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Produced Water Research Projects
Tom Hayes, GTI
RPSEA Unconventional Gas Conference 2010Golden, Colorado
April 7, 2010
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Challenges Produced Water (PW) comprises >90% of
total waste volume from gas development Produced Water (PW) is at ground zero in
debates over unconventional gas development
Many areas of the U.S. are running out of reinjection capacity (e.g. Rocky Mountain States, Appalacian areas, CBNG basins)
Energy planners and stakeholders need alternatives for PW mgt to avoid constraints to energy production
Major R&D Efforts on Produced Water Management
Industry Water Conservation Consortia Barnett Shale (BSWCMC)Appalachian Shale (ASWCMC)Marcellus Shale Coalition
Individual Developer Company Testing of Available Know-How
RPSEA Program NETL-DOE Program NYSERDA Project on Shale Gas Issues
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Major R&D Efforts on Produced Water Management
Industry Water Conservation Consortia Barnett Shale (BSWCMC)Appalachian Shale (ASWCMC)Marcellus Shale Coalition
Individual Developer Company Testing of Available Know-How
RPSEA Program NETL-DOE Program NYSERDA Project on Shale Gas Issues
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• GTI Shale Gas Water Mgt• GE Pretreatment R&D• CSM Tech Assessment
CSM Project: Integrated Framework for Treatment & Mgt of Prod Water
54 Technologies Reviewed and Assessed Evaluation Criteria Carefully Established Principles & Description of Each Process Commercial Application History Niche and Capabilities Projected for PW Costs Vendor Information 1st Edition Now Available
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Frac Water Composition
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Water90.6%
NYSERDA Report, 2009
Barnett Shale and Appalachian Shale Water Conservation Committees Demographic Surveys on Water Practices Identification of the Best Opportunity for
Water Conservation Expert Panels on Water Issues and Mgt Defining Water Conditioning Targets Establishing Present Day Best Practices Prioritizing R&D Directions Outreach to Stakeholders
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Components in Flowback Water
Constituents of Produced Water
Frac Job Additives
+
SandFriction ReducerOxygen ScavengersCorrosion InhibitorsScale InhibitorsBiocides
Natural Gas Industry Water Use in the Barnett Shale
Frac Jobs Drilling Other
10%
89%
Total Water Projected Use = 10,905 Ac-Ft(2006 Estimate)
<1%
Water Sources Used in the Barnett Shale for Natural Gas Development
Groundwater Surface Water Reuse and Recycle
<1%43%
56%
Total 2006 Water Use = 10,905 Ac-Ft/yrDaily Use = 9.7 MG
0
500
1000
1500
2005 2010 (Projected)
Mu
nic
ipal
Ste
amE
lect
ric
Irri
gat
ion
Man
ufa
ctu
rin
g
Liv
esto
ck
Min
ing
Bar
net
tD
rilli
ng
An
nu
al W
ater
Use
1000
’s A
cre-
Fee
t
Natural Gas Development
Freshwater Users in the Barnett Shale Region
Fountain Quail Mechanical Vapor Recompression Unit for Flowback Water Treatment and Reuse
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• At Devon Sites• 6,000 bbls/d/site• AquaPure Mfgr• Operated by Fountain Quail• Obtaining field Performance Information
Encana Ultrafiltration
Electrocoagulation Testing
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Reverse Osmosis Trials in the Barnett
Barnett Shale Expo Outreach
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BSWCMC Exhibits: 3 Yrs in a Row
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Currently Available Innovative Brine Management Technology Options
Fountain Quail (Thermal Processing for Water Recovery)
212 Resources (Thermal Processing for Water Recovery)
GE Thermal Processing (Thermal Processing for Water Recovery)
Intevras (Heat Recovery from Compressor Engines for Brine Evap)
GeoPure (UF / Reverse Osmosis) Ecosphere Technologies (Ozonation
and Reverse Osmosis)
Example Products from the BSWCMC Companies
Survey Results Water Data from Grab Samples Water Availability Assessment Reports Proceedings of the Frac Job Expert Panel Information from the review of equipment
vendors and solution providers Identified Friction Reducers that Perform
Well at High TDS Levels R&D Planning Reflecting Industry Priorities Website: www.barnettshalewater.org
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Recent Results from Sampling and Analysis of Flowback Water funded by the Marcellus Shale Coalition
New Data on Sampling and Analysis of Flowback Water Funding from MSC and ASWCMC
Industry Consortia Sampling from 19 locations Initiated and completed in 2009 Includes general chemistry and detailed
analysis of constituents of interest Lists of Constituents of Interest
provided by the USEPA, WV-DEP and PA-DEP
Over 250 determinations performed on samples
Comparison of FB Water with Conventional Produced Water
Parameter 14-d FB 14-d FB Ranges₣
pH 5.5 6.5 5 - 8
Alkalinity * 52 93 NA
TDS ** 112,000 105,000 20,000 - 200,000
Tot Susp Solids ** 17 197 0-250
Tot Org Carbon ** 34 39 NA
Biochemical Oxygen Demand ¥
149 2.8 NA
Oil & Grease ** 31 < 5 mg/l 3 – 100
Location A Location B
* mg/l as CaCO3** mg/l
¥ mg/l as O2
‡ ND = Nondetect NA = Not Available₣ IPEC, 2004; GRI, ‘94
Conv. PW
Cations and Anions in Influent and FB Water Samples from Two Locations
Parameter ** Influent 14-d FB Influent 14-d FBSodium (Na+) 6,190 32,500 88 31,500
Calcium (Ca2+) 2,990 12,500 21 7,820
Magnesium (Mg2+) 3.6 7.0 3.7 725
Iron (Fe2+) 11.6 39.8 0.9 41
Barium (Ba2+) 9.8 58 0.28 569
Chloride (Cl-) 10,700 78,600 75 67,100
Bicarbonate (HCO3-) 31 56 46 56
Ammonia (NH4+) 9.3 107 3.6 121
---- Location A ---- ---- Location B ----
** mg/l
Concentration of TDS in Flowback Water with Time During Well Completion: Location A
0 10 20 30 40 50 60 70 80 90 1000
50000
100000
150000
200000
250000
Total Dissolved Solids, mg/l
Days Following Hydraulic Fracturing
0 10 20 30 40 50 60 70 80 90 1000
50000
100000
150000
200000
250000
300000
Total Dissolved Solids, mg/l
Days Following Hydraulic Fracturing
Concentration of TDS in Flowback Water with Time During Well Completion: Location B
Categories of Chemicals of Concern
Volatile Organics Semivolatile Organics Pesticides Organophosphorus Pesticides PCBs Metals
Summary of Results of Volatiles Measurements in 14-Day Samples
Summary of Results Flowback water characteristics are
consistent with ranges observed with conventional produced water
Low suspended solids and TOC Man-made chemicals of concern are at
non-detect levels. BTEX and PAHs are at trace levels. Oils and greases are at non-problem levels,
but some control may be needed Soluble organics are highly biodegradable Heavy metals are lower than in Mun Sludge
Possible Treatment Needs Brine Volume Reduction with Water
Recovery (for reuse in future frac jobs) Removal of Polymers (Friction Reducer
Compounds) Scale Control (Including NORM Scale) Oil and Grease Control Soluble Organics: Decrease Total
Organic Carbon Control of suspended solids Microbial Control
Water Reuse Since the transportation & storage of
brines over 3,000 mg/l TDS requires added regulatory scrutiny, it may be desireable to achieve partial removal of salts from the water – a process called demineralization.
Demineralization can be achieved with thermal systems or with membranes.
Pretreatment is used to protect the demineralization processing stage.
Prevention of fouling of heat exchangers and membranes is important.
Water Reuse Flowsheet
Pre-Treat-Ment
De-Mineraliza-tion
Disposal ofSalt Brines and Solids:By-Prod RecDWILF
Make-upWater
Well A
Well B
Conc’dBrine
Bypass
ResidualsTo Landfill Recovered
Water
Brine
WaterBlend
RPSEA Funded Work
Barnett and Appalachian Shale Water Management and Reuse (GTI)
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Objective
Reduce demands for freshwater Reduce environmental impact of
brine disposal Ensure supplies of water for well
drilling and completions for natural gas development in the shale
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Develop water management methods and Technologies that:
Areas of Emphasis
Evaluation of commercially available technologies for water reuse
Development of novel coatings to improve performance of membrane of low cost treatment processes (fouling resistance)
Development of electrodialysis to reduce electrical energy use by 60%
Evaluation of alternate water sources for well completions
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Project Team
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Team Member Organization Tasks/Technologies
Dr. Tom Hayes
Dr. Blaine Severin
GTI
EPD
Principal InvestigatorWater CharacterizationElectrodialysis Engineering Analysis
Dr. Benny Freeman Univ. Texas Polymeric Coatings to Improve RO Membranes
Dr. Peter Galusky Texerra Feasibility of Early Flowback Water Capture
Dr. Jean Phillipe Nicot
BEG Alternate Water Sources
David Crowe GeoPure Pilot Prototype for the Field Testing of Novel Membranes
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Technical Tasks
Assemble a Water Characteristics Database (Task 4)
Collect composition data already available from the BSWCMC and the ASWCMC/MSC on flowback and produced waters
Where information gaps exist, conduct sampling and analysis on grab samples
Product: Database using MS Excel or Access.
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Determine the Feasibility of Collecting Low-TDS Early Flowback Water (Task 5) Goal: Determine the proportion of early
flowback water that can be captured as a lower TDS water stream suitable for reuse.
Conduct water sampling and analysis for water conductivity and composition on flowback waters from 3 to 4 locations.
Develop flowback water management strategies to maximize water recoveries at minimal cost.
Develop Equipment Design for PW Triage 40
Conceptual Example of Salt Concentration Versus Time in Flowback Water Collected with Time During Well Completion
0 2 4 6 8 10 12 14 160
20000
40000
60000
80000
100000
120000
Total Dissolved Solids, mg/l
Days Following Hydraulic Fracturing
Flo
w R
ate
TDS Builds up ---But Flow Rate Decreases.Therefore, early 20-50% of FBWater may be low in TDS
Alternate Water Sources (Task 6) Goal: Identify potential water sources
that do not compete with public water supplies
Interview industry operators to understand current practices in finding alternate water sources
Inventory unconventional water sources Obtain compositional data on these
sources and determine suitability for utilization in well completions
Product: Topical Report
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Engineering Evaluation of Performance and Cost of an Existing Evaporation Units for Flowback Water Reuse (Task 7) Cooperators: Devon Energy and
AquaPure/Fountain Quail Companies Describe the overall performance of the
treatment system (include mass and energy flow diagrams to discuss key examples) using field demonstration information.
Determine range of vendor costs and process economics.
Product: Engrg Guidance Document
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Fountain Quail MVR Field Performance in Flowback Water Reuse
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• Data Collected From 1 Site• 6,000 bbls/d/site• Obtaining field Performance Information at a Second Site Using GTI Sampling Plan
Development of Electrodialysis for the Demineralization of Flowback Water (Task 8) Electrically Driven Process Design and construct an integrated
laboratory electrodialysis (ED) treatment system
Determine performance using advanced commercial ED membranes using actual flowback water
Determine conditions that reduce energy costs by more than 60%.
Special Conditions: Partial Demineralization of High TDS Waters
Initial Experiment: Influent = 30,000 mg/l; Effluent > 5,000 mg/l TDS
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Influent
Schematic of Electrodialysis
Optimized to ReduceEnergy RequirementsBy 60% (< 0.1 kWh/lb salts Removed)
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Laboratory Prototype at GTI
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0 50 100 150 200 250 300 350 400 4500
5,000
10,000
15,000
20,000
25,000
30,000
35,000
0
0.5
1
1.5
2
2.5
Treatment of 3% Salt at 5 Volt
Dilute Concentration mg/L
Amperage
Time Minutes
TD
S a
s N
aC
l mg
/L
Am
pe
rag
e
Initial Results on Synthetic PW
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-1 1 3 5 7 9 11 13 150
0.1
0.2
0.3
0.4
Target < 0.1 KWHr/Lb
Initial Power Utilization Curve 3% NaCl
Volts
KW
Hr
/ L
b N
aC
l
Initial Results on Synthetic PW
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-1 1 3 5 7 9 11 13 150
0.1
0.2
0.3
0.4
Target < 0.1 KWHr/Lb
Initial Power Utilization Curve 3% NaCl
Volts
KW
Hr
/ L
b N
aC
l
Goal
Cost Advantages of ED Reduced operational voltage reduces
energy requirements (kWh/lb salt rem) Resists Fouling Electricity requirement <0.1 kWh/lb salt rem 1 Barrel of PW that has 50,000 mg/l salt
removed (17.5 lbs salt rem) would require only $0.18 of electricity at 10 cents/kWh.
Strategy: Remove >50% of the water with ED at < $1/bbl before processing with a thermal MVR at $4-5/bbl.
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Innovative Coatings for Improved Membrane Performance in the Demineralization of FB Water (Task 9) Membrane processes of emphasis:
ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO)
Synthesize fouling resistant coated materials: Polydopamine coatings.
Performance objectives: 1) Fouling resistance; 2) Reduced energy requirements
Results to date on synthetic FB water: Doubled RO flux for the same pressure dropDecreased energy requirement by 50%
Next: Test coated membranes in laboratory membrane separation units using actual flowback water.
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Field Evaluation of Improved Membranes in Field ETU (Task 10)
Conducted in the Second Year of the project.
Field ETU Skid for Integrated Membrane Testing was designed and constructed by GeoPure with cooperation of Texas A&M.
Install advanced coated membranes fabricated by UT and commercial partner
Test ETU at an actual shale gas flowback water management site
Duration of Testing up to 35 days.
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Strategy for Reducing Cost of Water Reuse
Highly Concentrated Brine to Class II Disposal or to By-Product Recovery
Pretreatment Processing for Salt By-Product Recovery (GE Research)
High-TDS
Low-TDS
• Survey water chemistry• Define specifications for water re-use• Evaluate Pretreat Options…performance, cost, waste streams
Suspended solidsMicrobiologicalsSilicaOilsIron, ManganeseBarium• Aspen/OLI Process Modeling
Approach of the GE Research
-Membrane testing…fouling, flux, rejection (DOE)
-Thermal process testing…foaming, scaling, corrosion, salt quality
(RPSEA)
Benefits and Impact to Industry
Reduce industry demand of fresh water for shale gas developments
Ease water availability constraints to well development and completion.
Decrease environmental impacts due to water transportation (i.e. air impacts, fugitive dust, traffic, and carbon footprint)
Reduced cost of water processing for reuse of flowback water for future well completions.
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For more informationContact Tom Hayes (847.768.0722)Email: [email protected]
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Increased Electrode Electrolyte Conc Improves Performance
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0
20
40
60
80
100
30 g/L Conventional 60 g/L 90 g/L
Effect of Electrolyte Concentration on Required Membrane Area
No
rmal
ized
Are
a (1
00%
= C
on
ven
tio
nal
)
RPSEA Funded Work
Barnett and Appalachian Shale Water Management and Reuse (GTI)
Pretreatment Technologies for By-Product Recovery from Brines (GE)
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Deliverables Database on Shale Gas FB and PW
Compositions Conceptual designs for low TDS FB water
segregation and mgt Guidance Document on best practices for
alternate water source utilization Engineering decision tool on mechanical
vapor recompression evaporative treatment processing
Electrically driven processing for low-energy partial demineralization
New Generation of coated membranes for improved UF/NF/RO capabilities
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RPSEA / DOE-NETL Projects at GE
Shale Water Mgt and Reuse (GTI) Hybrid Membrane and Thermal
Technologies for Demineralization (GE) Coatings for Fouling Resistance and
Increased Energy Efficiency of RO (UT) Feas of Early Flowback Water Capture (GTI) Development of Electrodialysis for
Reducing Energy Required for Demin (GTI) Engineering Decision Documents (GTI and
CSM)
Well 1
Well 2
Near-WellWater MgtDecisions
Pre-Concentrate
?
ConcentatorAlternatives
ThermalMembranesHybrid ProcessingEtc.
Final Disposal orUtilization Options
• Deep Well Injection (Class II) of Brines• Conventional Disp at POTWs• By-Product Salt Recovery• Landfill• Ocean Disposal• Etc.
Make-upWater
By-Pass
WaterRecoveredFor Reuse
PretreatOptions
ConditioningOptions
By-PassYes
No
FlowbackWater orPW
In-Field Near-Field Far-FieldWithin 2 mi Within 20 mi Within 200 mi
Generic Flowsheet of Management Options
Blend
Completion