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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

8

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

9

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: tom.hayes@gastechnology.org

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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