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D.B. Burnett Global Petroleum Research Institute Texas A&M University Rich Haut Houston Area Research Center Tom Williams Matagorda Redfish Society Marian Higgins CMGC Foundation

New Technologies for Gas Exploration and Production

GPRI

• EFD Program – an award winning program focused on reducing environmental footprint associated with oil and gas operations. Produced water and frac flowback brine emphasized

• Technology Integration Program– an $ 8 million program designed to bring new technology to field trials – gas shales

• Advanced Analytics Program – new program designed to identify and field trial advanced analytic methodology for high brine quantitative analysis.

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The Way We Used to Look at Petroleum Resources

A New Vision of Fossil Energy

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1970 1980 1990 2000 2010 2020

Barnett Shale

Fayetteville Shale Haynesville Shale

Marcellus Shale

Eagle Ford Shale

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Texas A&M University GPRI Team’s Successes: 1997 –First University Program Addressing Barnett Shale Productivity 2001 First Major University Research Program on Treatment of Produced Water 2005 First Functional Membrane Technology for Produced and Frac Flowback Brine 2005 First University Program Addressing Environmental Issues in Oil & Gas Drilling 2007 First EFD “Scorecard” Proposed 2008 “Disappearing Roads” Program 2009 University/National Labs Alliance 2009 Eagle Ford Shale EFD Study 2010 EFD A&M Marcellus Shale Pre-Treatment Field Demos 2010 EFD EU Program Started 2011 Frac Flowback Brine Analytical Technology Partnership 2012 Pennsylvania Field Trials – Pre-Treatment 2012 EFD Technology Program Funded

Advanced Water Treatment Technology

Details of Pre-Treatment Technology

Water

Identifying Key Technology Components

Micro Filtration (MF) (10-0.1µm) Bacteria, suspended particles

Ultrafiltration (UF) (0.05-0.005µm) Colloids, macromolecules

Nanofiltration (NF) (5e-3-5.e-4 µm) Sugars, dyes, divalent salt ppts.

Reverse Osmosis (RO) (1.e-4-1e-5 µm) Monovalent salts, ionic metals

Raw Water Source

Reverse Osmosis

One Day Supply Tank for Raw Water

Large particulate removal

Oil & Grease removal

BETEX Removal

TSS removal

Hardness Removal

Desalination

pH, Temp., Conductivity, turbidity,

Turbidity, O&G, BETEX

Turbidity, O&G

Turbidity, BETEX

Turbidity, BETEX, Conductivity

pH, Conductivity

pH, conductivity,

Process Component

Identity Description Analytical Tests

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How Frac Flowback Brine is Cleaned Up for Re-Use

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• Escondido Resources Webb Co. Texas - 2 week test

• Range Resources Washington Co. PA - A 5 week test BG Exco Group Tioga Co. PA -3 week test

Pre-treatment, oil removal, microfiltration, nanofiltration On-site analytical

Eagle Ford Field Trials

Mobile Unit On Site – New York

Mobile Unit On Site – Pennsylvania

Mobile Unit On Site – Pennsylvania

Suspended Solids Removal • Microfiltration reduces the need for

coagulation/flocculation chemicals • Important fact: IT’S THE WATER

CHEMISTRY! • The key to successful adoption of

micro-filtration for solids removal lies in the design of the process train that avoids filter fouling.

Suspended Solids Cont’d. • Spiral wound and hollow fiber (MF) • Most are made of polymeric materials,

for the most part asymmetric • The A&M system also uses UFs that can

be reverse washed to reduce fouling • Three types were employed in the trial,

ceramic, stainless steel, and capillary hollow fiber

Solids Removal

Suspended Solids Filter Assembly

Nano-Filtration • Selective for reducing alkalinity and

other certain dissolved solids • Not yet embraced by the O&G industry • Removes divalent ions to create

thermodynamically stable brine • Results Review

NF Results

Why is Treatment Important? Decline in productivity and that occurs in gas production – greater than reservoir engineering predictions

Treated and Untreated Frac Pond Brine, Eagle Ford, 2011

Example of Produced Water: Marcellus

Opposite the membrane wall is the counter for the analytical equipment.

WWW.efd-aas.org

Current Status of Gas Shale Industry Shale Gas Water Treatment Catalog

Treatment Type Water Treatment Category

Water Treatment Subcategory

Primary/Desalination

Thermal Distillation/Evaporation

Vapor Compression

Crystallization Evaporation

Membrane Reverse Osmosis Electrodialysis/

Electrodialysis Reversal

Pre/Post Suspended Solids/Heavy Metals

Media Filtration

Flocculation Settling

Water Softening Ion Exchange Microbe Removal Biocides

UV Light Ozone

Ultrasound Treatment

Considerations Scale Inhibitors

pH Adjustments Blending/Mixing

Treatment Vendor and Shale Gas Basin Matrix

Shale Gas Basins

Treatment Technology

Barrnett Marcellus

Haynesville

Fayetteville

Woodford

Thermal Distillation

Fountain Quail INTEVRAS GE Water & Process Tech.

Fountain Quail Aquatech AltelaRain INTEVRAS GE Water & Process Tech

Total Separation Solutions

Fountain Quail INTEVRAS GE Water & Process Tech.

Reverse Osmosis Geopure Ecosphere

Veolia MI SWACO

Ecosphere

Geopure Ecosphere

Crystallization INTEVRAS Veolia INTEVRAS Aquatech

UV Light Ecosphere Hailliburton

Ecosphere

Ecosphere

Ozone Ecosphere Ecosphere

Ultrasound Ecosphere Total Separation Solutions

Ecosphere

Ecosphere

Electrodialysis Use of this Technology has been considered but is currently not being utilized as a desalination treatment technology by the Shale Gas industry.

Electro - Membrane Electrodialysis Use of this Technology has been considered but is currently not being utilized as a

desalination treatment technology by the Shale Gas industry.

No current U.S. Patents for Industry Leaders No technical papers citing results in high brine systems Current literature reflects process designs for ultra pure water needs or specialized chemical reactions Research programs directed toward applied research “ research program concerning the use of electro-membrane processes in general and bipolar membrane technology in particular

www.gpri.org

Question and Thank You! Contact info:

Membrane Technology Projects: David Burnett, Frank Platt, Carl Vavra

Texas A&M- EFD Technology Phone: (979) 845-2272

E-mail: burnett@pe.tamu.edu