Causes and Impact of WFGD ORP

Worldwide Pollution
Control Association
WPCA-Duke Energy
FGD Wastewater
Treatment Seminar
March 7, 2013
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W
P
C
A
Causes & Impacts of WFGD ORP on

Effluent Composition
07 March 2013
Shannon R. Brown,
AQCS Engineer
Overview
Introduction into WWT for WFGD Blowdown
Important Chemical Parameters for Wastewater Treatment
Impact of ORP on WFGD Effluent Composition

Causes of Variation in WFGD ORP Levels
Mitigation Strategies for Improved Bleed Stream Composition
Conclusions & Path Forward
Proprietary and Confidential
2013 Babcock & Wilcox Power Generation Group, Inc. All rights reserved.
.2
Overview

.3
Technologies for Treatment of WFGD Effluent*

Settling Ponds
Other
6%
Mostly to reduce suspended solids
Chemical Precipitation
Targets mercury and arsenic removal
Settling Ponds
34%
Biological Treatment
Targets Selenium
Also removes nitrates & sulfates
Operating
Practices
Toward ZLD
38%
Operating Practices toward ZLD

Chemical
Precipitation
20%
Other
Vapor-Compression Evaporation
1 unit in US
Clarifiers
Constructed Wetlands
Commingling with other wastewater
Ash solidification
Biological
Treatment
2%
*As reported by the EPA in October 2009 report

.4
Brine Concentrator Systems(BCS) Overview

For FGD, Typically Two Steps:
1. Brine concentration using a falling film evaporator (FFE)
with mechanical vapor compression (MVC)
Reduces the water content of the wastewater by ~90%
2. Forced Circulation Crystallization(FCC) using either

steam or MVC as the energy source
Creates crystals by further evaporating water to
concentrate the stream to a value above the solubility
limits of the dissolved solids
Crystals are separated using a dewatering device such
as filter press
.5
BCS Pre-Treatment
Typical chemical precipitation (CP) system
Used for gypsum de-saturation & heavy metals removal
May prevent hazardous waste classification
Complete removal of Calcium & Magnesium via soda ash

softening is desirable from an operating standpoint
But very expensive with costs over 50 cents per pound of calcium
removed and $1 per pound of magnesium removed.
.6
Spray Dryer Evaporation Process Flow Diagram

Chloride Purge Stream from WFGD
Boiler
Slip Stream
FG Line
130 F
SDE
FF
AH
Precip, or
BH
WFGD
Main FG Line
SDE: Spray Dry Evaporator

FF: Fabric Filter
FG: Flue Gas
AH: Air Heater
.7
Overview
.8
WFGD Chemistry sets the Difficulty

of Effluent Treatment
WFGD Bleed to
Dewatering
Recycle
Wastewater
Treatment
Solids removed as gypsum product

Filtrate split between WGFD reclaim
and waste water treatment
Hydroclone tuning and split is important for

water balance, gypsum purity & chloride level
WWT operations needs to treat the bleed

stream as it comes, including phase
partitioning of regulated metals
.9
WFGD Effluent Composition

Nominal WFGD Effluent
Stream Composition
Typical WFGD Blowdown

Streams Pose
Challenges:
Species
mg/L
Boron
300
Calcium
5,000
High TDS
Magnesium
2,000
Selenite (IV)/Selenate (VI)
Sodium
1,000
Mercury
Chloride
11,000
Boron
Sulfate
5,000
TDS
25,000
High in Halogens
*As reported by the EPA in October 2009 report

.10
Overview

.11
The System View

Coal
Combustion
NOx &
Particulate
Control
Reaction
Tank ORP
WFGD
Operation
WFGD
Effluent
Chemistry
Wastewater
Treatment
.12
What is ORP?
Oxidation Reduction Potential (ORP)
A single voltage measurement against a reference electrode
Measurement technique similar to pH
Can be monitored on-line
The strength of oxidizers and reducers in a solution in relation to

their respective concentration
The more positive the voltage, the more strongly a solution would
oxidize (attract electrons from) other sources
Oxidizers accept electrons, reducers lose electrons.
ORP can be negative
.13
Why is ORP important?

ORP control the oxidation of slurry constituents
Knowledge of Slurry ORP, in combination with pH and chloride level,
can be used to predict WFGD chemistry
Think of ORP as a threshold value. Comparing the ORP to the
electronegativity and other known parameters, one can make
estimations of the thermodynamically preferred and most likely
state for each slurry constituent
At high ORP slurry constituents are oxidized
At low ORP slurry constituents are in lower oxidation states
Oxidation state often controls solubility & phase

partitioning of many species
WFGD Slurry ORP often follows and S-shaped curve,
rapidly escalating from 50-150 mV to >500 mV
.14
Impacts of ORP on WFGD Blowdown
ORP Levels
Reaction with
Halogens in
Solution
Redox Chemistry
in WFGD ART
Oxidation of
Selenium
More Selenate
(Se+6) to WWT
Selenate is
not removed
in WWT
Mercury
electrochem.
active
Local Reduction
of Hg
Hg Reemission
Event
Oxidation of
Manganese
Negative ORP
in Tank
Steady He
Reemission
Phase change
of other metals
Effective drop in
pH
MnxOy
Precipitation
Increase in
Reagent Feed
Aggressive
Corrosion
Materials
concerns
High level
of Oxidizer
in Bleed
Evolution of
Hypochlorite
species
Falsely
Elevated Acid
Gas Emission
Absorber
Bleed sent
to WWT
Potential
Bio-Reactor
Impact(s)
.15
Redox Chemistry within the WFGD

Mercury
Selenium
As ORP Selenate (Se+6) is dominant
At lower ORP, Se+4 is dominant
As ORP Mercury seems to shift from the

particle bound to the dissolved phase
Swinging or negative ORP may cause
reemission
ORP
Other Metals
pH & Oxidizer Content
Solubility & phase partitioning of many metals, Unreacted oxidizer(s) in the bleed stream may
such as manganese & cobalt may also be
disrupt downstream WWT
predicted
pH may drop due to oxidizer reactions
.16
Selenium
Selenite (IV) and Selenate (VI) are dominant forms in FGD waters
Selenate formation is problematic
Inability to be removed via chemicals
Removal via biological remediation
.17
Phase Partitioning Selenium
.18
Selenite vs. ORP

in WFGD ART Slurry
1000
900
Selenite ( g/L)
800
700
600
500
400
300
200
100
0
0
100
200
300
400
500
600
700
ORP (mV)
.19
Selenate vs. ORP

in WFGD ART Slurry
5000
4500
Selenate ( g/L)
4000
3500
3000
2500
2000
1500
1000
500
0
0
100
200
300
400
500
600
700
ORP (mV)
.20
Mercury Re-emission
ORP effects mercury emission in WFGD absorbers
Strongly reducing conditions within the scrubber will cause Hg+2 to
be reduced to Hg0 and re-emitted
Mercury is a very electrochemically active species
Transitions in ORP have been implicated in Hg re-emission events
.21
Phase Partitioning Mercury
.22
Dissolved Mercury vs. ORP

in WFGD ART Slurry
Ratio Dissolved/Total Hg
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0
100
200
300
400
ORP (mV)
500
600
700
.23
Phase Partitioning Manganese
.24
High ORP & pH Drop

High ORP results from a high concentration of strong
oxidizers
Oxidizers will continue to react with stream constituents
until equilibrium is reached.
WFGD absorber slurries are NOT at thermodynamic
equilibrium at the time of bleed
Strong oxidizers will react with the halogens in solution
liberating halogen containing gas
releasing hydronium ions in solution
pH would be lowered within the ART, but reagent buffers

this reaction
After buffering solids are removed, pH could decrease downstream
.25
Strength of Oxidizers
Fluorine
Atomic Oxygen
Ozone
Persulfate
Hyphochlorous acid
Chlorine
Bromine
.26
Overview

.27
The Relationship Between ORP

and Strong Oxidizer Concentration
Total Oxidizer Titration Results
Unit
ORP Profile
Oxidizer (ppm)
High ORP
1680
High ORP
1592
High ORP
1574
High ORP
1571
Low ORP
227
Low ORP
169
Low ORP
50
Low ORP
29
Low ORP
27
10
Low ORP
19
11
Low ORP
10
12
Low ORP
<2
.28
Prior to Testing:
What We Knew About Strong Oxidizer Formation
Strong
Oxidizer(s)
Sulfite
Concentration
Kinetics
Transition
Metal
Concentration
Mixing
S-N Chemistry
O:S
Stoichiometry
Ozone
Removal by
SO3 mitigation
Mn+3
Agitation
Nitrogen
Influx &
Speciation
Oxidation Air
Fe+3
Oxidation Air
SCR
Load
Ammonia Slip
Burner
Performance
Upstream
Oxidizers
Coal
Other?
Lots of Factors MAY

lead to strong oxidizer formation
B&W is performing testing
to explore possible causes
.29
Full Spectrum Gas and Slurry Field Testing

3rd Quarter 2012
Test Parameters:
Coal Type
O:S stoichiometry
ESP Operation
SCR Performance
Data Obtained
Full Spectrum Gas Analysis
FTIR, Inlet Velocity & SO3 Traverse,
Speciated Mercury Testing
Full Spectrum Analysis of the Slurry

for Metals
IC, ICP-MS, Speciated Se & Hg
.30
Preliminary Results of Field Testing

Able to cause ~300mV increase in scrubber ORP, raising
ORP to over 500 mV
Change occurred rapidly (~1 hour), as is observed in industry cases
ORP came down in a decay expected of a residence time

distribution after test parameter returned to normal
Test replicated 3 times with same result
Results are under review
Results to be verified through testing with another Utility

Potential for control of WFGD chemistry through tuning
.31
Overview

.32
System Tuning
Reaction
Tank
Chemistry
System
Inputs
WFGD
Operations
Tuning
WFGD Bleed Stream

Optimization for WWT
.33
Potential Mitigation Strategies

Integrated control & tuning of AQCS chain
System
Impact
Fine
Adjustment
Optimization of WFGD Chemistry & Control

Reduced Oxidation Air
Injection of Reducing Agents

Medicine
Other
?
.34
Overview

.35

Implementation of holistic control of the AQCS system
may provide tailored effluent stream composition(s)
Operation of upstream parameters impact WFGD ORP
and composition
WFGD design and operation also changes bleed stream chemistry
WWT performance optimization may thus be obtained by controlling
these parameters
WFGD Bleed stream composition is important to

performance of wastewater treatment operations
Oxidation state speciation and phase partitioning of metals
(Se, Hg, etc...)
pH, ORP, Dissolved halogen content (F-, Cl-, Br-, I-)
Further Research into how upstream changes

impact downstream chemistry
.36
Questions
.37

Causes and Impact of WFGD ORP

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Worldwide Pollution

Visit our website at www.wpca.info

Causes & Impacts of WFGD ORP on

Impact of ORP on WFGD Effluent Composition

Proprietary and Confidential

Impact of ORP on WFGD Effluent Composition

Proprietary and Confidential

Technologies for Treatment of WFGD Effluent*

Mostly to reduce suspended solids

Operating Practices toward ZLD

*As reported by the EPA in October 2009 report

Brine Concentrator Systems(BCS) Overview

2. Forced Circulation Crystallization(FCC) using either

Proprietary and Confidential

Complete removal of Calcium & Magnesium via soda ash

Proprietary and Confidential

Spray Dryer Evaporation Process Flow Diagram

SDE: Spray Dry Evaporator

Proprietary and Confidential

Proprietary and Confidential

WFGD Chemistry sets the Difficulty

Proprietary and Confidential

Solids removed as gypsum product

Hydroclone tuning and split is important for

WWT operations needs to treat the bleed

WFGD Effluent Composition

Typical WFGD Blowdown

Selenite (IV)/Selenate (VI)

*As reported by the EPA in October 2009 report

Impact of ORP on WFGD Effluent Composition

Proprietary and Confidential

The System View

Proprietary and Confidential

The strength of oxidizers and reducers in a solution in relation to

ORP can be negative

Proprietary and Confidential

Why is ORP important?

Oxidation state often controls solubility & phase

Impacts of ORP on WFGD Blowdown

Proprietary and Confidential

Redox Chemistry within the WFGD

As ORP Mercury seems to shift from the

pH & Oxidizer Content

Proprietary and Confidential

Proprietary and Confidential

Phase Partitioning Selenium

Proprietary and Confidential

Selenite vs. ORP

Proprietary and Confidential

Selenate vs. ORP

Proprietary and Confidential

Proprietary and Confidential

Phase Partitioning Mercury

Proprietary and Confidential

Dissolved Mercury vs. ORP

Proprietary and Confidential

Phase Partitioning Manganese

Proprietary and Confidential

High ORP & pH Drop

pH would be lowered within the ART, but reagent buffers

Impact of ORP on WFGD Effluent Composition

Proprietary and Confidential

The Relationship Between ORP

Proprietary and Confidential