demonstration testing results: oxidation, coagulant and ......hypochlorite, chlorine dioxide and...
TRANSCRIPT
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PRODUCEDWATEREVENTS.COM
Demonstration Testing Results: Oxidation, Coagulant and
Flocculant Demand in Reuse Applications
Buddy Boysen – Water Standard
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Water Use is Increasing: Reuse is Attractive
Photo Source: Fortune Magazine
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Overview
• Intro: Demonstration testing program
• Chemical pretreatment process development
• Key drivers
• Performance and critical variables
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Pilot Test Program OverviewKey Objectives:
Cost effective reuse of
flowback and produced
water
Reuse scenarios included:
Frac/drilling reuse
Industrial reuse
Surface water discharge
Evaluation of process
unit operations
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Water Variability: Unconventionals
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Produced Water Treatment
Testing needs varied by reuse applications
Core treatment requirements
Oil and grease
Suspended solids
Dissolved metals
Hydrogen sulfide
Bacterial inactivation
Advanced treatment
Electrochemical treatment
Biological nitrogen removal
DesalinationAdvanced
Treatment
Sedimentaiton/
Solids Separation
Chemical
Pretreatment
Desanding
Feed Tanks
If Required By
Reuse Application
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Chemical Pretreatment Process
Core treatment needs:
Oxidation of dissolved metals and H2S
Coagulation of fine suspended solids
and oils
Advanced treatment needs:
Conversion of dissolved organics
Process Focus
Performance
Overall treatment costs
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Typical Treatment Approach
Oxidation
Purpose is to precipitate metals and hydrogen
sulfide. TOC treatment may be beneficial.
Coagulation
Purpose is destabilization of colloidal material
to build larger particles (floc).
Flocculation
Purpose is to agglomerate coagulated solids.
Improve particle characteristics for separation.
Flocculation Separation
Oxidant
Coagulant
Flocculant
Produced Water and
Flowback
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Visual Process Overview
Raw PW Oxidized PW Coagulated PW Flocculated PW
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Chemical Oxidation
Chemical oxidants accept electrons to
prepare ions and molecules for separation.
Typically Targets
Dissolved metals
Hydrogen sulfide
Organics
Common Oxidants
Sodium hypochlorite
Chlorine dioxide
Hydrogen peroxide/caustic
Sodium/potassium permanganate
Ozone
Photo Source: Georgia State University
Hydrogen Peroxide2Fe+2 + H2O2 + 4OH- → 2Fe(OH)3 (precip.)
H2S + H2O2 → S0 + 2H2O
Chlorine Dioxide
Mn+2 + 2ClO2 + 4OH- → MnO2 + 2ClO2- + 2H2O
ClO2 + 5Fe(HCO3)2 + 3H2O → 5Fe(OH)3 + 10CO2 + H+ + Cl-
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Oxidant Comparison
Oxidant Relative Cost ($/lb) Performance
Sodium Hypochlorite $ +
Sodium Permanganate $$ ++
Chlorine Dioxide $$ ++
Hydrogen Peroxide $$ ++
Ozone $$$ ++++
Each product has benefits and
challenges.
Hypochlorite, chlorine dioxide and
ozone can be generated onsite with
varying complexity.
Bulk storage considerations also enters
into the discussion.
Ability to produce/maintain a
disinfectant residual and value to
project need to be considered.
Ozone performance was not evaluated as part of the
2018 study program.
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CoagulationCoagulants affect colloidal stability, increasing particle
collisions to promote the formation of larger particles
through absorption.
Target particles
Clays
Precipitated metals
Organic colloids
Typical coagulants
Alum
Ferric sulfate
Ferric chloride
Prehydrolyzed aluminum (PACl, ACH)
Photo Source: Koutsos et. Al, 2011
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Coagulants
Testing focus has been on polyaluminum
chloride and ACH products.
Range of polyaluminum chlorides provides an
ability to tailor product performance for
downstream processes.
Low Basicity PAC: Larger floc particles. Better settling.
More residual aluminum.
Medium Basicity PAC: Medium sized particles,
potentially better flotation. Slight residual aluminum.
ACH: Improved TOC removal and lowest residual
aluminum. Much finer particles. Potential issues with
separation process.
Source: Behn Mayer
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Flocculation
During flocculation, a bridging agent is added
to agglomerate destabilized colloids, small
particles and oil droplets.
Mechanisms
Bridging and Patch Flocculation
(Anionic-, Non-Ionic, Cationic+)
Some flocculating agents:
Polymers: HPAM/CPAM/APAM
Guar
Alginate-
Chitosan+
Photo Source: SSWM
Photo Source: M. Hubbe
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Flocculation
Most organic flocculants are a blend of polymers.
Each flocculant component alters the final solids
product.
Our focus has been on biopolymers that can
create bridging with minimal impact on
downstream processes.
This is very important when considering
membrane applications.
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Basic Treatment Goals
Typical Water Quality Targets
Free oil: <1.5 ppm (EPA 1664 MDL)
Turbidity: <5 NTU
Total iron: <5 NTU
Hydrogen sulfide: non-detect
Treatment beyond these levels requires
more advanced post treatment.
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Advanced Treatment Goals
Range of Water Qualities
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Advanced Treatment Goals
Floating vs. Settling Solids
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Additional Treatment Questions
How does the treatment process respond to upsets?Feed water quality changes
Chemical dosing upsets
What is the downstream impact of chemical treatment process upsets?
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Test Program Findings
All treatment objectives were achievable.
Secondary objectives, related to downstream
process performance, should be considered
when developing the chemical treatment
process.
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Questions/Contact Info
Buddy BoysenDirector of Engineering and Technology
Water Standard
Phone: 713-400-4777