02-10ER85986

Goals
The goals of this project are to (1) develop and improve several water treatment technologies to remove dispersed and dissolved organic species from produced water with a focus on flow back water treatment and (2) develop a production process to make these technologies commercially viable.

Performer
Absorbent Materials Corporation (ABS Materials), Wooster, Ohio 44691-0000

Background
The primary commercial and research focus of this project is the treatment of flow back water resulting from gas field hydraulic fracture stimulations. Unconventional natural gas is an important growing domestic energy supply typically found in shale plays. Access to shale gas has been made possible with the development of hydraulic fracturing technology (frac) where water, proppant (graded sand), and a mix of chemical additives are injected under high pressure to induce fractures in shale formations for gas extraction. At the conclusion of the frac process, the well is depressurized and 10-40% of the water is recovered from the system. This flow back water generally contains high levels of dissolved solids, fracing chemicals, and hydrocarbons extracted from the formation. The challenge industry faces is determining what to do with the flow back water. The Energy Information Agency (EIA) projects shale gas natural gas production will continue to grow, reaching 45% of the total volume of produced U.S. natural gas by 2035.Thus, advanced methods to treat flow back water are important for developing this substantial domestic energy source.

Flow back water is an amalgamation of dispersed oil, dissolved volatile and semi-volatile organics, organic acids, metal ions, radionuclides, oilfield treatment chemicals, salt, polymers, insoluble material (rock dust, organic species), or any combination of these. Several treatment techniques separate dispersed oils from water. These methods take advantage of the density difference between oil and water, thus functionally removing solids or dispersed oils from the water. However, very little effective technology exists to address dissolved hydrocarbons, slicking agents, and polymers, which can prevent flow back water from being recycled or discharged.

This project examines a novel and innovative solution to treat flow back water dissolved organics by using swelling glass - Osorb®, which is an engineered organosilica material with high porosity. Osorb functions as nanomechanical sponge since the porous matrix rapidly swells up to eight times its dried volume upon exposure to non-polar liquids. Osorb® does not swell in water, but is highly effective at removing a wide range of free or dissolved organics from water, including polar species (such as alcohols and carboxylic acids) and non-polar species (such as toluene, benzene, naphthalene, nonane, octane, and 90% of naturally occurring organic acids). The swelling process is completely reversible—with no loss in swelling behavior even after repeated use (at least 100 times)—when absorbed species are evaporated by heating the material. The goal is to engineer Osorb-based materials into systems that will reduce flow back fluid clean-up costs, effectively clean flow back water streams, and create purified water that can be safely discharged to the environment. Recovered hydrocarbon products can be sold or used as fuel to power the purification system.

Impacts
Successful development of the Osorb-based materials to remove hydrocarbons and organic process chemicals would benefit the treatment of flow back water and produced water in the following ways:

• Significantly reduce water storage and disposal costs.
• The portable treatment unit would reduce off-site water hauling and associated costs.
• Water can be recycled for fracking operations or returned as agricultural water in arid regions
• Modification of the base Osorb® formulation may allow for selective removal of metal and/or radionuclide contaminants from Marcellus Shale flow back and produced waters.

Accomplishments
The project has completed all Phase I objectives. ABS Materials, in conjunction with three global oil service companies, designed and built a trailer-mounted, 1,000 gallon per hour (gal/hr) flow back water purification system for field use. The trailer mounted system was demonstrated to several global oil company representatives at ABS’s Ohio headquarters. One major oil services company, with a scientific leadership present, contracted to conduct a full pilot test in the field using produced water from the Clinton formation (Ohio) in July 2010 and March 2011. Total petroleum hydrocarbon (TPH) levels were reduced from 227 mg/L to 0.1 mg/L during testing. TPH is a more stringent measurement than oil and grease indicating the treated water was well below the discharge threshold of 29 mg/L. This test successfully demonstrated the effectiveness of Osorb® in a large system.

A skid mounted unit using 3 kg of Osorb® was used in field tests conducted on Eagle Ford hydrocarbon-rich slop water at the Texas A&M Global Petroleum Research Institute. Independent laboratory testing was conducted on the water after testing in all trials with positive results. The unit decreased oil and grease levels from 11.5 mg/L to below detectable limits.

Current Status (November 2011)
Outside of this project, ABS Materials continues to further engineer its 1,000 gal/hr trailer mounted unit and plans for additional pilot testing in Ohio, Wyoming, and Calgary (Canada). The skid mounted unit will be tested in the Marcellus Shale during the same time period.

ABS Materials investigated high molecular weight polymer removal methods. The results were reviewed, and a major petroleum company will pilot test the trailer mounted system in the Wyoming unconventional gas fields.

ABS Materials has begun bench-scale testing to develop forms of Osorb® that co-extract radionuclides (ex. ²³⁵U, ²¹²Pb, ²²⁸Ac).

Project Start: June 19, 2010
Project End: August 14, 2013

DOE Contribution: $99,995
Performer Contribution: $75,000
Loan/Donated Materials: $100,000

Contact Information
NETL – John Terneus (john.terneus@netl.doe.gov or 304-285-4254)
Absorbent Materials Corporation (ABS Materials) – Paul Edmiston (p.edmiston@absmaterials.com or 330-234-7999)
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