Exploration and Production Technologies
Swellable Organosilica Materials to Clean Produced Water Last Reviewed November 2016

02-10ER85986

Goal
The project is targeted at a more general solution of improving refinery wastewater treatment. Successful completion of the revised Phase IIB goals will allow ABS Materials to provide a more applicable technology solution by capturing a broad range of organic compounds from a variety of refinery process waste streams. Some of these organics are valuable feedstock, so the capture and return function of Osorb Media is useful. Osorb Media is a regenerable, organically-modified silica adsorbent utilized for the treatment of oilfield water and gas streams. The project will create a commercial treatment system by building on development work performed recently and in the previous stages of this SBIR.

Performer
ABS Materials Inc., Wooster, Ohio 44691-9359

Background
The main goal of this project is to improve refinery wastewater treatment. A secondary emphasis of the project will be to recover adsorbates as new feedstock. Captured hydrocarbons regenerated from the Osorb Media will be in a manner where they can potentially be introduced back to the refining operations, reducing waste, and increasing output and revenue.

The integrated treatment system will be tested on wastewater from jet-fuel washing. Chevron has indicated there are waste streams from several other refinery processes that would benefit from use of this system. Two potential additional refinery wastewater streams identified are: 1) stripped sour water, and 2) desalter water. The project is aimed at general refinery wastewater treatment, applicable to all refineries and other industrial wastewater streams.

ABS Materials will utilize the Commercialization Assistance Program (CAP) support of DawnBreaker (a business acceleration company funded by the grant), to assist in identifying other applicable markets, obtain introductions to other refinery operators, and conduct reviews of Commercialization Plans.

Technical Objectives:

The project going forward has been divided into seven major sub-projects (A-G), with the first four sub-projects being completed concurrently. The last three sub-projects (E-G) will be completed sequentially after the first four sub-projects are finalized. These sub-projects and the goals of each are as follows:

 

Sub-project A: Define and refine the business value proposition to steer the treatment system designs toward providing high-value solutions to refinery wastewater problems.

 

Sub-project B: Identify which Osorb Media types provide the best value, including performance and cost.

 

Sub-project C: Design, fabricate, and evaluate a modular, integrated treatment system. There will be three versions of the integrated water treatment system: bench-scale and prototype systems are covered in sub-project C; a pilot unit for use in performing on-site treatment is covered in sub-project E. The goal is to create a rugged commercial system that conforms to industry requirements.

 

Sub-project D: Determine the effect of Osorb pre-treatment on bio-digestion (a typical wastewater treatment), to help quantify the value of the pre-treatment process with regards to removing compounds that hinder microbial action.

 

Sub-project E: Design and fabricate a pilot scale, 15 bbl/hr (10.5 gpm) modular water treatment system.

 

Sub-project F: Conduct field trials of the pilot system at a refinery test facility and other suitable industrial water sites.

 

Sub-project G: Prepare designs for a second generation 15 bbl/hr (10.5 gpm) modular water treatment system.

Accomplishments

Phase II, and IIB
ABS Materials has completed all Phase I objectives. ABS Materials, in conjunction with three global oil service companies, designed and built a trailer-mounted, 3,600 gallons per hour (gal/hr) flowback water purification system for field use. One major oil services company, with scientific leadership present, contracted to conduct a full pilot test in the field using produced water from the Clinton Formation in 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.

ABS Materials constructed PWU 1.5, a 65 gal/min fully automated treatment system mounted on a 53 ft. drop-deck trailer, and conducted successful wet testing in June 2012 with fresh water only. Wet testing with the addition of Osorb and the recovery of Osorb from the fresh water was successfully completed in August 2012. The recipient conducted a pivot based on the projected costs of running the PWU 1.5 system and the changing value proposition for onsite treating of flowback water vs. sending it to a disposal well. A pilot unit (VOC Capture Unit) capable of a 1 bbl/min flow rate was designed and built based on a replaceable cartridge design. The VOC Capture unit is being used on contaminated industrial waste and the lessons learned are being utilized to improve both the pilot unit design and provide a means to evaluate Osorb regeneration concepts. Industrial wastewater was used as a substitute for produced water in these field trials. The system is modular in design allowing for easy scale up to higher bbl/min flow rates. The replaceable cartridge design for the pilot system virtually eliminated the loss of Osorb during capture and regeneration processes. The two main cost drivers for using Osorb technology are the base cost and costs associated with regeneration. The project has focused significant effort on reducing the cost basis for Osorb through increased manufacturing procedures. A second equally important focus was on the regeneration process.

The cost basis for producing the base Osorb Media continues to be driven down through improved manufacturing processes, reduced labor, distillation and re-use of solvents, and improved particle grinding and recovery efficiencies. Additional cost reduction activities continue with 100 percent of the cost reduction goal expected to be met over the next 6 months ABS Materials initiated an additional regeneration approach to utilize liquid butane as the regeneration solvent plus heat process. The approach is to pass liquid butane through oil-laden Osorb to remove the oil via a gas reclamation pump. Pilot-scale testing has demonstrated 75 percent oil removal. A small-scale butane extraction system has been built to further explore this approach with the goal of replacing butane with liquefied petroleum gas in follow-on designs.
The liquid butane extractor was redesigned to improve cleaning effectiveness and perform regeneration of the contaminate-laden Osorb. The new design removed +99 percent of oil from water-wet Osorb. The project team demonstrated that other low boiling gases (LPG [liquefied petroleum gas] and refrigerant R134a) are suitable for use in the liquid-gas extractor for regeneration of Osorb.

Sub-Project A: Define and refine business value proposition.
The targeted industrial wastewater market (IWM) was segmented into 3 segments: 1. On-site, 2. Replace/enhance on-site tertiary treatment, and 3. Transfer Storage Disposal Facilities (TSDFs). Contact and lead development priorities were assigned to the three segments. The IWM companies in the six-state region centered on Ohio were identified by their EPA discharge permits. Nine field trials were conducted at four locations to test the method of identifying suitable target IWM companies based upon the EPA discharge permits. Specifics of the field trials are provided in sub-project E. Discussions with three subject matter experts in IWM were conducted to verify value propositions for Osorb technology. The Osorb water treatment technology was presented to three large, global water treatment corporations via their Innovation Portals, to gain faster market penetration by developing business relationships. The Osorb wastewater treatment technology is being marketed under the tradename, Regenex™ ITS.

Sub-Project B: Identify the Osorb media types with best value.
Past research was focused on ruggedness of the blended media developed previously. Preliminary testing within the prototype unit using the blended media resulted in an observed decreased capacity for contaminants as the water treatment/regeneration cycled. This likely indicates that the absorbent media is delaminating from the inert core in the blended media. To prevent this delamination from occurring, there has been an effort to functionalize the surface of the inert core to promote polymerization of the absorbent media onto the surface of the inert core. This modified blended media is currently being evaluated at lab-scale, and production scale-up will be planned for the coming months.

Additional R&D efforts have been focused on the development of media for the improved capture of mid-range partition coefficient contaminants (log Kows 1.3 to 1.9). A variety of media samples have been synthesized and evaluated at lab-scale for the removal of contaminants that are slightly more hydrophilic, which would expand our treatment capabilities. These medias have been made through modification of the polysilsesquioxane matrix to impart more hydrophilic chemical functionality and/or modify the pore structure of the media. This testing will continue into the third quarter of 2016.

Sub-Project C: Design, fabricate and evaluate a modular, integrated treatment system.
It was found that the blended media was not suitable for repeated regeneration cycles. The Sorbit media was found to be both effective at capturing contaminants and having excellent durability through 100 regeneration cycles.

The effectiveness of contaminated media regeneration was evaluated by analyzing the effluent and targeting the back diffusion of the target compound. As expected, the duration of the regeneration is directly correlated to effectiveness of the regeneration cycle. These duration values will be utilized as guidelines for regeneration cycles in the mobile, modular treatment system, sub-project E.

Sub-Project D: Determine the effect of Osorb pretreatment on bio-digestion.
Bioassay testing was performed using activated sludge and industrial wastewater to evaluate the effect of Osorb pre-treatment on biodigestion capacity. The industrial wastewater was obtained from one of the client sites. Significant results are that Osorb treated industrial wastewater exhibits minimal foaming vs. a non-treated wastewater in activated sludge units. The biodigestion rates were equivalent. Biodigestion rates were measured by chemical oxygen demand (COD) determinations. We conclude that Osorb treatment would be more feasible and beneficial after biological treatment processes as a polishing step.

Sub-Project E: Design and fabricate a pilot scale, 15 bbl/hr (10.5 gpm) modular water treatment system.
An industrial design firm was hired to conduct engineering and design work for the 10.5 gpm Regenex-Industrial Treatment System (ITS). A local (Cleveland, OH) manufacturing/fabrication firm was recommended and selected to build the first unit. The fabrication company specializes in oil and gas, and refrigeration equipment. The media regeneration process involves compressing hydrocarbon gas to liquefy it in a similar manner to refrigeration equipment. The final design of the unit includes two treatment vessels filled with ABS Materials’ regenerable media. The unit treats water in one vessel while the other is regenerated. Continuous operation (24/7) is obtained by switching vessels when the media in vessel one gets saturated, and regenerated while the media in vessel two comes online to treat the wastewater. The system will be 100% automated and configured by the fabricator.

The dimensions of the unit are 6 ft x 20 ft x 7 ft tall, and weighs 8,500 lbs. This first unit is intentionally being built with space between components. This component spread will facilitate improvement modifications, serve for highlighting unit features, and provide clear identification of components for prospective clients.

The fabricator is in the process of laying down the main components of the unit. The unit is expected to be completed and shipped to ABS Materials by July 2016 after acceptance testing. The completed unit will fit onto a covered, 24-foot trailer for easy field deployment and customer evaluation purposes.

Sub-Project F: Field Trials with 15 bbl/hr modular treatment system.
A portable 10.5 gpm (15 bbl/hr) treatment only unit was developed for field trials while the fabrication of the complete modular treatment unit (Sub-project D) is underway. A total of nine field trials were conducted at four client sites. The clients consisted of two, 10-day, Transfer Storage and Disposal Facilities (TSDF), one full service TSDF, and one industrial wastewater processor. Four trials were determined to be successful for Regenex because COD, chlorinated solvent or Oil and Grease (O&G) components were significantly reduced/eliminated from the treated effluent. Five trials were determined to be not suitable for Regenex because conventional filtering removed the suspended solids where the contaminants were adhered. Information gathered from all field trials are useful in identifying suitable wastewater markets. Additional field trial sites are continuing to be scheduled.

Sub-Project G: Design and fabrication of second generation 15 bbl/hr modular treatment system.
ABS Materials is working on the design for the second generation of the modular treatment system. The main goal is to shrink it in size and weight. The future modular system will be 6ft x 9ft x 6 ft tall. The unit will be more compact and enclosed.

ABS Materials is working on the bill of materials (BOM) provided by the fabricator. The goal is to identify individual components and their cost and look for alternative, less expensive options for lowering the cost of the second generation of Regenex ITS. ABS Materials’ goal is a 35% reduction on the total cost of the unit in both component and labor.

Current Status (November 2016)
Sub-Project A: Define and refine business value proposition.
Testing of market acceptance of Regenex technology was conducted in several market segments. Evaluation within the Essential Oils market space (mint oil) was found to have a favorable response. Market testing within the TSFDs space has also found acceptance in the capture of sparingly water-soluble, hazardous organic compounds, while those organic compounds that were water soluble were not favorable within this segment. Industrial wastewater from chemical plants shows promising results/acceptable in some circumstances. The industrial chemical plant wastewater needs to be devoid of water soluble polymers in order for successful contaminant capture/treatment. Industrial wastewater streams that are composed of a few organic chemicals vs. a “soup” of them are better suited for Regenex technology.

Sub-Project B: Identify the Osorb media types with best value.
The specially engineered Sorbit™ media is the appropriate Osorb technology based media for Regenex usage. The Sorbit media is a non-volumetric swelling version of Osorb media. Sorbit media has comparable capture efficiency and chemical holding capacity to the flagship standard Osorb media. There a manufacturing cost advantage for Sorbit media.
R&D efforts have been focused on the development of media for the improved capture of mid-range partition coefficient contaminants (log Kows 1.3 to 1.9). These medias have been made through modification of the polysilsesquioxane matrix to impart more hydrophilic chemical functionality and/or modify the pore structure of the media. Testing of these medias with benzaldehyde (log Kow 1.48) demonstrated a 10-30 % capture increase compared to standard Osorb media under test conditions. Sample media was provided to the target customer for their internal evaluations, and no feedback has been received as of this writing.

Sub-Project C: Design, fabricate and evaluate a modular, integrated treatment system.
The lab-scale integrated treatment system (0.15gpm) continuous to be utilized to conduct media regeneration studies of select organic compounds identified from field trial events. The effectiveness of liquefied propane and duration of recirculating the liquefied propane provides a decision basis for conducting a full field trial. The lab-scale unit continuous to provide R&D opportunities and validation for select short-term projects that support proposals for new business development.

Sub-Project D: Determine the effect of Osorb pretreatment on bio-digestion.
This portion of the project was completed during the spring of 2016. Details can be found in the “Accomplishments” section above.

Sub-Project E: Design and fabricate a pilot scale, 15 bbl/hr (10.5 gpm) modular water treatment system.
The final fabrication and acceptance testing of the fully integrated, operationally functional 10.5 gpm wastewater treatment unit was the main work focus during this reporting period. The industrial wastewater treatment technology is being commercialized under the tradename of Regenex. The Regenex pilot-scale treatment system was mounted on a gooseneck style trailer and is protected during over-the-road transit to field trial sites by a retractable tarping system. The Regenex 10 unit (pilot-scale) along with the design drawings, BOMs, and operating procedures are secured and stored at the ABS Materials HQ site.

Sub-Project F: Field Trials with 15 bbl/hr modular treatment system.
The Regenex 10 unit has been deployed on four field trial sites as of November 2016. The Regenex has been deployed to Indiana for essential oil market evaluation, to Michigan for TSDF market evaluation, to Ohio for Industrial wastewater market evaluation, and to Virginia for Chemical plant wastewater market evaluation. Lessons learned from each field trial location are being utilized to focus sales and marketing efforts to support the successes in those market segments.

Sub-Project G: Design and fabrication of second generation 15 bbl/hr modular treatment system.
Lessons learned during the operation and performance of the Regenex 10 unit while on these four field trials were prepared, collected, and analyzed. Re-design improvement needs were assembled for the next generation Regenex 10 units. The search for alternative heavy equipment manufacturers with the required capabilities is actively proceeding. Site visits to some potential manufacturers have been completed. Several potential manufacturers have provided building/manufacturing estimates. Additional potential manufacturers are scheduled for meetings within the next few weeks, with manufacturing estimates to shortly follow those meetings. The goal is to be able to leverage the various, potential suppliers to obtain a favorable manufacturing cost for the next generation Regenex units. The team envisions utilizing the engineering capabilities at the select firm(s) to design both the 50 gpm and 100 gpm Regenex units when these flow rate models are required.

Project Start: June 19, 2010
Project End: August 14, 2016

DOE Contribution: $2,074,036
Performer Contribution: $175,000

Contact Information
NETL – John Terneus (john.terneus@netl.doe.gov or 304-285-4254)
Absorbent Materials Corporation (ABS Materials) – Stephen Jolly (s.jolly@absmaterials.com) or 330-234-7999)