Exploration and Production Technologies
Swellable Organosilica Materials to Clean Produced Water Last Reviewed 6/30/2015

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 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. These combined improvements have resulted in achievement of 75 percent of the targeted cost reduction goal. 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. The potential for removing organics from jet-fuel wash water was investigated using a simple naphthenic acid (cyclo-pentyl-propionic acid [CPPA]).  Osorb media dosed with 25 weight percent CPPA was regenerated using liquefied butane (LB).  The LB removed 99+ percent of the CPPA from the Osorb media, enabling recovery of the neat CPPA.

Current Status (June 2015)

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

Initial market evaluations indicated that 89 of the 139 operating refineries within the USA process a significant volume of kerosene/jet-fuel from acid treatment plants (ATPs) and could be potential customers.  It was determined that some refineries use contract hazardous waste haulers/disposers to address hazardous wastewater disposal containing benzene and other ignitable substances at a $1.00/gallon rate.  The proposed solution would be able to remove the benzene and ignitable compounds at a lower cost, and return these recovered hydrocarbons to the refinery process stream.

 

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

Three months of analytical procedure development has provided the tools to measure both kerosene and naphthenic acid concentrations via GC-MS analysis with good reliability. Standard shake tests using jet-fuel wash water indicates that there are three versions of Osorb Media that exhibit adequate capture efficiencies. It was also determined that the hydrophobic Osorb Media was significantly more effective at capture of naphthenic acids at pH 2 than at pH 11 due to the protonation of the carboxylic acid moiety. Quantification work continues using a synthetic general industrial wastewater formulation to generate additional data for that market segment.

 

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

Modifications to the bench-scale liquid butane system were completed. They enabled investigation on capture and regeneration efficiencies of Osorb Media using a simulated wastewater. The simulated wastewater that was treated was a saturated aqueous toluene solution. This wastewater was successfully treated to >99% contaminant removal using Osorb Media. The Osorb Media was then regenerated using liquid butane to recover the absorbed toluene and enable additional treatment cycles. Osorb Media’s ruggedness was evaluated by conducting a thirty liquid butane regeneration cycles, with each cycle followed by thorough drying.  Any significant changes were tracked by particle size gradation changes and the capacity of the Osorb Media for toluene, following standard quality control methodologies. No significant differences from the starting data to the final (30th) regeneration cycle were observed.

 

The automated, prototype system is being constructed out of 316 stainless steel to duplicate the operational parameters of the bench-scale system. Final assembly is schedule for completion on June 5, 2015 and complete operational performance evaluation is scheduled for July 1, 2015. This system will be stressed by various wastewater streams. These waste water streams will include jet-fuel wash, and general industrial waste waters by ABS Materials. Changes in automation process flow, capture, recovery, and return of hydrocarbons features will be recorded for inclusion in the 15 gpm system of Sub-project E.


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

Ten liter glass bio-reactors have been prepared to conduct the comparative changes of bio-digestibility in Osorb treated vs. non-treated wastewater. An 8-foot fume-hood has been installed to conduct this research. Contractor delay in completing the exhaust duct work has put this installation behind by 2-weeks. Ducting for the fume hood is scheduled for completion the week of June 1-5, 2015. Initial experiments were moved into an alternative fume-hood and are progressing as scheduled.

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.

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