WO2014145825A1 - Procédé et système pour le traitement de l'eau et de fluides produits avec du dioxyde de chlore afin de les réutiliser - Google Patents

Procédé et système pour le traitement de l'eau et de fluides produits avec du dioxyde de chlore afin de les réutiliser Download PDF

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Publication number
WO2014145825A1
WO2014145825A1 PCT/US2014/030654 US2014030654W WO2014145825A1 WO 2014145825 A1 WO2014145825 A1 WO 2014145825A1 US 2014030654 W US2014030654 W US 2014030654W WO 2014145825 A1 WO2014145825 A1 WO 2014145825A1
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Prior art keywords
chlorine dioxide
aqueous
oxidant
fluid
treatment
Prior art date
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PCT/US2014/030654
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English (en)
Inventor
John Y. Mason
Original Assignee
Sabre Intellectual Property Holdings Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US13/837,936 external-priority patent/US9238587B2/en
Application filed by Sabre Intellectual Property Holdings Llc filed Critical Sabre Intellectual Property Holdings Llc
Priority to US14/776,403 priority Critical patent/US10442711B2/en
Priority to AU2014232430A priority patent/AU2014232430B2/en
Priority to RU2015143407A priority patent/RU2650168C2/ru
Priority to CA2906186A priority patent/CA2906186A1/fr
Priority to MX2015012320A priority patent/MX2015012320A/es
Publication of WO2014145825A1 publication Critical patent/WO2014145825A1/fr
Priority to SA515361073A priority patent/SA515361073B1/ar
Priority to US16/552,269 priority patent/US20200198999A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B11/00—Oxides or oxyacids of halogens; Salts thereof
    • C01B11/02—Oxides of chlorine
    • C01B11/022—Chlorine dioxide (ClO2)
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/29—Chlorine compounds

Definitions

  • the recited claims relate generally to methods and systems for treating produced water associated with gas and crude oil drilling, pumping and production, including but not limited to hydraulic fracturing. More particularly, the recited claims relate to an improved method and system of treating produced water, flowback water, source water or other industrial aqueous fluids in order to reduce contamination and bring the treated water to appropriate standards that allows the treated water to be reused for hydraulic fracturing.
  • the present invention provides a process to treat produced water and achieve standards that will allow the treated produced water to be reused in a subsequent hydraulic fracturing process.
  • Various methods and systems for the treatment of produced water have been explored and are known in the art. Examples of these technologies are reverse osmosis, microfiltration, electrocoagulation, and other technologies. These technologies have severe limitations regarding the variety of contaminants they can deal with in a single step, and high operating costs with relatively low throughput treatment rates.
  • RO reverse osmosis
  • Wastewater associated with the production of crude oil i.e. oilfield water
  • oilfield water and fracturing fluids can be contaminated with, for example, bacteria, naturally-occurring organics in the formation, organic treatment chemicals (such as viscosifiers, emulsion stabilizers, etc), and production chemicals (such as scale reducers, friction reducers, anti-corrosive chemicals, pH modifiers, etc.), and/or other contaminants that result in a high percentage of TDS.
  • organic treatment chemicals such as viscosifiers, emulsion stabilizers, etc
  • production chemicals such as scale reducers, friction reducers, anti-corrosive chemicals, pH modifiers, etc.
  • other contaminants that result in a high percentage of TDS.
  • the presence of these contaminants can interfere with later re -use of the water, storage and/or disposal (e.g. injection into disposal wells or sent to municipal treatment facilities).
  • the methods and system disclosed herein will reduce and/or effectively eliminate bacterial contamination, hydrocarbon metals, inorganic contaminants or metal ions, phosphates, VOCs, TSS, TDS and other contaminants from oil and gas wastewater in order to ultimately reduce the water footprint associated crude oil production, and provide the ability to reuse treated produced water as hydraulic fracturing fluid. More specifically, the novel, high-efficiency treatment method and system disclosed herein is extremely and unexpectedly effective in treating highly contaminated produced water by the removal and/or reduction of certain inorganic contaminants such as Ca, Mg, Na, Fe, CI, Mn, TDS, CaC10 3 , S0 4 , Ba, as well as hydrocarbons, biological contamination and other colloidal material. Furthermore through adjustment of physical and chemical process parameters, some contaminants can be selectively targeted at higher removal rates.
  • Chlorine dioxide's unique chemical and physical properties make it ideal for use in treatment of fracturing fluids. As an oxidant, it is able to penetrate hydrocarbons and break emulsions allowing for the separation and recovery of hydrocarbons, as well as the reduction and/or elimination of biological contamination. Because of its specificity, its oxidation power can be directed at contaminates such as sulfides and residual polymers without creation of undesirable by-products and, unlike bleach or chlorine, chlorine dioxide does not form chlorination by-products that can cause operational or environmental concerns.
  • Chlorine dioxide (and/or chlorite), however, is heavily regulated and caution is necessary in its generation, handling and storage. Furthermore, it can be very costly depending on the chlorine dioxide demand of the wastewater and/or source water.
  • the various embodiments of the invention use the oxidative power of chlorine dioxide together with oxygen (or air) to achieve unexpected results, unexpected increase in efficiency, and unexpected capacity for treatment for these waters that have not been achieved prior to the disclosure herein.
  • a combination of chlorine dioxide disinfection and oxygenation is used to provide a faster-acting treatment for wastewater.
  • Such methods and systems result in increased chlorine dioxide capacity and increased efficiency in relation to volumes of water treated, which provides for reduced chemical usage, reduced energy, and reduced effluent, which in turn results in a reduced burden on the environment and reduced cost.
  • the use of chlorine dioxide in a closed loop system to treat tanks storing oilfield wastewater, or produced water has the unexpected potential to reduce bacterial contamination, Ca, Mg, Na, Fe, CI, Mn, TDS, CaC10 3 , SO 4 , Ba, oil, grease, and combinations thereof, thus providing reduced treatment costs, fluid disposal costs and make-up water purchases (by allowing for greater reuse of the oilfield wastewater as hydraulic fracturing fluid), and reduced environmental and safety concerns.
  • chlorine dioxide can also be used for the pretreatment and disinfection of fracturing fluids prior to their use in crude oil production and/or hydraulic fracturing operations, including but not limited to surface water, produced water, municipal water, flowback water, or any combination thereof.
  • the invention relates to a method comprising the following steps
  • Step 1 Produced fluids are transferred into a vessel that allows between 30 minutes and 60 minutes of residence time.
  • Step 2 Fluid is withdrawn from the first vessel via a pump pass through a venturi and returned to the first treatment vessel. Air is introduced into the venturi to provide for a finely divided and or dissolved airstream returning to the first vessel. Also introduced in the return is a solution of sodium chlorite or a combination of sodium chlorite and sodium hydroxide or those two chemicals as separate feeds. Alternatively, another feedstock can be added to facilitate the precipitation of a target compound.
  • the supply stream is drawn from a level approximately 20% up from the bottom of the vessel.
  • the discharge of the fluid is through a distribution line at the midline of the vessel.
  • the first vessel has provision for skimming of hydrocarbons or other low specific gravity material, and provision for removal of high density solids.
  • Step 3 Fluid is discharged from the first vessel to the centerline of a second vessel. Chlorine dioxide gas is introduced and the transfer line. Chlorine dioxide dosage is sufficient to achieve a residual in the second vessel.
  • Step 4 The second vessel has a residence time of approximately 30 to 60 minutes.
  • the second vessel has a underflow to the third vessel.
  • the second vessel has provision for skimming of flocculate material that is of low specific gravity.
  • Step 5. The third vessel has a residence time of approximately 10 to 30 minutes. This vessel has an overflow to a third vessel or clear well. This vessel also has provision for removal of high density solids from the bottom of the vessel.
  • Chlorine Dioxide Demand The amount of chlorine dioxide (or other oxidant) consumed by background, reactive impurities (both inorganic and organic materials) in a given sample of wastewater (i.e. oilfield water), fracturing fluid, treatment or other target fluids. Chlorine dioxide demand is determined by subtracting the amount of chlorine dioxide remaining after a specified time from the amount of chlorine dioxide initially added to a system.
  • Free Residual or Residual- The amount of chlorine dioxide (or other oxidant) present at a given time to react with biological species after background
  • Biocide - chemical agent capable of killing living microorganisms, often in a selective way also referred to as bactericides or antimicrobials.
  • Biological Contamination any living microorganism or by-product of a living microorganism found in wastewater (i.e. oilfield water), fracturing fiuids, treatment fluids, source water or other target fluids.
  • wastewater i.e. oilfield water
  • fracturing fiuids fracturing fiuids, treatment fluids, source water or other target fluids.
  • Biocidally-Effective Amount An amount that will control, kill or otherwise reduce the bacterial or microbial content of the wastewater (i.e. oilfield water), fracturing fluids, treatment fluids, source water or other target fluids at issue.
  • Well Fluid, Fracturing Fluid or Frac Fluid Any fluid used in any of the drilling, completion, work over and production of subterranean oil and gas wells. It generally includes a source (or raw, or base) water feed (e.g. Frac Water) plus any additives.
  • Frac Water - Raw water feed used in hydraulic fracturing process from any source, including but not limited to surface water, municipal water or treated fiowback or produced water.
  • Fiowback Water - Recovered fracturing fluids that flow back to the surface after being pumped down into a subterranean formation as part of a hydraulic fracturing or crude oil operation.
  • Oilfield Water - includes production water, fiowback water and other fluids that are the by-products of crude oil production, hydraulic fracturing, or other petroleum production processes.
  • FIG. 1 is a schematic of a typical water treatment system in accordance with an exemplary embodiment of the invention.
  • FIG. 2 is a schematic diagram illustrating another embodiment of the invention.
  • FIG. 3 is a schematic diagram illustrating yet another embodiment of the invention.
  • FIG. 4 is a schematic diagram illustrating yet another embodiment of the invention.
  • FIG. 5 is a schematic diagram illustrating yet another embodiment of the invention.
  • FIG. 6 is a schematic diagram illustrating yet another embodiment of the invention.
  • FIG. 7 is a schematic diagram illustrating yet another embodiment of the invention.
  • FIG. 8 is a schematic diagram illustrating yet another embodiment of the invention.
  • FIG. 9 is an illustration of one embodiment of the invention.
  • a step of a method or an element of a device that "comprises”, “has”, “includes” or “contains” one or more features possesses those one or more features, but is not limited to possessing only those one or more features.
  • a device or structure that is configured in a certain way is configured in at least that way, but may also be configured in ways that are not listed.
  • chlorine dioxide can be used to treat oilfield water (including production water, flow-back water and surface water) in order to reduce both the biological load and to aid in the breakdown of residual organic contamination in the water.
  • oilfield water including production water, flow-back water and surface water
  • one or more embodiments of the present invention may be used for the treatment of produced or flowback water prior to disposal or reuse.
  • Both produced and flowback water tend to have substantial biological contamination, as well as a high load of organic contaminants (such petroleum hydrocarbons, oil and grease, diesel-related organics, BTEX), polymers (such as polyacrilamides), iron (Fe), VOCs, inorganic transition metals or metal ions, suspended solids, and other contaminants.
  • the methods disclosed herein can be used in a continuous, closed-loop system to treat produced or flow-back water before the water is reused in a subsequent hydraulic fracturing operation.
  • the methods can also be used as a pretreatment for frac water, including but not limited to a pretreatment "on the fly"; before the water is deposited in storage pits/tanks/lagoons; or as part of a wide variety of other oilfield production systems.
  • one embodiment is a process for treating produced water that provides for a substantial reduction in bacterial contamination, hydrocarbon metals, inorganic contaminants or metal ions, phosphates, volatile organic compounds (VOCs), total dissolved solids (TDS) and other contaminants from oil and gas wastewater as compared to
  • the treatment system and method disclosed herein resulted in the unexpected and commercially unavailable reduction of metal ions including iron, calcium, manganese, magnesium and barium.
  • the amount of chlorine dioxide required to treat the produced water is substantially less than what would be expected by those of ordinary skill in the art and is substantially less as compared to what would be required if one were to use chlorine dioxide in isolation, thus also providing substantial financial and economic benefits for large scale commercial use.
  • FIG 1 illustrates one embodiment of a closed loop treatment system 150 in accordance with certain embodiments of the invention.
  • raw produced fluid 2 is transferred into, or enters, a first treatment vessel 101 through treatment system inlet 17, via pump 18.
  • first treatment vessel 101 is a frac tank located onsite at an oil and gas production site.
  • fluid 2 Prior to transfer into first vessel 101, fluid 2 can be stored in one or more storage frac tanks 500 (as shown in FIG 1).
  • fluid 2 can be transferred directly from, for example, a truck, pipe, pit or well using various transfer methods and apparatus known in the art into first vessel 101.
  • raw produced fluid 2 is a highly contaminated wastewater stream from an oil and gas application containing high levels of contaminants selected from the group consisting of bacterial contamination, Ca, Mg, Na, Fe, CI, Mn, TDS, CaC10 3 , S0 4 , Ba, oil, grease, and combinations thereof.
  • fluid 2 undergoes initial hydrocarbon separation techniques prior to being transferred into first treatment vessel 101 using techniques known in the art.
  • fluid 2 Prior to entering vessel 101, fluid 2 (e.g. raw, untreated produced water) has a first initial demand 200, which can be determined using tests known in the art.
  • the wastewater to be treated e.g. produced water
  • fluid 2a the wastewater to be treated, e.g. produced water, that is contained in vessel 101 is referred to herein as fluid 2a.
  • First treatment vessel 101 provides fluid 2a with a residence time of about 15 minutes to 60 minutes.
  • the total residence time required for fluid 2a will vary and depend on the characteristics of the fluid and other environmental factors. For example, in some
  • the residency time will be 15, 18, 20, 22, 25, 27, 30, 35, 40, 45, 50, 55 or 60 minutes, including any and all ranges and subranges therein (e.g., 15 to 60 minutes, 18 to 55 minutes, 15 to 30 minutes, 20 to 30 minutes, 15 to 20 minutes, 20 to 25 minutes, 18 to 25 minutes, 25 to 50 minutes, etc.).
  • oxidant 40 which in the embodiment shown here is air, is introduced into venturi 4 to provide for a finely divided or dissolved stream of air in return fluid 2a as it returns to first vessel 101.
  • Air or oxidant 40 is introduced at a rate to avoid air stripping so that the removal of volatile reductants (i.e. hydrogen sulfide) is via oxidation, rather than physical purging or stripping.
  • oxidant 40 is air.
  • oxidant 40 can be oxygen, oxygen-enriched air, or any chemical oxygen source or combination that is stable with chlorite.
  • ozone it should not be used in combination with chlorine dioxide in the first step because ozone consumes chlorine dioxide.
  • oxidant 40 can be introduced into fluid 2a via means other than venturi 4, such as an injection boom, pressurized source, aerator, mechanical agitation, air sparger, diffuser, sprayer or other means for injecting and diffusing air known in the art.
  • means other than venturi 4 such as an injection boom, pressurized source, aerator, mechanical agitation, air sparger, diffuser, sprayer or other means for injecting and diffusing air known in the art.
  • oxidant 40 dosage required will depend on the characteristics of fluid 2 (e.g. initial demand 200), the treatment system, and the intended use or application, together with other considerations known to those of ordinary skill in the art.
  • oxidant 40 is added at an appropriate dosage and period of time to achieve an overall dosage ranging from about 20 mg/kg to about 2000 mg/kg of oxidant 40 to the total volume of fluid 2a to be treated, with a more preferred dosage of about 20 mg/kg to about 1000 mg/kg of oxidant 40 to the total volume of fluid 2a to be treated.
  • the dosage comprises 20, 30, 50, 100,
  • oxidant to the total volume of fluid to be treated, including any and all ranges and subranges therein (e.g., 20 to 2000 mg/kg, 100 to 2000 mg/kg, 300 to 2000 mg/kg, 500 to 2000 mg/kg, 1000 to 2000 mg/kg, 20 to 1000 mg/kg, 50 to 1000 mg/kg, 100 to 1000 mg/kg, 500 to 1000 mg/kg, 20 to 500 mg/kg, etc.).
  • a solution of sodium chlorite (chlorite 30b) is introduced either at the same time as oxidant 40 or substantially contemporaneously therewith.
  • chlorite 30b a 25% sodium chlorite solution, commercially available as DiKlor® from Sabre Oxidation Technologies, Inc. is used as chlorite 30b.
  • DiKlor® commercially available as DiKlor® from Sabre Oxidation Technologies, Inc.
  • chlorite 30b is added at an appropriate dosage and period of time to achieve a dosage ranging from about 10 mg/1 to about 500 mg/1 in fluid 2a to be treated.
  • the chlorite 30b dosage comprises 10, 20, 23, 27, 30, 50, 100, 120, 180, 230, 250, 300, 420, 500 mg/1, including any and all ranges and subranges therein (e.g., 10 to 500 mg/1, 25 to 500 mg/1, 25 to 300 mg/1, 10 to 300 mg/1, 10 to 100 mg/1, 25 to 200 mg/1, 50 to 500 mg/1, 50 to 420 mg/1, 23 to 420 mg/1, 27 to 420 mg/1, 23 to 300 mg/1, 27 to 300 mg/1, 23 to 230 mg/1, etc.).
  • returned fluid 2a is discharged back into vessel 101 through distribution line 5 and/or other distribution means known in the art for uniformly distributing fluid 2a within first vessel 101.
  • returned fluid 2a is discharged back into vessel 101 at the centerline or midline 8a (half way up the vertical height of fluid volume contained in the vessel), or substantially about the midline, of first vessel 101.
  • a number of different means can be used to distribute fluid 2a during this step, including but not limited to a submergible boom 19 (stationary or movable) with openings for discharging fluid 2a as shown in FIG 1 , or other similar types of sparging or uniform distribution mechanisms known in the art of wastewater treatment.
  • this first stage, or phase, that combines oxidant 40 and chlorite 30b (and optionally caustic) results in a high reduction in the initial demand 200, or high percentage of contaminant reduction, as compared to oxidation/aeration with only air/oxygen.
  • the reduction of initial demand 200 in treatment vessel 101 can be as much as 70- 80% during phase 1 of the disclosed process.
  • treatment system 150 can be set up so that chlorine dioxide (30a) can be introduced into fluid 2a instead of, or in combination with, chlorite 30b during Phase 1.
  • first treatment vessel 101 has skimming means 6 for removing hydrocarbons or other low specific gravity material that has risen to the top of fluid 2a.
  • Skimming means 6 are well known in the art of wastewater treatment, and include oil skimmers, (e.g. a paddle type), conveying belt, dissolved air flotation or other equipment known in the art to remove lighter solids, hydrocarbons or floe from the surface of a treatment tank.
  • the amount of hydrocarbon removed at this phase can be in the range of about 1-2% of fluid 2a.
  • first treatment vessel 101 also has a separation system (or removal means) 7 for removing precipitated or settled high density solids from the bottom of treatment vessel 101.
  • Separation system, or removal means, 7 include mechanical equipment known in the art of wastewater treatment that can removed settled solids from the bottom of a treatment tank, and can include, for example, an auger or scraper mechanism.
  • the auger or other scraping mechanism sits at the bottom of the vessel 101, pulls the settled solids to center of the tank, where these is a pit, and the solids are pumped out of vessel 101 through the pit.
  • treated fluid 2a is pulled or discharged from first treatment vessel 101 to the centerline 8b of a second treatment vessel 102 via transfer line 9.
  • Chlorine dioxide gas is introduced into fluid 2a at injection port 29 via transfer line 9 and prior to distribution into second vessel 102 as fluid 2b.
  • the chlorine dioxide dosage introduced into fluid 2a is sufficient to achieve a chlorine dioxide residual in fluid 2b within second treatment vessel 102 and is dependent on the amount of biological contamination in the fluid.
  • the chlorine dioxide 30a dosage comprises about 10 mg/1 to about 500 mg/1, for example, 10, 20, 25, 47, 50, 100, 120, 150, 210, 230, 250, 300, 335, 350, 400, 500 mg/1, including any and all ranges and subranges therein (e.g., 10 to 500 mg/1, 10 to 335 mg/1, 25 to 500 mg/1, 25 to 335 mg/1, 25 to 230 mg/1, 45 to 335 mg/1, 45 to 500 mg/1, 47 to 335 mg/1, 50 to 400 mg/1, 20 to 230 mg/1, 20 to 47 mg/1, 10 to 50 mg/1, etc.).
  • the amount of biological contamination can be determined or monitored prior to introducing raw fluid 2 into treatment vessel 101,
  • in-line monitoring equipment may be coupled at various places along the treatment system to allow for continuous monitoring of biological contamination. Testing can be accomplished by test known to those skilled in the art for determining biological demand and/or microbial kill.
  • the target residual concentration of chlorine dioxide in the treated fluid 2b depends on the intended storage period prior to reuse as, for example, a hydraulic fluid.
  • the desired chlorine dioxide residual of fluid 2b is between about 0.1 mg/1 and about 20 mg/1, preferably between about 0.5 mg/1 and about 5 mg/1. If, on the other hand, fluid 2b is to be stored for several days or more before being reused as a hydraulic fluid, the target residual
  • concentration of chlorine dioxide should be between about 5 mg/1 and about 50 mg/1, preferably between about 20 mg/1 and about 50 mg/1.
  • concentration of chlorine dioxide should be between about 5 mg/1 and about 50 mg/1, preferably between about 20 mg/1 and about 50 mg/1.
  • One of ordinary skill in the art can calculate and determine the required target residual, and thus dosage required, depending on the characteristics of fluid 2b, intended storage time, intended use and other factors.
  • the target residual comprises 0.1 mg/1, 0.2 mg/1, 0.3 mg/1, 0.5 mg/1, 1.0 mg/1, 1.5 mg/1, 3 mg/1, 5 mg/1, 10 mg/1, 15 mg/1, 20 mg/1, 25 mg/1, 40 mg/1, or 50 mg/1, including any and all ranges and subranges therein (e.g., 0.1 to 50 mg/1, 0.1 to 20 mg/1, 0.1 to 10 mg/1, 0.1 to 5 mg/1, 0.1 to 2 mg/1, 0.5 to 20 mg/1, 0.5 to 10 mg/1, 0.5 to 5 mg/1, 1.0 to 20 mg/1, 1.0 to 10 mg/1, 5 to 10 mg/1, 5 to 40 mg/1, 5 to 50 mg/1, 10 to 50 mg/1, 20 to 50 mg/1, etc.).
  • chlorine dioxide solutions can be produced by treatment of chlorite salt solutions (e.g.
  • the present invention provides a process that comprises producing chlorine dioxide by using an apparatus such as a chlorine dioxide generator, e.g. as disclosed and claimed in U.S. Pat. No. 6,468,479, the disclosure of which is incorporated herein by reference.
  • the chlorine dioxide is generated either directly as a gas, or preferably as an aqueous (or other suitable liquid carrier) chlorine dioxide mixture.
  • the generator is preferably run using an excess of sodium chlorite to reduce the possibility of generating chlorine gas as an impurity.
  • chlorine dioxide generator 75 is placed in line with the treatment system, and the chlorine dioxide precursors (hydrochloric acid, sodium chlorite, and sodium hypochlorite are stored in tanks 76, 77 and 78, respectively.
  • Venturi 28 has a water stream flowing there through which establishes a vacuum and draws the chlorine dioxide from the reaction column of the generator into the water stream to form aqueous chlorine dioxide.
  • second treatment vessel 102 has a residence time for fluid 2b of approximately 10 to 30 minutes, although reaction time will vary depending on the nature of fluid 2b.
  • the residency time will be 10, 13, 15, 18, 20, 22, 25, 27 or 30 minutes, including any and all ranges and subranges therein (e.g., 10 to 30 minutes, 12 to 30 minutes, 15 to 30 minutes, 20 to 30 minutes, 10 to 20 minutes, 10 to 25 minutes, 15 to 25 minutes, etc.).
  • Second vessel 102 has underflow means 13 to a third treatment vessel 103.
  • Underflow means 13 can include a conduit, pipe, transfer line, or any other means for allowing fluid 2b located at the bottom of vessel 102 to flow into vessel 103 that are well known in the art for wastewater treatment systems.
  • second vessel 102 also comprises skimming means 14 (not shown) to remove light flocculate material, or other materials with low specific gravity, off the surface or top of second treatment vessel 102.
  • skimming means 14 are well known in the art and may include, for example oil skimmers, (e.g. a paddle type), conveying belt, dissolved air flotation or other equipment known in the art to remove lighter solids, hydrocarbons or floe from the surface of a treatment tank.
  • Third treatment vessel 103 contains fluid 2c.
  • Vessel 103 has a residence time of approximately 10 to 30 minutes, although reaction time will vary depending on the nature of fluid 2c.
  • the residency time will be 10, 13, 15, 18, 20, 22, 25, 27 or 30 minutes, including any and all ranges and subranges therein (e.g., 10 to 30 minutes, 12 to 30 minutes, 15 to 30 minutes, 20 to 30 minutes, 10 to 20 minutes, 10 to 25 minutes, 15 to 25 minutes, etc.).
  • Third vessel 103 has overflow means 15 (not shown) to a fourth vessel 104 or clear well.
  • overflow means 15 are well known in the art and may include, for example, a conduit, pipe, transfer line, or any other means for allowing fluid 2c to flow from the top of vessel 103 into vessel 104 that are well known in the art for wastewater treatment systems.
  • Third vessel 103 also has means for removal of high density solids from treated fluid 2d from the bottom of vessels 103, examples of which are well known in the art and may include, for example, scrapers or augers at the bottom of the tank.
  • treatment vessels 101-104 are frac tanks located on site at a oil and gas production site, and the disclosed and claimed produced water treatment system is integrated with a closed loop system already in place at the site.
  • the above method and system can be modified yet still fall within and be consistent within the invention disclosed herein.
  • FIG. 2 a closed loop treatment system 150 in accordance with the claims of the invention is shown.
  • closed loop treatment system 150 comprises a venturi 20, a fluid stream 100 (e.g. wastewater 15) to be treated, treatment/storage vessel or system 50, chlorine oxide 30 and oxidant 40.
  • Fluid stream 100 comprises wastewater 15, for example, a wastewater fluid stream from an oil and gas site.
  • wastewater 15 is raw produced water 2.
  • a combination of a chlorine oxide 30 and an oxidant 40 is introduced into a fluid stream 100.
  • Chlorine oxide 30 preferably comprises chlorite (30b), but it can also include chlorine dioxide (30a), or a combination of chlorite (30b) and chlorine dioxide (30a), which are introduced into stream 100.
  • sodium chlorite i.e. chlorite 30b
  • one of ordinary skill in the art could use techniques known in the art for introducing, mixing and/or diffusing chemicals within a treatment system, either directly in the tank or in a fluid flow line, including but not limited to inductor pumps, high pressure injectors, pumps, flow lines, conduits, mixers, spargers or a combination of the same.
  • oxidant 40 can be air, oxygen, oxygen-enriched air, or any chemical oxygen source or combination that is stable with chlorine dioxide (30a) and/or chlorite (30b), or some combination of the same. And, in one or more embodiments of the invention, oxidant 40 is introduced via direct injection into the wastewater in fine bubbles (i.e. air sparging, a pressurized source, an aerator, mechanical agitation, a diffuser, spraying, or eduction via venturi 20 (4, 28) (see, e.g., FIGs 1-9). If ozone is used as oxidant 40, it should not be used in combination with chlorine dioxide in the first step because ozone consumes chlorine dioxide.
  • storage/treatment vessel (or system) 50 contains wastewater 15, which is supplied by a source 10.
  • Source 10 comprises a source of produced water.
  • source 10 comprises flowback water, surface water, municipal water, frac water, wastewater, or any combination thereof.
  • wastewater 15 can be any water or target aqueous fluid that is contaminated (for example, with organics and/or microorganisms) and is being recycled or treated for reuse, storage and/or discharge back into the environment, regardless of industry.
  • the oxidant demand of the contaminants in wastewater 15, prior to treatment is from about 30 mg/1 to about 5000 mg/1, preferably from about 50 mg/1 to about 500 mg/1.
  • the oxidant demand comprises reducing agents including, but not limited to, reduced sulfur compounds, biomass and other biological by-products, and reduced metals including but not limited to iron (Fe) II.
  • the oxidant demand comprises 30, 50,
  • venturi 20 is used to both generate and introduce chlorine oxide 30 (i.e. chlorine dioxide (30a), and/or a combination of chlorine dioxide (30a) and chlorite (30b)) into fluid stream 100 and, additionally, to then introduce oxidant 40.
  • separate Venturis are used (e.g. venturi 4 & 28 in FIG 1).
  • a drive fluid 33 for venturi 20 comes directly from storage vessel 50.
  • Vessel 50 contains wastewater 15, i.e. the wastewater to be treated, or a combination of treated wastewater (or other target fluid) and the wastewater to be treated.
  • drive fluid 33 can come from any available water source placed in line with system 150.
  • storage/treatment system 50 comprises a single tank or vessel.
  • vessel system 50 comprises multiple tanks, pits or ponds, or any other storage means (e.g. reservoir, container, or lagoon) that stores, holds, transports or contains wastewater 15 from source 10.
  • Vessel system 50 may comprise one or more treatment tanks, vessels, containers or other wastewater treatment systems suitable for treating wastewater 15.
  • vessel 50 actually comprises four treatment vessels 101-104 and storage tanks 500.
  • chlorine oxide 30 and oxidant 40 are applied at such a rate that the removal of volatile reductants (i.e. hydrogen sulfide) is via oxidation, rather than physical purging or stripping.
  • volatile reductants i.e. hydrogen sulfide
  • the reductants are oxidized in situ rather than purged.
  • the goal is to add oxidant 40 to the fluid at a flow rate that brings it into contact with the sulfides to allow oxidation to occur.
  • a flow rate that results in the addition of air being violent, and thus stripping the sulfides before they can oxidize should be avoided.
  • the volume of fluid to be treated in vessel system 50 will directly affect the range of flow rates that can be used to avoid off-gassing/purging and, thus, the appropriate range is widespread. For example, a small tank would require a much lower air flow rate than a deep pond. However, one of ordinary skill in the art will be able to determine the appropriate flow rate to avoid purging, or stripping, of the volatiles, depending on the volume, depth and/or size of vessel system 50 (or fluid to be treated), the treatment system as a whole, and oxidant demand. [0080] In FIG. 3, a diffuser 70 is used to introduce oxidant 40. In one or embodiments, and as shown in FIG.
  • oxidant 40 is added directly to wastewater 15 via a pressurized source 80 near the bottom of vessel 50 and mechanical action can thereby be used to enhance mixing of wastewater 15 within vessel 50. If a single point introduction method is used, it is preferred that the injector be movable throughout the horizontal plane of vessel 50 (not shown).
  • chlorine oxide 30 and oxidant 40 are introduced into wastewater 15 as follows. Initially, chlorine oxide 30 is introduced for a sufficient amount of time and at a sufficient dosage to reduce the chlorine dioxide demand of the wastewater 15 in the range of about 10 percent to about 20 percent, including all ranges and subranges therein (e.g. 12 percent, 15 percent, etc). The amount of time and dosage required will depend on the characteristics of wastewater 15 (e.g. chlorine dioxide demand), the treatment system, and the intended use or application. In one or more embodiments, during this initial (or first) stage of treatment, chlorine oxide 30 comprises chlorite (30b) only.
  • the step of introducing oxidant 40 may be (and, in many instances, is preferred to be) performed soon after, simultaneously, substantially simultaneously, or substantially contemporaneously therewith (See, e.g. FIG 1, description for FIG 1 and examples herein).
  • chlorite 30b is added at an appropriate dosage and period of time to achieve a dosage ranging from about 10 mg/1 to about 500 mg/1 in fluid 2a to be treated.
  • the chlorite 30b dosage comprises 10, 20, 23, 27, 30, 50, 100, 120, 180, 230, 250, 300, 420, 500 mg/1, including any and all ranges and subranges therein (e.g., 10 to 500 mg/1, 25 to 500 mg/1, 25 to 300 mg/1, 10 to 300 mg/1, 10 to 100 mg/1, 25 to 200 mg/1, 50 to 500 mg/1, 50 to 420 mg/1, 23 to 420 mg/1, 27 to 420 mg/1, 23 to 300 mg/1, 27 to 300 mg/1, 23 to 230 mg/1, etc.).
  • chlorine oxide 30 may be chlorine dioxide (30a), chlorite (30b) or a combination thereof.
  • chlorine dioxide reacts as a free radical and, therefore, reacts almost instantaneously, chlorine dioxide cannot be added at high rates or concentrations at the same time as when a large volume of oxidant 40 is being added. Therefore, if chlorine oxide 30 comprises chlorine dioxide (30a) during this initial step (or a combination of chlorite (30b) and chlorine dioxide (30a)), oxidant 40 cannot be added at the same time until all of the chlorine dioxide (30a) has converted to chlorite (30b) or, if performed simultaneously, oxidant 40 must be added at a rate low enough to make sure any chlorine dioxide is not stripped, or purged, from wastewater 15 before it disperses through the fluid body.
  • caustic 90 can be added either prior to treatment with chlorine oxide 30, or concurrently therewith, to raise the pH of wastewater 15 to about 7 - 10.
  • sodium hydroxide (caustic 90) is added to achieve a pH of about 8.5.
  • contaminant metals for example, iron (Fe)
  • the first step of adding chlorine oxide 30 can be skipped, depending on the chlorine dioxide demand and the application/system at hand.
  • Oxidant 40 is introduced into wastewater 15 either prior to treatment with chlorine oxide 30, or substantially concurrently therewith.
  • Oxidant 40 is added at an appropriate dosage and period of time to achieve an overall dosage ranging from about 20 mg/kg to about 2000 mg/kg of oxidant 40 to the total volume of wastewater 15 to be treated, including all ranges and subranges therein, with a more preferred dosage of about 20 mg/kg to about 1000 mg/kg of oxidant 40 to the total volume of fluid to be treated.
  • the amount of time and dosage required will depend on the characteristics of wastewater 15 (e.g. chlorine dioxide demand), the treatment system, and the intended use or application, together with other mechanical considerations known to those of ordinary skill in the art.
  • the application of oxidant 40 consumes, in total, from about 10 percent to about 90 percent of the total chlorine dioxide demand, preferably from about 60 percent to about 90 percent of the chlorine dioxide demand.
  • the oxidant will consume 10, 20, 25, 40, 50, 60, 65, 70, 80, or 90 percent of the chlorine dioxide demand, including any and all ranges and subranges therein (e.g., 10 to 25 percent, 10 to 70 percent, 15 to 90 percent, 20 to 80 percent, 50 to 85 percent, 60 to 80 percent, 60 to 90 percent, etc.).
  • the step of introducing oxidant 40 can be performed substantially
  • chlorine oxide 30 is introduced at a dosage sufficient to achieve a target C102 residual in the fluid, which is based upon the oxidant demand in the fluid.
  • a target residual of chlorine dioxide is reached.
  • chlorine oxide 30 may comprise one or more of chlorine dioxide (30a), chlorite (30b) or a combination thereof. It can be, but does not have to be, the same chlorine oxide that was used in the first initial step.
  • the target residual concentration of chlorine dioxide in the treated fluid or wastewater depends on the intended storage period prior to reuse as, for example, a hydraulic fluid.
  • the desired chlorine dioxide residual of fluid 200 exiting the system is between about 0.1 mg/1 and about 20 mg/1, preferably between about 0.5 mg/1 and about 5 mg/1, and including any and all ranges and subranges therein (See 64-65).
  • the desired chlorine dioxide residual of fluid 200 exiting the system is between about 0.1 mg/1 and about 20 mg/1, preferably between about 0.5 mg/1 and about 5 mg/1, and including any and all ranges and subranges therein (See 64-65).
  • the target residual concentration of chlorine dioxide should be between about 5 mg/1 and about 50 mg/1, preferably between about 20 mg/1 and about 50 mg/1, and including any and all ranges and subranges therein (See 64-65).
  • chlorine oxide 30 comprises only chlorine dioxide (30a) during the last stage of the treatment process. During this treatment step, chlorine oxide 30 (in the form of chlorine dioxide (30a)) and oxidant 40 cannot be added to stream 100 at the same time.
  • the total treatment time required for wastewater 15 to achieve oxidation and/or disinfection is less than 24 hours, preferably less than 8 hours, if storage/treatment system or vessel 50 comprises a tank, pit, pond, or lagoon. In still other embodiments, the total treatment time required for wastewater 15 to achieve oxidation and/or disinfection is less than about 60 minutes, and preferably less than about 15 minutes, if system/vessel 50 is a pipeline, or a combination pipeline and a tank, such as would be used for "on the fly" operations out in the field (see, e.g., FIGs 1, 6-8), when there is a limited residency time and treated fluid 200 is to be used immediately.
  • FIGs 2-5 various embodiments of treatment system 150 are shown.
  • air injection is used to introduce oxidant 40 into vessel 50 via diffuser 70 and a pressurized source 71.
  • a chemical tank and pressurized source 80 is used to introduce oxidant 40.
  • diffuser 70 and pressurized source 71, placed in-line, are used to introduce oxidant 40 into stream 100.
  • mechanical agitator 92 is used.
  • treatment system 150 comprises an "in-line" treatment system 250, for example, a frac-on-the-fly treatment system or any other industrial water treatment system that is placed in-line for immediate use.
  • oxidant 40 is introduced in-line via venturi 20 from chemical source 72.
  • a chemical tank 80 is used in-line to introduce oxidant 40 into stream 100.
  • air injection is used to introduce oxidant 40 into stream 100 via diffuser 70 and a pressurized source 71.
  • treatment system 150/250 may also include a source, a means for introducing, caustic 90 as well as other wastewater treatment methods known in the art, such as mechanical agitators, overflow systems, defoaming agents, and electronic sensors and monitoring devices.
  • chlorine dioxide solutions can be produced by treatment of chlorite salt solutions (e.g. NaC10 2 ) with an acid solution to produce acidic solutions that contain C10 2 , which can be then be flushed as a gas into water to produce aqueous C10 2 .
  • chlorite salt solutions e.g. NaC10 2
  • Other precursors such as sodium chlorate can also be used.
  • the chlorine dioxide should be of the highest possible purity. More specifically, chlorine gas should be present in the introduced chlorine dioxide gas at a level less than about 5%, preferably less than about 0.5%.
  • the present invention provides a process that comprises producing chlorine dioxide by using an apparatus such as a chlorine dioxide generator, e.g. as disclosed and claimed in U.S. Pat. No. 6,468,479, the disclosure of which is incorporated herein by reference.
  • the chlorine dioxide is generated either directly as a gas, or preferably as an aqueous (or other suitable liquid carrier) chlorine dioxide mixture.
  • the generator is preferably run using an excess of sodium chlorite to reduce the possibility of generating chlorine gas as an impurity.
  • the generator preferably uses wastewater 15 as the drive fluid for generating chlorine dioxide and brings chlorine dioxide gas into contact with wastewater 15 under a vacuum pressure such that the chlorine dioxide gas is drawn into wastewater 15 to form a chlorine dioxide aqueous solution.
  • the fluid to be treated is circulated through a closed- loop system and treated in situ in accordance with the methods and systems disclosed herein, in repetition, until the contaminants are oxidized and the appropriate residual of chlorine dioxide is achieved prior to discharge from system 150.
  • the treated fluids after treatment with chlorine oxide 30 and second oxidant 40, the treated fluids are allowed to stand in vessel 50 for an appropriate period of time to allow the solids to settle and free oil to be skimmed prior to reuse or discharge using wastewater treatment methods known in the art.
  • the fluid treated is used (or reused) immediately after treatment for subsequent crude oil, hydraulic fracturing, or other industrial applications.
  • FIG 9 is an schematic iillustration of another embodiment of the invention.
  • the treatment system and method disclosed herein may be coupled, upstream or downstream, to treatment units or systems already in place for treating or transferring produced water.
  • the treatment system claimed herein can be added into a system already located at an oil and gas production site.
  • the concentration of biological contaminants, particulate size, volatile compounds, TDS, and inorganics may be monitored as the treated fluid 2d exits vessel 104 and/or the treatment system. Monitoring can be continuous or periodic. If the fluid exiting the treatment system is not within a predetermined acceptable range, the fluid may be recycled back into the treatment system and/or the amount of oxidant and/or chlorine dioxide introduced into the treatment system may be modified.
  • all or a portion of the stream flowing out of the treatment system may be recycled through the treatment system via one or more recycle lines (not shown). Recycling the fluid stream through the system for a number of passes may allow for significant reduction of the concentration of contaminants.
  • a portion of the stream exiting the system may be mixed with a portion of the stream entering the treatment system inlet 17.
  • the frac water to be injected into the subterranean formation would be treated using the methods disclosed herein out in the oilfield, ahead of the well head.
  • vessel 50 e.g. onsite frac tanks, located at the frac site/oilfield
  • source water that needs to be treated prior to introduction into the well.
  • the water could comprise surface water, municipal water, produced water, flow back water, or any combination of the above (“commingled water").
  • system or process disclosed herein may be combined with one or more traditional or nontraditional biocides, either oxidizing or non-oxidizing, to achieve a synergistic biocidal effect.
  • treatment processes known in the art can be incorporated in line or elsewhere in the system (either prior to treatment in accordance with this invention, or subsequent thereto) in either batch or continuous operation.
  • treatment processes to remove oil and/or solids can be incorporated into the system, or if foaming occurs, one might incorporate a chlorine dioxide compatible defoamer.
  • the method and system disclosed herein can be added to, or retrofitted into, a preexisting recycling or treatment system, and it can be conducted continuously in-line or in selected quantities in a batch process.
  • chlorine dioxide residual can be determined and/or calculated using Method 4500-C1O2 E Amperometric Method II described in Standard Methods the Analysis of Water and Wastewater, or via modified versions of the same, wherein Standard Method 4500-C1O2 E Amperometric Method II uses the following calculations:
  • Chlorite (mg/L) D x 0.00564 x 16,863 / 200
  • Chlorine (mg/L) [A - (B - D) / 4] x 0.00564 x 35,453 / 200,
  • chlorine dioxide residual can be determined spectrometrically or by measurement of oxidation reduction potential (ORP), each of which are incorporated herein, or via modified versions of the same.
  • Embodiments of the present invention include but are not limited to, the following:
  • a method for treating an aqueous system comprising:
  • an oxidant into the aqueous volume at a flow rate that avoids off-gassing of volatile reductants from the aqueous volume, wherein said oxidant is selected from oxygen, air, oxygen-enriched air, and a combination of the same; combining the aqueous volume and oxidant for a minimum residence time sufficient to lower the initial oxidant demand to a reduced oxidant demand;
  • aqueous volume combining the aqueous volume and a quantity of at least one chlorine oxide in an amount sufficient to eliminate the reduced oxidant demand, wherein said at least one chlorine oxide is selected from chlorine dioxide, chlorite, and a combination of the same.
  • step of combining the aqueous fluid volume and a quantity of at least one chlorine oxide comprises the steps of:
  • the source of the aqueous volume is chosen from the group consisting of an aqueous fluid stream, a vessel, tank, pit, lagoon, or pond for storing waste water, a water treatment plant, a hydraulic fracturing tank, or a piece of equipment, pipeline or vessel used for hydraulic fracturing or crude oil production.
  • aqueous system is chosen from the group consisting of hydraulic fracturing, crude oil production, water distribution systems, fluid transporting pipelines, wastewater treatment facilities, storage tanks, food and beverage processing lines, machining coolant or metalworking fluid (MWF) systems, coal and mineral slurries, metal leaching fluids, acid mine drainage, or any aqueous system contaminated by biological species or sulfur compounds.
  • MVF metalworking fluid
  • aqueous system comprises one or more separation apparatus for removing precipitated contaminants from the aqueous volume either during, before or after treatment.
  • a method for reducing, inactivating, destroying, removing, or eliminating from an aqueous fluid contaminants selected from the group consisting of Ca, Mg, Na, Fe, CI, Mn, CaC103, S04, Ba, hydrocarbons, total dissolved solids, biological contamination, and combinations thereof, comprising the steps of introducing an oxidant and introducing at least one chlorine oxide, wherein said oxidant is selected from the group consisting of oxygen, air, oxygen-enriched air, and combinations thereof and said at least one chlorine oxide is selected from the group consisting of chlorine dioxide, chlorite, and combinations thereof.
  • step of introducing the at least one chlorine oxide comprises the steps of:
  • the method according to claim 15 further comprising the step of generating the chlorine dioxide aqueous solution by using a portion of the aqueous fluid to be treated.
  • the source of the aqueous fluid stream or volume is chosen from the group consisting of a vessel, tank, pit, lagoon, or pond for storing waste water, a water treatment plant, a hydraulic fracturing tank, or a piece of equipment, pipeline or vessel used for hydraulic fracturing or crude oil production.
  • a method for treating an aqueous system comprising:
  • an oxidant into an aqueous volume at a flow rate that avoids off-gassing of volatile reductants from the aqueous volume prior to introducing chlorine dioxide into the volume, wherein said oxidant is selected from the group consisting of oxygen, air, oxygen- enriched air, and combinations thereof, and wherein the oxidant provides synergistic oxidation activity in the presence of the chlorine dioxide such that the chlorine dioxide is introduced at substantially reduced amounts as compared to a predetermined chlorine dioxide demand.
  • a method according to claim 20 comprising the additional step of introducing sodium chlorite into said volume prior to the step of introducing the oxidant.
  • a method for treating an aqueous system comprising:
  • an oxidant into the aqueous volume, wherein said oxidant comprises oxygen, air, oxygen-enriched air, or a combination of the same, at a flow rate that avoids off- gassing of volatile reductants from the aqueous volume;
  • a method for treating an aqueous system comprising:
  • an oxidant into the aqueous volume at a flow rate that avoids off-gassing of volatile reductants from the aqueous volume, wherein said oxidant comprises oxygen, air, oxygen-enriched air, ozone or a combination of the same;
  • aqueous volume combining the aqueous volume and a quantity of at least one chlorine oxide in an amount sufficient to eliminate the reduced oxidant demand, wherein said at least one chlorine oxide comprises chlorine dioxide, chlorite, or a combination of the same, provided that if the at least one chlorine oxide comprises chlorine dioxide than said aqueous volume does not comprise an ozone residual.
  • a method for treating wastewater comprising the following steps:
  • introducing a wastewater stream to a fluid treatment system comprising at least one first treatment cell, at least one second treatment cell, and at least one third treatment cell;
  • a source of the wastewater stream is chosen from the group consisting of an aqueous fluid stream, vessel, tank, pit, lagoon, or pond for storing waste water, a water treatment plant, a hydraulic fracturing tank, or a piece of equipment, pipeline or vessel used for hydraulic fracturing or crude oil production.
  • first treatment cell is a vessel chosen from the group consisting of a storage tank, hydraulic fracturing tank, or other onsite vessel used for hydraulic fracturing or crude oil production.
  • second and third treatment cell are located within a single vessel chosen from the group consisting of a storage tank, hydraulic fracturing tank, or other onsite vessel used for hydraulic fracturing or crude oil production.
  • a fluid treatment system for in-line use at a hydrocarbon producing well site comprising: at least one first treatment cell, at least one second treatment cell, and at least one third treatment cell;
  • At least one first fluid flow line for flowing a wastewater stream with an initial oxidant demand into the at least one first treatment cell, said at least one first treatment cell having at least one outlet in fiuid communication therewith;
  • At least one second fluid flow line for circulating wastewater from the at least one first treatment cell, said at least one first treatment cell having at least one outlet and at least one inlet in fluid communication therewith;
  • At least one first eductor disposed in fluid communication with the at least one second fluid flow line and at least one oxidant source, for introducing at least one oxidant into the at least one second fluid flow line in controlled quantities and at a controlled flow rate;
  • At least one second eductor disposed in fluid communication with the at least one second fluid flow line and at least one chlorine oxide source, for introducing at least one first chlorine oxide into the at least one second fluid flow line in controlled quantities;
  • At least one third fluid flow line for transferring treated wastewater from the at least one first treatment cell to the at least one second treatment cell, wherein said at least one third fluid flow line is in fluid communication with at least one outlet of said at least one first treatment cell and at least one inlet of said at least one second treatment cell;
  • first treatment cell comprises at least one skimming apparatus, at least one separation apparatus for removing precipitated contaminants from the at least one first treatment cell, and a residence time of between about 15 minutes to about 60 minutes;
  • second treatment cell comprises at least one skimming apparatus, at least one underflow outlet that discharges into the at least one third treatment cell, and a residence time of about 10 minutes to about 30 minutes;
  • said third treatment cell comprises at least one separation apparatus for removing precipitated contaminants from the at least one third treatment cell, at least one overflow outlet, and a residence time of about 10 minutes to about 30 minutes.
  • oxidant is selected from the group comprising oxygen, air, oxygen-enriched air, and combinations thereof.
  • a method for treating wastewater comprising the follow steps: introducing a wastewater stream to a fluid treatment system, the fluid treatment system comprising at least one first treatment cell, at least one second treatment cell, and at least one third treatment cell;
  • an oxidant into the withdrawn portion of the wastewater through at least one in-line oxidant treatment point within the first fluid flow line under conditions sufficient to produce thorough mixing of the oxidant within the wastewater and at a controlled flow rate to avoid off-gassing of volatile reductants from the wastewater, wherein said oxidant is selected from the group consisting of oxygen, air, oxygen-enriched air, and combinations thereof, and introducing at least one chlorine oxide into the withdrawn portion of the wastewater through at least one in-line chlorine oxide treatment point within the at least one first fluid flow line to produce treated wastewater;
  • Example 1 The following experiment was conducted to determine how significantly the addition of air/oxygen affects chlorine dioxide (and/or chlorite) treatment of a sample of oilfield wastewater.
  • the experimental results demonstrate that the combination of air/oxygen with chlorine dioxide or chlorite has an unexpected, beneficial result of substantially reducing the oxidant dosage required for oxidation of sulfides present in oilfield wastewater. Additionally, the combination of air/oxygen with chlorine dioxide unexpectedly achieves bacterial kill at significantly reduced dosages.
  • air/oxygen addition alone is not sufficient over a reasonable period of time to remove sulfides from wastewater or to kill bacteria present therein, and the addition of alternative oxidants (i.e. nitrogen) do not have the same synergistic effect.
  • Control A A 200 ml portion of the sample was treated with 335 mg/1 chlorine dioxide over a 15 minute period while stirring to achieve a trace ( ⁇ 1.0 mg/1) residual of chlorine dioxide in solution.
  • the sample quickly turns from a black coloration to a brown/orange with the insoluble solids settling quickly and an iron type floe forming. There was also a slight sheen of hydrocarbon on the surface of the treated sample. No further change in appearance of the treated fluid was observed over 5 minutes.
  • the solids (sludge) and fluid were analyzed for sulfide content using a Garret Gas Train. No detectable sulfides were found in the solids or fluids. Sulfur reducing and general aerobic bacteria were cultured from the sample, demonstrating no bacterial growth.
  • Control B A 200 ml portion of the sample was treated with 230 mg/1 chlorine dioxide over a five minute period while stirring. The sample quickly turns from a black coloration to a grey brown/orange with the insoluble solids settling quickly and an iron type floe forming. No further change in appearance of the treated fluid was observed over 5 minutes.
  • the solids (sludge) and fluid were analyzed for sulfide content using a Garret Gas Train. There was 31 mg/1 and 51 m/kg found in the fluid and sludge, respectively. No chlorine dioxide residual was present. Sulfur reducing and general aerobic bacteria were cultured from the sample, demonstrating bacterial growth over 10 6 cfu/ml.
  • a 200 ml portion of the sample was treated with 420 mg/1 of chlorite (560 mg/1 as sodium chlorite) while stirring.
  • the sample turns from a black coloration to a brown/orange with the insoluble solids settling and an iron type floe forming over a ten minute period.
  • No further change in appearance of the treated fluid was observed after 10 minutes.
  • the solids and fluid were analyzed for sulfide content using a Garret Gas Train. No detectable sulfides were found in the fluids, however the solids contain approximately 15 mg/1 sulfide. Sulfur reducing and general aerobic bacteria were cultured from the sample, demonstrating growth over 10 6 cfu/ml.
  • Control D A 200 ml portion of the sample was sparged with air through a fine diffuser stone at a rate of 2 SLPM for 30 minutes. Over the 30-min period, the sample turns from a black coloration to a grey coloration.
  • the solids (sludge) and fluid were analyzed for sulfide content using a Garret Gas Train. The fluid contains 60 mg/1 sulfide and the solids contain 75 mg/1 sulfide. Sulfur reducing and general aerobic bacteria were cultured from the sample, demonstrating growth over 10 6 cfu/ml.
  • Experiment E A 200 ml portion of the sample was sparged with air through a fine diffuser stone at a rate of 2 SLPM for four (4) minutes. Initiated concurrently, a dose of 230 mg/1 chlorine dioxide was added over a five (5) minute period, with the last minute of dosing being added without air sparging.
  • C102 is added at a low enough rate with a volume and flow rate of air that does not strip the chlorine dioxide before it reacts.
  • the sample quickly turns from a black coloration to a brown/orange with the insoluble solids settling quickly and an iron type floe forming upon the cessation of sparging. No further change in appearance of the treated fluid was observed over five (5) minutes.
  • the solids (sludge) and fluid were analyzed for sulfide content using a Garret Gas Train. There were no detectable sulfides in the solids or fluid. Sulfur reducing and general aerobic bacteria were cultured from the sample, demonstrating no bacterial growth.
  • Experiment F A 200 ml portion of the sample was sparged with nitrogen through a fine diffuser stone at a rate of 2 SLPM for four (4) minutes. Initiated concurrently, a dose of 230 mg/1 chlorine dioxide was added over a five (5) minute period, with the last minute of dosing being added without nitrogen sparging. The sample quickly turns from a black coloration to a brown/orange with the insoluble solids settling quickly and an iron type floe forming upon the cessation of sparging. No further change in appearance of the treated fluid was observed over 5 minutes. The solids (sludge) and fluid were analyzed for sulfide content using a Garret Gas Train. There were 7 mg/1 and 160 mg/1 sulfides remaining in the fluid and the solids, respectively. Sulfur reducing and general aerobic bacteria were cultured from the sample, demonstrating over 10 6 bacterial growth.
  • Experiment G A 200 ml portion of the sample was sparged with air through a fine diffuser stone at a rate of 2 SLPM for 15 minutes. Initiated concurrently, a dose of 300 mg/1 of chlorite (402 mg/1 as sodium chlorite) was added over a five (5) minute period. The sample turns from a black coloration to a brown/orange with the insoluble solids settling quickly and an iron type floe forming upon the cessation of sparging. No further change in appearance of the treated fluid was observed over 15 minutes. The solids (sludge) and fluid were analyzed for sulfide content using a Garret Gas Train. There were no detectable sulfides in the solids or fluid.
  • Example 2 A tank containing about 30,000 barrels (bbl) of produced fresh and flow back water was analyzed and found to contain 16,000 mg/1 TDS, over 10 6 cfu/ml bacteria, and 40 mg/1 sulfides in the homogenized fluid at a pH of 7.8.
  • the chlorine dioxide demand of the fluid to be treated was determined to be 180 mg/1.
  • the amount of 50% sodium hydroxide required to maintain the pH was determined to be 630 gallons.
  • generator would be a Sabre BB series portable DiKlor® generation system with a maximum capacity of 24,000 lbs. per day continuous production.
  • This system is self-contained and has a distribution system that allows it to circulate fluids in the tank. More specifically, a drive fluid stream was withdrawn from the tank and circulated through a chlorine dioxide generator by means of a centrifugal pump at a rate of 320 gallons per minute.
  • the generator is arranged so that the suction for the drive fluid stream is pulled from the lowest end of the tank, and the discharge solution containing chlorine dioxide and/or air was returned to the tank and discharge to the bottom of the tank via a movable injection boom. (See FIG. 5 & 8).
  • the injection boom was continuously moved around the tank at a rate of 50 feet per minute.
  • Sodium hydroxide was added to the tank with enough sodium chlorite to absorb approximately 10 percent of the theoretical chlorine dioxide demand.
  • the amount of sodium chlorite required to absorb 10% of the chlorine dioxide demand was a dosage of approximately 23 mg/1 chlorite.
  • the sodium hydroxide and chlorite were added over a sixty minute period with air at a rate of 125 SCFM. In this embodiment, air was introduced via a venturi. At the end of the 60-minute period, the injection of air is discontinued, and chlorine dioxide demand was retested and found to be 27 mg/1. Chlorine dioxide then was introduced via a venturi at an appropriate rate to achieve a dosage of 47 mg/1 over a 30 minute period. No air was introduced during the chlorine dioxide step.
  • the resulting fluid was clear with orange/brown sediment and had a thin layer of floe on top that was determined to be 98% inorganic material and 2% hydrocarbons. 8 mg/1 chlorine dioxide was found as a residual in the fluid.
  • the fluid, sludge, and floe were analyzed by garret gas train and determined to contain no sulfides. No bacterial growth was found by culture analysis.
  • the fluid was analyzed to determine suitability for "gelling" for fracturing use. The fluid gelled and cross linked without difficulty. This method resulted in a 75% reduction in the amount of chlorine dioxide required to achieve the target chlorine dioxide residual and no bacterial grown.
  • Example 3 A tank containing about 30,000 bbl of produced fresh and flow back water was analyzed and found to contain 16,000 mg/1 TDS, over 10 6 cfu/ml bacteria, and 40 mg/1 sulfides in the homogenized fluid at a pH of 7.8.
  • the chlorine dioxide demand of the fluid was determined to be 180 mg/1.
  • the tank was rigged to a chlorine dioxide generator where the suction for a drive fluid stream is pulled from the lowest end of the tank, and the discharge solution containing chlorine dioxide and/or air was returned to the tank and discharge to the bottom of the tank via a movable injection boom.
  • the injection boom was continuously moved around the tank at a rate of 50 feet per minute.
  • chlorite was not added directly to the system as sodium chlorite. Instead, chlorine dioxide was added to the tank initially (which converted to chlorite), followed by air and then a second dosage of chlorine dioxide as set forth below. More specifically, 1) from time zero (0) and over the first 10 minutes, chlorine dioxide was added to provide 20% of the total dosage; 2) from minute 10 through minute 30, the solution was circulated; 3) from minute 30 to minute 60, air was added; and 3) from minute 60 through minute 80, the remaining 80% of the chlorine dioxide was introduced into the tank.
  • step 2 the tank was treated with 110 mg/1 chlorine dioxide over an aggregate (but, nonconsecutive) 50-minute period.
  • step 2 one of ordinary skill in the art will recognize that, when a big tank is used, one has to be careful not to get localized "hot spots" and allow the chlorine dioxide to disperse a bit.
  • step 3 air was added in isolation through a venturi at a rate of 100 SCFM to tank 250 from minute 30 to minute 60.
  • Sodium hydroxide was added concurrently to maintain stable pH.
  • the fluid was analyzed post treatment. The resulting fluid was clear with orange/brown sediment and had a thin layer of floe on top that was determined to be 98% inorganic material and 2% hydrocarbons. 12 mg/1 chlorine dioxide was found as a residual in the fluid.
  • the fluid, sludge, and floe were analyzed by garret gas train and determined to contain no sulfides. No bacterial growth was found by culture analysis.
  • Example 4 A tank contained 4200 gallons of produced water. The homogenized fluid was analyzed and found to contain 23,000 mg/1 TDS, over 104 cfu/ml bacteria, and 175 mg/1 sulfides with a pH of 7.8. The chlorine dioxide demand of the fluid was determined to be 580 mg/1.
  • the tank was rigged to a chlorine dioxide generator where the suction for the drive fluid stream is pulled from the lowest end of the tank, and the discharge solution containing chlorine dioxide and/or air via a perforated pipe along the length of the bottom of the tank.
  • the fluid is withdrawn from the tank and circulated through the chlorine dioxide generator by means of a centrifugal pump at a rate of 320 gallons per minute.
  • Example 5 A tank contained 4200 gallons of produced water. The homogenized fluid was analyzed and found to contain 23,000 mg/1 TDS, over 104 cfu/ml bacteria, and 175 mg/1 sulfides with a pH of 7.8. The chlorine dioxide demand of the fluid was determined to be 580 mg/1.
  • the tank was rigged to a chlorine dioxide generator where the suction for the drive fluid stream is pulled from the lowest end of the tank, and the discharge solution containing chlorine dioxide and/or air via a perforated pipe along the length of the bottom of the tank.
  • the fluid is withdrawn from the tank and circulated through the chlorine dioxide generator by means of a centrifugal pump at a rate of 320 gallons per minute.
  • chlorite was introduced directly at a rate to achieve a dosage of 120 mg/1 over the first minute.
  • Chlorine dioxide also was added at a rate to achieve a dosage of 210 mg/1 over an aggregate five (5) minute period. Specifically, chlorine dioxide was added from time zero (0) to minute one (1), and then again from minute six (6) to minute ten (10). Air was added through a venturi at a rate of 50 SCFM to the tank from minute zero to minute nine. Sodium hydroxide was added concurrently to maintain stable pH. The fluid was analyzed post treatment.
  • the treated fluid was clear with orange/brown sediment and had a thin layer of floe on top that was determined to be 96% inorganic material and 4% hydrocarbons. 7 mg/1 chlorine dioxide was found as a residual in the fluid.
  • the fluid, sludge, and floe were analyzed by garret gas train and determined to contain no sulfides. No bacterial growth was found by culture analysis. This method resulted in about a 43% reduction in the amount of chlorine oxides required to achieve a target chlorine dioxide residual and no bacterial grown.
  • Example 6 A treatment train is arranged for a typical produced fluid (2) from northern Texas production. Approximately six barrels per minute of fluid is transferred via a circulation pump (3) to a 500 barrel frac tank (first frac tank 101) at a steady flow rate.
  • Approximately four barrels per minute of fluid is withdrawn from a level 2 feet above the bottom of the first frac tank (101).
  • This fluid (2a) is passed through a venturi (4) where air (40), sodium chlorite (30b) and sodium hydroxide (90) are added to the fluid stream.
  • the fluid stream (2a) that reenters the first frac tank (101) containing the air (4), chlorite (30b) and caustic (90) is introduced along the centerline (8a) of the tank (101) through a distribution bar (19) running the length of the tank (101).
  • chlorite (30b) is introduced to achieve a dosage of 50 mg/1
  • oxidant (40) is added to achieve a dosage of 400 mg/1.
  • a skimmer (6) is placed into the top of the first frac tank (101) to recover floating material.
  • Fluid (2a) is withdrawn to a second frac tank (102) via a discharge approximately 2 feet from the bottom of the first frac tank (101).
  • the fluid (2a) is introduced into the second frac tank (102) at approximately the 2 foot level.
  • Chlorine dioxide (30a) is injected into the fluid stream between the first and second frac tanks (101, 102).
  • chlorine dioxide (30a) is added to achieve a dosage of 25 mg/1.
  • Fluid (2b) from the second frac tank (102) under flows to the third frac tank (103).
  • Fluid (2c) from the third frac tank (103) overflows to the clear well (104).
  • the produced fluid (2) that flowed into the first frac tank (101) originally contained approximately 1% by volume petroleum hydrocarbon.
  • the free hydrocarbon was predominantly recovered at the surface.
  • iron sulfide FeS
  • FeS iron sulfide
  • the low density solids formed by this reaction and additional hydrocarbons further liberated were recovered by a surface skim of the second frac tank.
  • the high density solids that were formed as part of this process dropped to the bottom of the common second and third tanks.
  • the third tank (103) overflowed into a clear well (104).
  • the treated fluid (2d) was pumped out of the clear well (104) for further storage.
  • Treated fluid has a chlorine dioxide residual of 20 mg/1.
  • Tables 1A-1C denotes the results obtained by the above method and system.
  • Example 7 A treatment train is arranged for a typical produced fluid from
  • Permian Basin production Approximately six barrels per minute of fluid is transferred via a pump to a 500 barrel frac treatment tank (101) at a steady flow rate from a bank of six frac storage tanks (500). The six storage frac tanks (500) are filled by truck from the field.
  • Approximately four barrels per minute of fluid is withdrawn from a level 2 feet above the bottom of the first frac treatment tank (101).
  • This fluid (2a) is passed through a venturi (4), where air (40), sodium chlorite (30b) and sodium hydroxide (90) are added to the fluid stream.
  • the fluid stream that reenters the first frac treatment tank, and which contains air (40), chlorite (30b) and caustic (90) is introduced along the centerline of the first frac tank (101) through a distribution bar (19) running the length of the tank (101).
  • chlorite (30b) is introduced to achieve a dosage of 50 mg/1
  • oxidant (40) is added to achieve a dosage of 400 mg/1 (e.g. 2200 mg/1 air).
  • a skimmer (6) is placed into the top of the tank (101) to recover floating material.
  • Fluid is withdrawn to a second frac tank (102) via a discharge approximately 2 feet from the bottom of the first tank (101) and is introduced into the second tank (102) at approximately the 2 foot level.
  • Chlorine dioxide (30a) is injected into the fluid stream between the first and second tanks (101, 102).
  • chlorine dioxide (30a) is added to achieve a dosage of 25 mg/1.
  • Fluid (2b) from the second tank (102) under flows to the third tank (103).
  • Fluid (2c) from the third tank (103) overflows to the clear well (104).
  • the free hydrocarbon was predominantly recovered at the surface.
  • iron sulfide oxidized by the chlorine dioxide reacted to form iron three hydroxide.
  • the low density solids that were formed by this reaction and the hydrocarbon that was liberated was recovered by a surface skim of this tank.
  • the high density solids that were formed dropped to the bottom of the second and third cells/tanks..
  • the third cell/tank (103) overflowed into a clear well (104). Fluid (2d) was pumped out of the clear well (104) for further storage.
  • Treated fluid has a chlorine dioxide residual of 20 mg/1.
  • the inlet fluid measured 60 ppm by volume of petroleum hydrocarbon in grab samples. This measurement was inaccurate, however, due to the nature of the truck transfer. Some trucks that came in had no visible hydrocarbon, while others contained several percent due to slugs of hydrocarbon that went into the system. A large amount of hydrocarbon was recovered from the first and second tanks by skimming, representing 1.72% of the total fluid feed. There was no visible hydrocarbon present in the third frac tank and the fluid grab samples in the discharge from the last tank showed an average of 45 ppm total hydrocarbon.
  • Tables 2A-2C denotes the results obtained by this treatment.
  • the process of the present invention is unexpectedly and economically effective at removing contaminants from highly contaminated, hydrocarbon-bearing produced water streams.
  • the reduction of most of the contaminants is in the range of 75 - 98% as shown in Tables 1 and 2.
  • the treated water is acceptable to be used as a hydraulic fracturing fluid without further treatment, in most cases, or as a feed stream that can be further treated (if necessary) for disposal to the environment.
  • the removal of a high level of contaminants, such as Ca, Mg, Na, Fe, CI, Mn, TDS, CaC10 3 , S0 4 , Ba, hydrocarbons and biological contamination, as achieved by the claimed process is highly desirable for treating the large quantities of produced water contaminated waste streams created by oil field applications.
  • the process also beneficially, and significantly, avoids off-gassing of harmful, regulated volatile compounds such as hydrogen sulfide.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Physical Water Treatments (AREA)

Abstract

Des modes de réalisation de l'invention concernent de manière générale des procédés et des systèmes pour traiter des systèmes aqueux avec des applications aux eaux usées industrielles, en particulier le forage, le pompage et la production de gaz et de pétrole brut, afin de réduire ou d'éliminer la contamination et permettre de réutiliser l'eau qui est traitée, en particulier de la réutiliser pour la fracturation hydraulique.
PCT/US2014/030654 2013-03-15 2014-03-17 Procédé et système pour le traitement de l'eau et de fluides produits avec du dioxyde de chlore afin de les réutiliser WO2014145825A1 (fr)

Priority Applications (7)

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US14/776,403 US10442711B2 (en) 2013-03-15 2014-03-17 Method and system for the treatment of produced water and fluids with chlorine dioxide for reuse
AU2014232430A AU2014232430B2 (en) 2013-03-15 2014-03-17 Method and system for the treatment of produced water and fluids with chlorine dioxide for reuse
RU2015143407A RU2650168C2 (ru) 2013-03-15 2014-03-17 Способ и система для обработки при помощи диоксида хлора пластовой воды и текучих сред для повторного использования
CA2906186A CA2906186A1 (fr) 2013-03-15 2014-03-17 Procede et systeme pour le traitement de l'eau et de fluides produits avec du dioxyde de chlore afin de les reutiliser
MX2015012320A MX2015012320A (es) 2013-03-15 2014-03-17 Metodo y sistema para el tratamiento de agua y fluidos producidos con dioxido de cloro para su reutilizacion.
SA515361073A SA515361073B1 (ar) 2013-03-15 2015-09-13 طريقة ونظام لمعالجة ماء وموائع منتجة باستخدام ثاني أكسيد كلور لإعادة الاستخدام
US16/552,269 US20200198999A1 (en) 2013-03-15 2019-08-27 Method and system for the treatment of produced water and fluids with chlorine dioxide for reuse

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US13/837,936 US9238587B2 (en) 2013-03-15 2013-03-15 Method and system for the treatment of water and fluids with chlorine dioxide
US13/837,936 2013-03-15
US201461930688P 2014-01-23 2014-01-23
US61/930,688 2014-01-23

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US16/552,269 Continuation US20200198999A1 (en) 2013-03-15 2019-08-27 Method and system for the treatment of produced water and fluids with chlorine dioxide for reuse

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WO2017106685A1 (fr) 2015-12-18 2017-06-22 Sabre Intellectual Property Holdings Llc Procédés d'extraction d'huiles et de graisses à partir d'une matière solide à l'aide de dioxyde de chlore
WO2017106696A2 (fr) 2015-12-18 2017-06-22 Sabre Intellectual Property Holding Llc Mélanges contenant du dioxyde de chlore et traitements en vrac au dioxyde de chlore pour améliorer la récupération du pétrole et du gaz
CN107098436A (zh) * 2017-05-10 2017-08-29 大唐鸡西热电有限责任公司 一种用于阳床内钠离子浓度检测的辅助平衡罐
US10308533B2 (en) 2013-03-15 2019-06-04 Sabre Intellectual Property Holdings Llc Method and system for the treatment of water and fluids with chlorine dioxide
US10442711B2 (en) 2013-03-15 2019-10-15 Sabre Intellectual Property Holdings Llc Method and system for the treatment of produced water and fluids with chlorine dioxide for reuse
US10526530B2 (en) 2013-04-24 2020-01-07 Sabre Intellectual Property Holdings Llc Flooding operations employing chlorine dioxide
WO2020129013A1 (fr) 2018-12-21 2020-06-25 Jeanologia, S.L. Système et procédé de traitement des eaux usées industrielles pour la la finition de vêtements, et l'industrie des jeans et du denim

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US20020125196A1 (en) * 2001-03-08 2002-09-12 Cdg Technology, Inc. Methods of treating water using combinations of chlorine dioxide, chlorine and ammonia
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Publication number Priority date Publication date Assignee Title
US10308533B2 (en) 2013-03-15 2019-06-04 Sabre Intellectual Property Holdings Llc Method and system for the treatment of water and fluids with chlorine dioxide
US10442711B2 (en) 2013-03-15 2019-10-15 Sabre Intellectual Property Holdings Llc Method and system for the treatment of produced water and fluids with chlorine dioxide for reuse
US10526530B2 (en) 2013-04-24 2020-01-07 Sabre Intellectual Property Holdings Llc Flooding operations employing chlorine dioxide
WO2017106685A1 (fr) 2015-12-18 2017-06-22 Sabre Intellectual Property Holdings Llc Procédés d'extraction d'huiles et de graisses à partir d'une matière solide à l'aide de dioxyde de chlore
WO2017106696A2 (fr) 2015-12-18 2017-06-22 Sabre Intellectual Property Holding Llc Mélanges contenant du dioxyde de chlore et traitements en vrac au dioxyde de chlore pour améliorer la récupération du pétrole et du gaz
CN106446587A (zh) * 2016-11-02 2017-02-22 中国石油化工股份有限公司 一种气井压裂返排率校正方法
CN106446587B (zh) * 2016-11-02 2019-02-19 中国石油化工股份有限公司 一种气井压裂返排率校正方法
CN107098436A (zh) * 2017-05-10 2017-08-29 大唐鸡西热电有限责任公司 一种用于阳床内钠离子浓度检测的辅助平衡罐
WO2020129013A1 (fr) 2018-12-21 2020-06-25 Jeanologia, S.L. Système et procédé de traitement des eaux usées industrielles pour la la finition de vêtements, et l'industrie des jeans et du denim

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AU2014232430B2 (en) 2018-03-29
RU2015143407A (ru) 2017-04-24
MX2015012320A (es) 2016-04-25
SA515361073B1 (ar) 2017-07-24

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