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Status Review of the RPSEA Project on Flowback Water
ManagementBarnett Shale Water
Conservation and Management Committee
February 16, 2011
New RPSEA Project on Shale Water Management and Reuse
Duration: 2 yrs. Total Budget: $2.5 million Budget provided to meet with BSWCMC Tasks of Project require input and
cooperation from BSWCMC companies
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Balanced Approach
Document successfully implemented reuse strategies
Describe best management practices in water conservation and management
Improve existing demineralization technologies that compliment current water management and processing
Conduct substantial technology transfer and information dissemination
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Major Participants
BSWCMC & ASWCMC GTI Staff and Consultant University of Texas Bureau of Economic Geology Texerra GeoPure/Texas A&M
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Project ElementsTask Topic Perf Orgs Goals
4 Water Database GTI 2, 35 Early Flowback Texerra 26 Alt Water Sources BEG 57 Distillation Perf & Econ GTI 49 Imp Coatings UF/RO UT 48 ED Treatment Feas GTI 5
10 Field Eval of RO ETU GeoPure 43 Information Dissem GTI & Others 6-8
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Work Scope Summary
Investigators Description
Tom Hayes, GTI Coordination, Engrg Evaluations of In-Field Perf & Cost, Water Char Database, Information Dissemination
Benny Freeman Mukul Sharma, UT
Innovative Coatings to Improve UF, NF, RO Membrane Processes
GeoPure/A&M Experimental Test Unit (ETU) for Evaluation of UF & RO Membranes Under Actual Field Conditions
JP Nicot, BEG Feasibility of Alternate Water Supplies
GTI & Dr. Severin Electrodialysis Process Development
Peter Galusky, Texerra
Feasibility of the Capture of Low-TDS Early Flowback Waters at the Wellhead
Deliverables Database on Shale Gas FB and PW
Compositions. (Apr 2011)
Conceptual designs for low TDS FB water segregation and mgt (Feb 2011)
Guidance Document on best practices for alternate water source utilization (Year 1 Topical - Done)
Engineering decision tool on evaporative treatment processing (Mar 2011)
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Deliverables New generation of coated membranes
with improved performance characteristics for UF, NF and RO: Extended Life, Lower Pressure Drop, etc.(Year 1 Topical Report - Done)
Electrically driven processing for low-energy partial demineralization (Year 1 Topical – Done)
Topical Report: Field Performance Verification of Improved Membranes (Test Plan Done; Draft Report Done)
Final Report (Due Dec 2011)9
T4 Flowback Water CharacterizationAccomplishments Sampling Completed
Field Sampling Plan and QAPP document have been finalized
Sampling has been completed at four locations.
Sampling performed at 0, 1, 5, 7 and 12 days
Samples analyzed by Test America
Future Directions Barnett Data to be
Combined with data from MSC
Information Base constructed in Excel Spreadsheet Format.
Information Base and Topical Report Deliverables Apr 2011
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Constituents and Measurements pH, Acidity, Alkalinity, Total Hardness Total Suspended Solids, Turbidity TOC, DOC, O&G, COD, BOD, Volatiles,
Semivolatiles, Total Volatile Acids, Phenolics
Total Dissolved Solids, Conductivity, Anions (SO4, Br, Cl, NO3, NO2 by ion chromatography), Sulfide, Total Cyanide, 22 Heavy Metals
Ammonia, Total Kjeldahl Nitrogen, PO4 5 Alcohols, 2 Glycols Gross Alpha/Gross Beta
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Summary of Results of Volatiles Measurements in 14-Day Samples
01020304050607080
Non-Detect Trace ppb level 1 ppm or more
A B C D E F G H
Zero Constituents
BTEX, Acetone1, 2, 4 – Trimethylbenzene1, 3, 5 - Trimethylbenzene
Number of Chemical Constituents
(< 2 µg/l forMost Constituents)
Locations
Summary of Results of SemivolatileMeasurements in 14-Day Samples
0
20
40
60
80
100
120
Non-Detect Trace ppb level 1 ppm or more
A B C D E F G H
Zero Constituents
Number of Chemical Constituents
Naphthalene2-MethylnaphthalenePhenanthrenePyridine
(< 0.5 µg/l forMost Constituents)
T5 Feasibility of Early FlowbackWater Capture
Accomplishments On Schedule.
Frequent measurements of cumulative volumes collected and conductivity.
Sampling has been completed at two locations.
Future Directions One more location will
be selected in the Barnett for sampling
Barnett Data to be Combined with data from MSC
Deliverable Completed Mar 2011
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Conceptual Example of Salt Concentration Versus Time in Flowback Water Collected with Time During Well Completion
0
20000
40000
60000
80000
100000
120000
0 5 10 15Days Following Hydraulic Fracturing
Total Dissolved Solids, mg/lFlow
Rate
TDS Builds up ---But Flow Rate Decreases.Therefore, early 20-50% of FBWater may be low in TDS
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Example Flow Correlations
0
5,000
10,000
15,000
20,000
25,000
30,000
35,000
40,000
0 20 40 60 80 100
Days after Fracture
Cum
mul
ativ
e B
arre
ls
Site H
Site S
Site B
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Example Concentration Correlations
0
50,000
100,000
150,000
200,000
250,000
300,000
350,000
400,000
0 20 40 60 80 100
Days after Fracture
TD
S m
g/l
Site H
Site S
Site B
0
50,000
100,000
150,000
200,000
250,000
300,000
0
2,000
4,000
6,000
8,000
10,000
12,000
14,000
16,000
18,000
20,000
0 20 40 60 80 100
Wel
l Hea
d C
once
ntra
tion
PPM
Col
lect
ed W
ater
BB
L
Days after Fracture
Median Flowback Event
Median Recovery
Median Well Head Concentration
Potential for Combined Options
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ED / RO
>
T6. Technical and Economic Feasibility of Using AlternativeWater Sources in the Barnett Shale Area (BEG/Nicot)
Objectives of Proposed Work
Inventory water sources not used for residential and community water supplies
Establish their water quality relative to standards determined by industry experts
Provide a feasibility study of use of alternate water with acceptable quality
2-year 330k effort (~30k cost-share) Led by BEG - ~State Geological Survey of
Texas but received very limited state funding, run mostly on soft money
Task List T1: Gather baseline data and determine current
and predicted water use for all purposesGather baseline data and determine current and
predicted water use Interview and interact with industry operators
T2: Inventory water sources Conventional and unconventional Determine possible interaction between sources
T3: Determine water chemical composition Frac job water quality specifications Alternate water sources
T4: Explore technical and economic feasibility T5: Management and outreach
Barnett Shale extent (blue)
Trinity outcrop (solid green)
Trinity subcrop(stippled light green)
Hill
Bell
Clay
Ellis
Erath
Jack Wise
Llano
Milam
Falls
Mills
Burnet
Coryell
Dallas
BrownColeman
Young
Cooke
Mason
Parker
Baylor Archer
Denton
Bosque
Tarrant
Knox
San Saba
EastlandCallahan
Williamson
McLennan
McCulloch
Collin
Grayson
Stephens
Haskell
Palo Pinto
Montague
Hamilton
Wilbarger
Comanche
Wichita
JohnsonHood
Kimble
Foard
Menard
Lampasas
LeeGillespie
Shackelford
Taylor
Concho
Throckmorton
Travis
Navarro
Burleson
Hardeman
Robertson
Blanco
Somervell
Rockwall
Brazos¹0 20 40 60 8010
Miles
Structural boundariesof the Barnett Shale
Available Barnett Shale well locations on 02/2011 (>15,000)
Structural boundariesof the Barnett Shale
Inventory all sources and document water chemistry
Waste water treatment plants and other unconventional sources: TCEQ/EPA databases, contact operators
Surface water: understand water availability and volumes and history of use of the industry as a whole: satellite imagery through time
Groundwater: catalog water quantity, quality, and productivity of subsurface water bodies
Municipal and industrial waste water 1/3 Queried TCEQ central database and other
auxiliary databases as well as EPA ECHO system
Collected information about rate, chemical and physical characteristics
100+ facilities with very variable characteristics
Municipal and industrial waste water 2/3
Sum of WWTP outfalls between 1 and 5 MGD in most counties
1 or 2 “large” (county seat) and up to 10 much smaller
In addition, 75 MGD in Denton and 116 MGD FW WWTP)
Municipal and industrial waste water 2/3
Municipal and industrial waste water 3/3 Many small communities at <0.025 MGD A few >1 MGD Not counting City of FW and Denton County:
30 MGD “available” BOD, pH, TSS, etc within EPA standards:
25th and 75th percentiles are:BOD5: 3 – 7.5 mg/LTSS: 3.5 – 14.0 mg/lChlorine: 1 – 3.5 mg/LpH: 6.9 – 7.9DO: 5 – 7 mg/L
Surface water 1/4 Inventory all non-state water bodies Understand industry use of farmer ponds
and other small water bodiesas a function of dry/wet year and before/after gas wells
Surface water 2/4
Somervell/Erath county line
Surface water 3/4
Somervell/Erath county line
Surface water 4/4 1 to 10
thousand acres / county
Depth still unknown
1 AF = 0.32 Mgal
Split between stored groundwater and surface water runoff still unknown
0
2,000
4,000
6,000
8,000 1
997
199
9
200
3
200
4 2
005
200
6 2
007
200
8
200
9 2
010
Calendar Year
Cum
ulat
ive
Are
a of
Wat
er B
odie
s (A
cre)
Erath County Pre-activity dry month
Pre-activity wet month
Groundwater 1/4
Many small aquifers of mostly brackish water (outside of the Trinity Aquifer)
Ogallala
Trinity
Edwards-Trinity
Several smaller aquifersWith mostly brackish water
Groundwater 2/4
Slightly brackish water can be found in:
Jack and Palo Pinto counties outside of Trinity footprint
Montague, Wise, Parker, Hood, and Erath counties on Trinity outcrop which thin in much of or in the western half of the counties
Barnett
Trinity Aquifer
Shallow Paleozoic Aquifers(becoming brackish quickly with depth
Groundwater 4/4 Aquifers are small (footprint < 1 county area)
Summary of aquifer samples
Pumping rate / yield: median is 20 gpm (95th percentile: 60 gpm)
PercentileBicarb
(mg/l)Sulfate
(mg/l)Chloride
(mgl/) pH TDS Alkalinity
95th 749 593 1,700 8.8 3,796 638
70th 518 151 235 8.3 1170 434
50th 425 78 120 8.1 758 357
30th 353 45 52 7.7 545 296
5th 213 15 14 7.2 334 182
Project status
Year1 deliverables:Milestone report on inventory of water sources Interim report on current practices
Further work: Proceed with feasibility/economic analysisPossibly field sampling and chemical analyses of
ponds, water wells, WWTP outflow
Trinity Aquifer footprint
Project status Year1 deliverable:Done. Interim report on current practices
(operators are being contacted, literature search/meetings, integration at the play level)
Further work: Finish up detailed inventoryProceed with feasibility/economic analysisPossibly field sampling and chemical
analyses of ponds, water wells, WWTP outflow
T7 Engineering Analysis of MVR Accomplishments On Schedule
Sampling has been completed at the Devon Maggie Spain Water Reuse Facility operated by Fountain Quail
Sampling performed twice weekly
Monitoring time: 8 weeks.
Future Directions Complete plots
Fate of constituents of interest / mass flow analysis
Energy inputs tracked
Cost information collected.
Deliverable: Engineering Guide Evaluating MVRs - Apr 2011 41
Constituents and Measurements pH, Alkalinity, Total Hardness Total Suspended Solids TOC, BTEX, O&G, TPH Total Dissolved Solids, Conductivity,
Anions (SO4, Cl, NO3), Phosphorus Total Heavy Metals Total Ammonia
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Sampling Points Raw Water Pretreated Water Concentrate Streams Product Water Streams
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T8. Development of Electrodialysis for the Demineralization of FlowbackWater
Objectives
Determine the technical feasibility of using electrodialysis to demineralizeflowback water
Evaluate the potential of advanced electrodialysis membranes to improve electrodialysis demineralization of flowback water
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Influent
Schematic of Electrodialysis
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The Electrodialysis Alternative Electrically driven Widely used in other industries for 30
years Applied successfully to brackish water
treatment Applied in the past to low to moderate
TDS produced waters to generate a product water of 1,000 mg/l TDS or less
Less prone to membrane foulingElectrodialysis reversal (EDR)Effective clean-in-place (CPI) procedures
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Industrial Electrodialysis Facility for Water Treatment
Tasks Design and construct an integrated
laboratory electrodialysis treatment system Perform treatment tests on integrated
system Determine performance using conventional
membranes using actual flowback water Determine potential improvements with
advanced membranes Determine conditions that meet
demineralization specs at reduced energy costs.
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Laboratory Hardware
Batch electrodialysis unit owned by GTI Commercial prototypes EurodiaGESiemens
One commercial unit will be selected for testing.
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Electrodialysis Pilot Unit Selected to reduce TDS from about 30,000-
60,000 down to 15,000 mg/l Scaleable pilot unit obtained from Aqualytics
(Graver Corp.) Batch volume = 20 gal Electrical power consumption measured for
each effluent condition15,000 mg/l10,000 mg/l5,000 mg/l1,000 mg/l
Performance Goals
Determine conditions that decrease electrical energy costs from 0.25-0.50 kWh/lb salts removed down to less than 0.1 kWh/lb salts removed.
Achieve product water recoveries of greater than 70%.
Minimal fouling tolerance
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Laboratory Prototype
Novel Operating Conditions for Electrodialysis Have Advantages Targeting a higher TDS for the product
water destined for reuse Resistance is greatly reduced Electrical energy costs are reduced by
more than 70%.
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Placement in the Treatment Train
FlowbackWater<50,000 ppm TDS
Pretreatment Electrodialysis Diluate
Water for Reuse
10,000 ppmTDS
Concentrate
Brine for Thermal
Treatment
Maintenance
Routine
FlowbackEventFlow Segregation
Evaluate Treatment Cost
Baseline operation power costs (kWhr/lb TDS)
Baseline capital (minimum membrane area)
Pretreatment costs (quality of feed stock)
Maintenance costs (membrane and electrolyte)
Value of the outputs (diluate/concentrate)
Approach
1. Capacity and power requirements; improvements as necessary
2. Mitigate problems as they occur under increasingly complex conditions
3. Relate data in context to the treatment train
4. Demonstrate operation with field water
Results Summary Year 1Identify power requirements for laboratory
conditions
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0 20,000 40,000 60,000 80,000
Initial Concentration (TDS mg/l)
kW
h pe
r lb
tran
sfer
red
Results Summary Year 1Identify capacity for laboratory conditions;
electrolyte improvements
ConventionalElectrolyte
100%
Ion Balanced124%
Ion and pH Balanced
143%
0
20
40
60
80
100
120
140
160
100%
= C
onve
ntio
nal I
on F
lux
Mitigate problems under increasingly complex conditions
First problem encountered; 4000 mg/l Ca++
Solution to Calcium Problem
Protection of Electrolyte at the Cathode Membrane
0
0.5
1
1.5
2
2.5
0 10,000 20,000 30,000 40,000 50,000
Diluate Concentration (ppm)
Amps
at 5
V St
ack
Pote
ntia
l
Test J, Catode Protected, 3% NaCl Only
Test K, Cathode Protected, 3% NaCl + 4000 mg/L Ca++
Test F, Cathode Unprotected 3% NaCl + 4000 mg/l Ca++
Summary Results Year 2
Continued Tests with Water Chemistry
30,000 ppm NaCl
4000 ppm Ca++
400 ppm Mg++
400 ppm Ba++
40 ppm Fe+++
Is cathode protection sufficient to mitigate other multi-valent cations?
Electrolyte Protection Part of Solution
0
0.5
1
1.5
2
2.5
3
0 10,000 20,000 30,000 40,000 50,000
Diluate Concentration (ppm)
Am
ps a
t 5V
Stac
k Po
tent
ial
Test J, 3% NaCl Only
Test K, 3% NaCl + 4000 mg/L Ca++
Test Q, 3% NaCl with 600 mg/l Mg++
Test R, 3% NaCl with Ca++, Mg,++, Ba++
Test T, 3% NaCl with Ca++, Ba++,Mg++,Fe+++
Mechanistic View of Cation ControlThree Types of Resistance
Electrolyte incursion and fouling Mostly solved with protective membrane
Stack precipitation and fouling Iron needs to be controlled in the feed
Ionic barrier Large cations inhibit flow of sodium ions
Mechanistic View of Cation ControlThree Types of Resistance
ElectrolyteFouling
StackFouling
IonicBarrier
Mg++ No No Yes
Ca++ No No Yes
Ba++ No No Yes
Fe+++ No Yes Yes
No No problem anticipated
No Crosses membrane, but controllable
Yes Reduces flux, but not a cleaning problem
Yes Pretreatment required
Performance of Selective Cationic Membrane in Protecting Electrolyte Solution
0102030405060708090
100
Ca Mg Ba Fe
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(4000 mg/l) (400 mg/l)
(400 mg/l) (40 mg/l)%
Rej
ectio
n of
Mul
tival
ent C
atio
n
Primary Treatment for Iron Removal
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Rapid Mix Agglomeration& Settling
Clarifier
Influent
Clarified Effluent
68
0
10
20
30
40
50
60
0 10 20 30 40 50 60 70
Post Clarifier Influent
Time, Days
Iron
Con
c., m
g/l
Iron Removal
Electrodialysis: Continued Development
Test Water from Field Samples Economic Evaluation Inclusive of
1. Capital costs 2. Operating costs3. Cleaning and Maintenance4. Pretreatment Needs
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T9. Innovative Coatings for Improved Membrane Performance in the Demineralization of FlowbackWater - UT (Benny Freeman and Mukul Sharma)
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75
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Estimated Energy Savings for Membrane Processes
UF PS-20*
(GE)PA XLERO*
(Dow Filmtec)
Qp2/Qp1
(after 1 hour of filtration)
2.35 1.26
Same transmembrane pressure differencewas applied to both PDOPA-unmodifiedand unmodified membranes. The flux ratiorepresents the increase in permeatevolume produced by the membranes usingthe same amount of energy.
Qp2/Qp1 = Ratio of permeate flow rate of PDOPA-modified and unmodified membranes
* Membranes were treated with 2 mg/mL DOPA in Tris-HClbuffer pH 8.8, and 1 hour deposition time. 1500 ppm soybeanoil/DC193 (non-ionic surfactant)/water emulsion was used asfouling solution in the filtration experiment.
0.5
1
1.5
2
2.5
3
0 0.2 0.4 0.6 0.8 1
PS-20 UF membrane (GE)PA XLERO (Dow Filmtec)
Qp2
/Qp1
Time (hours)
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T10. Membrane Experimental Test Unit - GeoPure/Hydro Geo.
Progress To Date Field Unit Operated
for 31 days in Nov and Dec of 2010.
Data collection completed
Unit moved from the site.
Future Directions Draft Report is
Complete
Under Review.
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Field Unit Operated by GeoPure/Advanced Hydro/UT
•Devon Energy Host / Maggie Spain Site•UltraFiltration / RO•With and Without Polymeric Coatings
Produced Water Pilot – Water Quality
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Turbidity
TDS
Temperature
High TOC - 90 mg/LHigh TDS – 39,000 mg/LMed Turbidity – 9 NTU
• 40-50% higher flux for coated• 30% lower TMP for coated• 80-90% higher specific flux (Flux/TMP) for coated• Higher recovery during HWC clean for coated
HWC 1
HWC 1
HWC 1RO water
back flushCIP
Produced Water Pilot – Outside-in UF
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Flux Trans-membrane Pressure -TMP
HWC 1 HWC 1
HWC 1
CIP CIP CIP
Produced Water Pilot – RO
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Flux
Trans-membrane Pressure -TMP
- Using ~6 hr EFM cycle, sustained flux of 35GFD was achieved with coated flat-sheet UF membranes
- Excellent recovery during CIP or HWC cleans
Produced Water Pilot – RO
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Normalized Flux % Rejection
- Higher and very stable salt rejection with coated membrane
- No Significant fouling during 30 days of operations
- Lower recovery during high TDS feed water (as expected)
TDS vs % Recovery
Summary Project on Schedule Five Deliverables completed in 2010. Four Deliverables by Apr 2011. Energy savings greater than 35% is
possible using novel UT coatings Energy savings of greater than 40% is
reflected in GTI work with electrodialysis On track with achieving performance
goals
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Thanks