Exploration and Production Technologies
Swellable Organosilica Materials to Clean Produced Water Last Reviewed 11/30/2015

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 full-scale 60 bbl/hr (42 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 (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 the business value proposition

Received refinery wastewater contact list from DawnBreaker as part of the CAP (commercialization assistance program). Conducted SWOT (strengths, weaknesses, opportunities, threats) of the refinery wastewater treatment process and learned that most refineries utilized LEEFs (large environmental engineering firms) 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 ITS (Industrial Water Treatment System) for 1st qtr 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.  Results for this phase of testing are anticipated for December 2015.

(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 (industrial treatment system) unit, (ITS-10).  The engineering firm is conveniently located in Wooster, OH.   For this phase of the project, the company will provide design services e.g., 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.

 

Several possible equipment builders have been identified and contacted.  They are being evaluated currently, for constructing the pilot scale unit and possibly commercial units starting in 2016.

Current Status (November 2015)

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

Continuing contacting the LEEFs (large environmental engineering firms) to present and inform them of the novel wastewater treatment technology. Sales calls and soft scheduling pilot unit ITS field trials are proceeding with a goal of two dozen field trials scheduled by 2nd quarter 2016.

 

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

Blended media

R&D efforts have been focused on the production of media for the treatment of high volumes of water with low (<10 ppm) contaminant levels. Water velocity through a fixed bed must be below a maximum limit so pressure drop and pumping energy are not excessive. This new blended media is useful in situations where large amounts of media are required to keep flow velocity below the maximum limit. It is significantly less expensive, so large amounts can be used without driving the system cost up. It has less capacity than other Osorb media, but this reduced capacity is adequate for water with low concentration of contaminants. This media has been evaluated at lab-scale, and production scale-up is planned for the coming weeks.

 

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

Operational data is being collected on the prototype to extend learning's about water treatment performance, media degradation, butane/propane consumption, and operational costs.  Design characteristic will be updated from the prototype unit to guide the 15 bbl/hr (10.5 gpm) pilot scale unit, sub-project E.  Information will come from the 100-cycle Sorbit and the follow-on 100-cycle testing of the blended media

 

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

Further bioassay testing is scheduled in Q1 – Q2 2016 using real industrial wastewaters with modification of current experimental set-up,

 

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

For this phase of the project, the contracted design engineering company will provide design services e.g., 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.

 

Several possible equipment builders have been identified and contacted. They are being evaluated currently, for constructing the pilot scale unit and possibly commercial units starting in 2016.

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.