1

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

2

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

3

4

Major Participants

BSWCMC & ASWCMC GTI Staff and Consultant University of Texas Bureau of Economic Geology Texerra GeoPure/Texas A&M

5

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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7

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)

8

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

42

Sampling Points Raw Water Pretreated Water Concentrate Streams Product Water Streams

43

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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

66

(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

67

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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73

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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