Turbidity
removal
Disinfection
Combined ion exchange (CIX)
&
×
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Ion exchange
Microscale
+
++
+
Cl–
Cl–
Cl–+
Cl–
Cl–
X–
X–
X–
X–
Anion
exchange
resin
Contaminant ion
Mobile
counterion
Macroscale
Contaminant
Contaminant-free
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Regeneration
+
++
+
Cl–
Cl–
Cl–
+
Cl–
Cl–
X–
X–
X–
X–
NaCl
NaCl +
contaminants
X–
Na+
Na+
Na+
Na+
Na+
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Combined ion exchange (CIX)
+
++
+
Cl–
Cl–
Cl–+
Cl–
Cl–
X–
X–
X–
X–
––––
Na+
Na+
Na+
Na+
Y+ Y+
Y+
Y+
Y+
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CIX: DOC and hardness removal
+
++
+
Cl–
Cl–
Cl–+
Cl–
Cl–
DOC–
DOC–
DOC–
DOC–
–––
–
Na+
Na+
Na+
Na+
Ca2+ Ca2+
Ca2+
Ca2+
Ca2+
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CIX & multi-contaminant removal
+
++
+
Cl–
Cl–
Cl–+
Cl–
Cl–
X–
X–
X–
X–
––––
Na+
Na+
Na+
Na+
Y+ Y+
Y+
Y+
Y+
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Ion exchange reactors
• Fixed bed reactor
• Completely mixed reactor with resin recycle
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• Apell, J.N., Boyer, T.H., 2009. Simultaneous removal of dissolved organic
matter and hardness by combined ion exchange. AWWA Water Quality
Technology Conference and Exposition Seattle, Washington, 15–18
November 2009, 8 p.
• Apell, J.N., Boyer, T.H., 2010. Combined ion exchange treatment for
removal of dissolved organic matter and hardness. Water Research 44,
2419–2430.
Proof of concept
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• Groundwater from Cedar Key
• DOC: 5.6 mg/L
• Hardness: 275 mg/L as CaCO3
• Anion exchange resin: 2 mL/L MIEX-Cl
• Cation exchange resin: 16 mL/L MIEX-Na
• Single-loading jar tests
• Simultaneous: MIEX-Cl + MIEX-Na
• Sequence 1: MIEX-Cl → MIEX-Na
• Sequence 2: MIEX-Na → MIEX-Cl
• NaCl regeneration
Proof of concept
Experimental design
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• 70% DOC removal and 55% hardness removal
Apell & Boyer, 2010. Water Res.
Proof of concept
MIEX-Na MIEX-Cl MIEX-Cl + MIEX-Na0
10
20
30
40
50
60
70
80
90
100
Ion exchange treatment
Re
mo
va
l (%
)
Hardness
DOC
UV254
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Apell & Boyer, 2010. Water Res.
Proof of concept
Parameter MIEX-Cl + MIEX-Na Finished drinking
watera
pH 7.7 8.1
DOC (mg C/L) 1.7 1.1
Hardness (mg/L as
CaCO3)
112 173
Chloride (mg/L) 49 60
Sulfate (mg/L) 3.1 1.1
a Cedar Key Water & Sewer District; August 2009.
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• Decrease in hardness removal and increase in DOC removal after 3
regeneration cycles
• Simultaneous and sequential ion exchange showed similar
removals after 3 regeneration cycles
Apell & Boyer, 2010. Water Res.
Proof of concept
fresh resin regen. 1x regen. 2x regen. 3x0
10
20
30
40
50
60
70
80
90
100
Test conditions
DO
C r
em
ov
al (%
)
MIEX-Cl + MIEX-Na
MIEX-Cl MIEX-Na
MIEX-Na MIEX-Cl
fresh resin regen. 1x regen. 2x regen. 3x0
10
20
30
40
50
60
70
80
90
100
Test conditions
Ha
rdn
es
s r
em
ov
al (%
)
MIEX-Cl + MIEX-Na
MIEX-Cl MIEX-Na
MIEX-Na MIEX-Cl
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• MIEX-Cl and MIEX-Na can be used in a single completely
mixed vessel to simultaneously remove DOC and hardness
• MIEX-DOC and MIEX-Ca can be effectively regenerated
using NaCl in a single completely mixed vessel
• Simultaneous and sequential ion exchange showed
approximately equal removal after three regeneration cycles
• NaCl regeneration solution prepared using tap water (i.e.,
containing hardness and alkalinity) provided the same
regeneration efficiency as NaCl regeneration solution prepared
using hardness-free, deionized water
Proof of concept
Conclusions
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• MIEX-Na removed DOC in addition to hardness. This
was unexpected because DOC is negatively charged.
• Combined ion exchange is expected to be an effective
pretreatment to reduce membrane fouling, i.e.,
decrease organic fouling by DOC and inorganic
scaling by calcium minerals
Proof of concept
Observations
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• Indarawis, K.A., Boyer, T.H., 2012. Alkaline earth metal cation exchange: Effect of
mobile counterion and dissolved organic matter. Environmental Science & Technology
46, 4591–4598.
• Indarawis, K.A., Boyer, T.H., 2013. Superposition of anion and cation exchange for
removal of natural water ions. Separation and Purification Technology, 118, 112–119.
• Indarawis, K.A., Boyer, T.H., 2014. Evaluation of ion exchange pretreatment options
to decrease fouling of a reverse osmosis membrane. Desalination and Water
Treatment, 52(25–27), 4603–4611.
Focus on cation exchange
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• Synthetic water to mimic Cedar Key groundwater
• Suwannee River NOM (~5 mg/L DOC)
• Hardness as Ca2+, Mg2+, and Ca2+/Mg2+ (~250
mg/L as CaCO3)
• Cation exchange resin
• 16 mL/L MIEX-Na
• 3.1 mL/L Purolite C106-Na
• Resin-Na, -Ca, -Mg, -Sr, and -Ba
• Batch equilibrium experiments
Focus on cation exchange
Experimental design
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• DOC removal by magnetic cation exchange resin
• No DOC removal by non-magnetic cation exchange resin
Indarawis & Boyer, 2012. Environ. Sci. Technol.
Focus on cation exchange
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
MIEX-Na MIEX-Ca MIEX-Mg MIEX-Sr MIEX-Ba
DO
C, C
/Co
Ca Hardness
Ca/Mg Hardness
Mg Hardness
No Hardness
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
DO
C,
C/C
o
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Combined ion exchange, revisited
• Combined ion exchange is additive
Indarawis & Boyer, 2013. Separation and Purification Technology
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• DOC removal was approximately 20% for MIEX-Na
resin with no hardness cations in solution
• DOC removal by MIEX resin increased when the
presaturant ion was a divalent metal cation or divalent
metal cation was present in solution or both
• There was no measureable DOC removal by the non-
magnetic cation exchange resin for all conditions of
presaturant ion and metal cations in solution, with the
exception of barium as the presaturant ion
• Combined ion exchange is additive
Focus on cation exchange
Conclusions
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• Comstock, S.E.H., Boyer, T.H., 2014. Combined magnetic ion exchange
and cation exchange for removal of DOC and hardness. Chemical
Engineering Journal, 241, 366–375.
Combined ion exchange (CIX)
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• Cedar Key, Yankeetown, Palm Springs groundwater
• DOC: 3–10 mg/L
• Hardness: 300–440 mg/L as CaCO3
• Anion exchange resin: MIEX-Cl
• Cation exchange resin: Amberlite 200C-Na
• Multiple-loading jar tests
• Bed volumes (BVs)
• 1000 BVs MIEX-Cl
• 250 BVs A200C-Na
• NaCl regeneration (2%, 20%)
Experimental design
CIX treatment of groundwater
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Comstock & Boyer, 2014. Chem. Eng. J.
CIX treatment of groundwater
• 67–85% DOC removal, 1000 BV anion exchange (composite)
• ~50% hardness removal, 250 BV cation exchange (composite)
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• NF concentrate from 2 membrane plants in FL
• DOC: 33, 56 mg/L
• Hardness: 960, 1000 mg/L as CaCO3
• Sulfate: 830, 71 mg/L
• Anion exchange resin: MIEX-Cl
• Cation exchange resin: Amberlite 200C-Na
• Multiple-loading jar tests
• 200 BVs MIEX-Cl
• 83 BVs A200C-Na
• NaCl regeneration (30%)
Experimental design
CIX treatment of NF concentrate
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• 70–80% DOC removal, 50% sulfate removal, 90% hardness
removal
Comstock & Boyer, 2014. Chem. Eng. J.
CIX treatment of NF concentrate
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• CIX produced similar water composition as NF feed water
Comstock & Boyer, 2014. Chem. Eng. J.
Primary NF – CIX – Secondary NF
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• CIX treatment of groundwater achieved >70% DOC
removal (MIEX-Cl resin) and >50% hardness
removal (A200C-Na resin) in composite samples
corresponding to 1000 BVs of anion exchange and
250 BVs of cation exchange depending on 2% or 20%
NaCl regeneration solution
• CIX removed DOC, sulfate, and hardness from NF
concentrate to produce treated concentrate with
similar characteristics as NF feed water
Conclusions
CIX
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Combined ion exchange (CIX) pilot plant
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• Cedar Key
• DOC: ~5 mg/L
• Hardness: ~300 mg/L as CaCO3
• Anion exchange resin (AER): A-72 Thermax
• Cation exchange resin (CER): T-42 Thermax
• Pilot plant operation
• Down flow columns
• Resin ratio: 4 L AER-to-4 L CER
• 0.5 gpm
• Regeneration: NaCl vs KCl regeneration (12% m/v)
Experimental design
CIX pilot plant
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• Regeneration operation, e.g., precipitation
• Effectiveness of NaCl vs. KCl regeneration; disposal
• Lead–lag column operation
• Completely mixed CIX
• NaCl vs. NaHCO3 regeneration (anion exchange only)
• Process modeling (w/ USF, WINSSS)
• Life cycle assessment (w/ USF, WINSSS)
• Decision support tool (w/ USF, WINSSS)
CIX pilot plant, ongoing work
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• Regeneration operation, e.g., precipitation
• Effectiveness of NaCl vs. KCl regeneration; disposal
• Lead–lag column operation
• Completely mixed CIX
• NaCl vs. NaHCO3 regeneration (anion exchange only)
• Process modeling (w/ USF, WINSSS)
• Life cycle assessment (w/ USF, WINSSS)
• Decision support tool (w/ USF, WINSSS)
CIX pilot plant, ongoing work
Mining ProcessingCIX
regeneration
CIX treatment
Disposal
Freshwater
Soil
Wastewater
Multi-contaminants Safe drinking water
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Treavor Boyer
Arizona State University
Thank you
• Hu, Y., Foster, J., Boyer, T.H., 2016. Selectivity of bicarbonate-form anion
exchange for drinking water contaminants: Influence of resin properties.
Separation and Purification Technology, 163, 128–139.
• Boyer, T.H., 2015. Removal of dissolved organic matter by magnetic ion
exchange resin. Current Pollution Reports, 1(3), 142–154.
• Zhang, J., Amini, A., O'Neal, J.A., Boyer, T.H., Zhang, Q., 2015. Development
and validation of a novel modeling framework integrating ion exchange and
resin regeneration for water treatment. Water Research, 84, 255–265.
• Maul, G.A., Kim, Y., Amini, A., Zhang, Q., Boyer, T.H., 2014. Efficiency and
life cycle environmental impacts of ion-exchange regeneration using sodium,
potassium, chloride, and bicarbonate salts. Chemical Engineering Journal, 254,
198–209.
Other resource on Ion Exchange and CIX