Exploration and Production Technologies
Swellable Organosilica Materials to Clean Produced Water Last Reviewed 6/3/2016

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, OH 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.

 

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 fracturing 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 flowback and produced waters.

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, 3600 gallon 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 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 (liquefied petroleum gas [LPG] and refrigerant R134a) are suitable for use in the liquid-gas extractor for regeneration of Osorb.

Sub-project A: Define and refine the business value proposition

Received refinery wastewater contact list from DawnBreaker as part of the CAP. Conducted an analysis of the strengths, weaknesses, opportunities, and threats (SWOT) of the refinery wastewater treatment process and learned that most refineries utilized large environmental engineering firms (LEEFs) to manage their waste treatment. Determined that “selling” to the LEEFs was the best market entry strategy to gain access to refineries and to general industrial wastewater treatment. Developed a list of LEEFs and other competitors/potential customers for industrial wastewater treatment applications. Conducted SWOT of these companies for the mid-west region. Hired (contracted) an environmental engineer salesman to gain access to this market segment. Contacted many of these LEEFs and industrial wastewater treaters and have soft booked the pilot-scale Industrial Water Treatment System (ITS) for the first quarter of 2016 at three locations. Sales presentation prepared to explain advantages of using the regenerable Osorb media powered ITS unit.

Sub-project B: Identify the Osorb media types with best value Media Update

Determined that several industrial water treatment situations are present in the market.

 

Several absorbent medias were evaluated for potential use in the Industrial Water Treatment Unit.   Specifically, two different medias were invented for water treatment and regeneration: (1) Sorbit™ media and (2) a newly developed, blended, low-cost silica-based media.

(1) Sorbit media

Sorbit media is an absorbent organosilica that was specifically designed for use in a fixed-bed, flow-through column system. The Sorbit media has been fully characterized at lab-scale.  Scale-up production was accomplished.  Sorbit media is in testing for toluene removal and 100-cycle regeneration in the prototype unit and is acceptable. 

 

(2) Blended media

Is in the R&D process; see current status.

 

Previous efforts had been focused on the development of absorbent coated sand materials, which resulted in an inert silica core with tens of micron thick coatings of absorbent media covalently attached to the surface. This media lacked in capacity due to the very low weight percentage of active media (<0.1% by weight absorbent media), and was determined to be better suited for water polishing applications.

 

Sub-project C: Design, fabricate, and evaluate a modular, integrated treatment system.

A prototype system was designed, fabricated, and automated that can treat contaminated water at a flow rate of 0.5 L/min.  The prototype unit was designed with integrated regeneration and is capable of continuous running. The regeneration is accomplished by flowing liquefied gaseous hydrocarbons through the laden Osorb media. The prototype unit was stress tested by continuously running 100-cycles of water treatment and butane regeneration. Additional stress testing continued by running 100-cycles of water treatment and regeneration to evaluate the lower-cost propane. The prototype unit achieved water treatment reduction of around 98% of dissolved aqueous contaminants. Operational data was collected on the prototype to learn about water treatment performance, media degradation, butane/propane consumption and operational costs. Design characteristic were developed from the prototype unit to guide the 15 bbl/hr (10.5 gpm) pilot scale unit, sub-project E.

 

Sub-project D: Determine the effect of Osorb pretreatment on bio-digestion (typical wastewater treatment)

The 60-day bioassay testing was performed using activated sludge with synthetic wastewater to compare changes of biodigestion capacity in Osorb treated vs. non-treated wastewater. The results showed that Osorb pretreatment not only provides a significant removal efficiency of recalcitrant contaminants from water, but also acts as a buffer that minimizes high stress conditions in biodigestion processes. Excessive foaming problems were observed in the non-treated activated sludge unit over time while no foaming issues were observed in the Osorb treated activated sludge unit. This indicates that biologically toxic contaminants in the non-treated water can cause activated sludge process upset, creating foaming problems.  Initially 5-10% faster degradation rate, measured by chemical oxygen demand (COD), was observed in the Osorb treated unit compared to the non-treated unit.  However, no significant difference of biodigestion rate between the non-treated and treated unit was observed over time even though there appeared to be a distinctive difference of the foaming problems.

 

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

An engineering firm that specializes in equipment and complete system design was contracted to scale-up and design the equipment package for the pilot scale ITS unit, (ITS-10).  The engineering firm is conveniently located in Wooster, OH.   For this phase of the project, the company will provide design services including, Process Flow Diagrams, Process and Instrumentation Drawings (P&IDs), Electrical Control Schematics, and the other usual design products. This process is about 30% complete at this writing and the complete design package is due mid-December 2015.

 

Current Status (June 2016)

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 U.S. Environmental Protection Agency (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.

Current research has focused on ruggedness of the blended media that was previously developed. 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 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-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 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 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.     

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)
If you are unable to reach the above personnel, please contact the content manager.