Problems and Solutions

The current approach to managing these wastes is an unsystematic collection of waste treatment and disposal methods, impacting both in and out of state facilities and involving hundreds of subcontractors, each with a defined approach and small part of an overall solution.

There are two fatal flaws currently inhibiting effective treatment of high volumes of oil-and-gas generated wastewater and solids:

(1) Dissolved organics and monovalent salts (Na+ and Cl-) in wastewater are not easily removed to concentrations that would allow for large-scale water treatment technologies to prosper.  The required level oftreatment needed to deploy larger wastewater treatment systems is 5 ppm total organics (TOC and/or total VOCs) and 10,000 ppm TDS with few divalent cations present and no TENORM.

Similarly, organic concentrations less than 500 mg/kg and chloride leaching less than 250 mg/l are desired for solids.  If an integrated waste processing system can achieve these levels, then larger establishedsystems deploying reverse osmosis, nanofiltration, or accelerated land farming can be used to treat high volumes to very clean standards for potable or agricultural use or for beneficial reuse.

(2) The cost of treatment must be economical with high throughput. Operators identify $1.00/bbl cost and 10,000 bbl/day as breakeven points to economically treat wastewater.  Similarly, Solid waste disposalfees at $30.00/bbl and 2,000 bbl/day are desired.  These conditions are not currently met in the industry and a myriad of “new” technologies are deployed annually to attempt to solve the stated concerns.Current economics define wastewater treatment costs at >$7.50/bbl to as high as $12.00/bbl with throughput values commonly around 2,500 bbl/day. 

Solid treatment costs for cuttings are approximately $65/bbl and technology-limited to 1,000 bbl/day. Solid waste petroleum concentrations rarely fall below 10,000 mg/kg and are commonly seen at 50,000mg/kg.

Land farming fails to achieve the desired treatment levels.  

Landfill liners generally fail in less than a year or two and large major drill cutting pits and piles are known to leach salts and VOCs in plumes as large as tens of miles, threatening clean surface andgroundwater resources. Wet solids also present issues since the liquid must be sorbed prior to transport to eliminate free water.

Stabilizing agents such as fly ash, gypsum, and peat moss have been used. These additives increase waste volumes by a factor of 1.5 to 5 times the original value and fail to inhibit leaching even thoughfree water is temporarily bound for transport. Many of the stabilizing agents used add toxicity to the waste.

Denexyl® 201X effectively removes dissolved organic concentrations to levels less than 5 ppm total VOCs and TOC. Concurrently, vapor is mitigated reducing air pollution and odor.  By removingorganics, pulse electrocoagulation processes can effectively eliminate divalent cations without scaling including TENORM.  Finally, nanofiltration coupled with ion exchange can effectively remove TDSvalues by replacing Na+ ions with an atomic weight of 23 to H+ ions with an atomic weight of 1.

Chemionyx® systems can operate at a rate of 6,000 bbl/day at a cost of $1.20/bbl. Water treatment solids containing TENORM are bound in Ceramyx® and will not leach TENORM, salts, heavy metals orpetroleum organics.

Similarly, wet solids are also treated.  Denexyl® 103 and Denexyl® 104, at concentrations of 0.2%, effectively aid in extracting oil from solids and in enhancing demulsification of liquids from dewatering. Treated filter cake is rapidly treated in an accelerated landform with final concentrations at free- release values of 500 mg/kg or less.  The volume of oil recovered from water and solids is increased three-fold.

Produced and frack flow back waters contain waste that requires special treatment.  A number ofgeneral and specific issues with wastewater are noteworthy. In general, two conditions must be avoided:

(A) Drilling sometimes requires the use of dispersants to maintain drilling mud viscosity in porous media. The dispersants are organic emulsifiers containing anionic surfactants. These chemicals can foul anion exchange media (if used) and typically are companioned with high concentrations of condensate.

(B) Oil field maintenance often results in wastewater being removed from lagoon or tank bottoms. In these cases, waste constituents are concentrated at the bottoms and the wastewater can reach solid levels exceeding 25%, fouling electrocoagulation processes.

Specific chemical issues associated with wastewater must also be noted:

(1) Floating oil and sand must be removed before active treatment can proceed.

(2) Dissolved organics include both VOCs and SVOCs remain after treatment. Without removal, these petroleum contaminants render the wastewater unmanageable by membrane filtration. These organics have solvent characteristics and can dissolve expensive filtration membranes.

(3) Heavy metals present specific concerns as well including recalcitrant metals from the geology penetrated duringdrilling such as arsenic, chromium, manganese and selenium; all with unique valence potentials that allow them toremain uncaptured in typical pH ranges. Two other metals occur in predominant concentrations due to treatmentformulations including iron and aluminum. One anion – sulfate also occurs in relatively high concentrations. Theseelements/ions are floc‐forming. However, floc smaller than 25 microns is more difficult to remove and the interaction ofthese compounds in the presence of bacteria from drilling water, causes oxidation to occur and the fine floc settles atthe pond bottom. This black sludge can induce anaerobic conditions. As weather changes from winter to summer,turnover occurs and releases odor from this sludge.

Additionally, oil and gas practices add heavy metals of concern not identified in the lithology such as boron from borate molecules in frack packages, lithium from lubricants, and barium from barite in drilling mud. Some of these metals exceed background values and must be addressed for alternative disposal limits.

(4) TENORM is represented as a category of its own even though it is a heavy metal concern. The elements constituting TENORM are at the end of the radiological decay chains for parent materials of uranium and thorium. Theelements of interest are radium-226, radium-228 and lead-210. Only one of these is an alpha emitter.   Care must beexercised to not allow TENORM to concentrate in scale, filter cartridges or pond bottoms.

(5) Salts are also a concern primarily due to the issue that monovalent ions such as sodium and chloride are moredifficult to remove and concentrate in final solutions. Chlorides have a tendency to concentrate at higher levels thansodium due to their presence in gel frac packages.

Similar circumstances exist for solids as described with water chemistry. As a general concern the following must beobserved:

(A) Most drilling waste is fine grained materials in the #50 to #300 mesh size range with high concentrations of clay.Such materials are more difficult to treat due to expansive surface area and the tendency to form emulsions in thepresence of oil.

(B) In the presence of Barites and polymers used in gel fracking, solids often retain liquid gel characteristics. The gelmust be “broken” to enhance treatment.

A few specific issues associated with solids chemistry and handling are noted below:

(1) pH in solids is altered high to eliminate leaching.

(2) Drilling mud (invert) becomes unusable after 5-­‐7 drilling iterations and this “spent” mud must be stored in frack tanks. These tanks require special emptying and cleaning procedures.

(3) Wet solids must be off‐loaded into a sloped wedge shape tank with settling and pumping capacity.

(4) Effective solids treatment requires that the waste must not exceed 30% solids concentration.

(5)   Demulsification requires a minimum of 20 minutes and is typically a mechanical and not a chemical emulsion wheregun‐barrel systems will perform well.

Denexyl® insures that recalcitrant organic compounds are reduced to simple fatty acids and that heavy metals at risk of leaching are permanently bound in solids by altering the pH upward (>7.5 units), eliminating free ion status.

Ceramyx® and Plasmarok® ensure that high concentrations of heavy metals and/or organic residuals remain non‐leaching in beneficial use products, with little to no risk of dissolution back toelemental states. These solids handling concepts are incorporated into the designs referenced in this patent.

Several agencies are engaged oil and gas waste management practices, including State and County environmental agencies, State oil and gas commissions, Regional EPA offices,and federal agencies including the Bureau of Land Management, and United States Forest Service, depending on where wells are located.  These agencies must address oil andgas operator, waste facility owner, and public concerns. The oil and gas industry is under high scrutiny related to TENORM and fracking – both hot issues to environmentalists.The need for national petroleum independence and cost control is also critical in an industry recognized as a world economic driver.

Solution 3: The Recycled Material Facility (RMF) and development of a Public-­ Private-­Partnership brings interested parties together to control wastes produced in the oil and gas industry.

 The RMF concept creates a platform where all permitting (air, wastewater, solid waste, water quality, beneficial use) areas are represented. In this manner a comprehensive oversight program is automatically established. Twokey features of the RMF are also noteworthy regarding flexibility to adopt to changes in feedstock and or regulations: (A) the facility includes an injection well. Any liquid wastes of concern can be accommodated by the well.Deep injection may be preferable to land application at some point. (B) Wet solids are dewatered and the water created is recycled back to the treatment facility maximizing clean water outputs. In this regard, new legislation isbeing adopted to divert the use of freshwater from fracking to recycled water. Management of water in ponds and effective treatment creates clean recyclable water. This need is increasing with time to allow potable oragricultural grade water to be provided in drought stricken areas either for immediate use or aquifer recharge – even direct discharge to surface waters. The RMF is an excellent water management tool in an industry that useshigh volumes of water. From a different perspective, TENORM in oil and gas waste is a growing concern. The RMF provides the ability to effectively manage TENORM including waste produced by oil and gas and TENORMcurrently disposed in community landfills. By controlling blending using both community and oil and gas waste, TENORM can be easily maintained below levels of concern. This diverts a billion dollars of TENORM wastedisposal economy back to the community rather than to out-­‐of-­‐State hazardous waste facilities.

The greatest impacts are on traffic with increasing trucks on the highways. This degrades highways and bridges and increases the risk of accidents.  Oil and gas productiondemands immediately impact community waste services, including landfills and sewage from increased population and from some oil and gas waste streams that can belandfilled.

The pace of growth creates big environmental issues with waste disposal sites for solids. Millions of tons of cuttings are disposed either in pits at the drill pad or in a common landfill.  Oil and gas waste has organic potency and within less than year or two of disposal, often breaches synthetic liner systems, because petroleum waste includes organics with solvent properties incompatible with liners that ends up dissolving them. This leads to the development of contamination plumes typically containing benzene that leach into underlying aquifers and move towards lakes and streams placing them at risk of contamination.

Regulatory agencies struggle with deciding if it better to have 1,000 scattered out small pits or a few large ones. Neither solution addresses the issue.

Landfills are also expensive. Communities cannot afford to lose landfill space to oil and gas booms and be forced to construct new RCRA Subtitle C or D landfills with cell costs exceeding tens of millions of dollars for only several years of disposal. As an oil and gas production unit descends on a community, sewage systems are immediately overwhelmed and simple upgrades to them require years of approval and millions of dollars.

An RMF facility immediately removes the burden from the community with minor impacts focused only to the existing landfill and POTW.  A PPP designed around an integrated RMF would ensure that thecommunity and facility owner work and profit together with required public involvement. The community benefits by saving landfill space and having their waste contribute to energy production with profit.Often, the fees for water, sewage and garbage can be reduced or eliminated.  RMFs are also able to slowly mine existing landfills, especially at the end of the oil field’s life.  This allows the landfill to remain inuse without the need to construct expensive new cells.

More importantly, wastes seen by environmental activists as dangerous are removed from waste manifesting and are physically transformed into beneficial use products. This action eliminates the risk of thegroundwater and surface water pollution.  In consideration of the oil field’s life, even on‐pad pit and ponds can be mined and converted to energy and beneficial use products.  RMF permitting includes everyenvironmental department in State and local government and many in federal departments. This ensures that a multi‐agency and wide-spectrum stakeholder approach on media control basis to managingsensitive environmental targets in and around the RMF is considered.  Such interactions reduce environmental risk and provide comfort to the public.

Plasma Development Competitive Advantages:

  • A turnkey Recycled Material Facility (RMF) utilized as one‐stop‐shop for all oil and gas wastes of concern including wastewater and solids. The RMF adopts closed loop processing concepts on a regional basis with substantial benefits including: (a) total waste management, breaking the waste manifest process by creating beneficial use products and energy from waste; (b) reduction of truck traffic impacts on the community; (c) lengthening community landfill life and reducing the cost of POTW operations.

  • The RMF concept combines community waste with oil and gas waste for the ultimate benefit of the public through a negotiated Public‐Private-Partnership (PPP) with the impacted community and the waste facility representing the oil and gas operator’s waste interests. Principal benefits of the PPP are: (a) jobs, (b) revenue to the community from energy, (c) control of environmental risk including TENORM, (d) valuable products at a savings to community including road spray, road base and construction materials.

  • Chemionyx® technology provides two trade secret chemicals ‐ Denexyl® and Ceramyx®. Each chemical used in waste treatment overcomes past oil and gas waste treatment difficulties (wastewater and solids) and allows for high volume and efficiency treatment of wastes at low cost.

  • Gasplasma® technology converts community waste, oil and gas waste, and treatment process residues from the Chemionyx® technology to energy and inert Plasmarok®. This non-incinerating process is clean and green technology that can be sustained and controlled on a regional level with public input.