SA515361073B1 - Method and system for the treatment of produced water and fluids with chlorine dioxide for reuse - Google Patents

Abstract

Embodiments of the invention relate generally to methods and systems for treating aqueous systems associated with industrial wastewater applications, in particular gas and crude oil drilling, pumping and production, in order to reduce or eliminate contamination and allow the water that is treated to be reused, in particular, to be reused for hydraulic fracturing. Fig 1

Description

1 Method and system for treating water and produced fluids using chlorine dioxide for reuse

Method and system for the treatment of produced water and fluids with chlorine dioxide for reuse The pumping and production of 985 gas and crude oil with the identification of more protection elements mentioned in an improved manner and a Jhydraulic fracturing system or a flowback water source water source to treat the produced water; Other 0 backflow water until contaminants are reduced Industrial aqueous fluids Industrial aqueous fluids and conversion of treated water to compliant standards that allow reuse of treated water for hydraulic fracturing. In gas production operations in arid oil regions; Huge amounts of water are used as part of the overall process. The primary benefit is the large amount of water that is used to crack the PE to enhance production from a given formation. The water ofl Or gas wells of oil or gas wells that will be used in this process must be free of pollutants that could affect the efficiency of the hydrocarbon process 619a180. particulary; Hydrocarbon process metal ions inorganic contaminants inorganic contaminants 05 volatile organic compounds phosphates phosphates 10 and other contaminants can lead to (TDS) total dissolved solids Total dissolved solids (VOCs) used to produce fracturing and/or to hold sand in suspension polymers Impairment of polymer efficiency Bacterial It is also important to reduce or remove bacterial and/or contaminants to form 505060500. polymer that can lower the efficiency of the polymer bacterial contamination that can cause bacterial contamination (JE production).

The formation leads to damming or loss of production and causes formation of hydrogen sulfide which affects the workability of well al) and the value of the resulting product. The present invention provides a process for treating the produced water and achieving standards that will allow the treated waste water to be reused in a subsequent hydraulic fracturing process. Various methods and systems for treating the resulting water have been explored and are known in the art. Examples of these technologies are reverse osmosis technologies; microfiltration, electrocoagulation, and other technologies. These techniques have severe limitations regarding the range of contaminants that can be handled within a single step; And high operating costs with low total treatment rates KI for example JB although reverse osmosis 05000515 reverse (RO) 0 is YE in removing ionic contaminants contaminants can lead to hydrocarbon contaminants 0007© to severely block and/or damage the membrane (reverse osmosis) making the technology commercially inflexible. cially the presence of certain 05 cations and certain 801005 anions can cause fouling, scaling or other forms of interference. Vo Waste water associated with the production of crude oil “crude oil” i.e.; Jas water daa, (oilfield water in general) consists of two primary sources: return effluent and product water. Reuse of that water is typically difficult due to high contamination and bacterial loading (iS) with the specification of jis Oil field water and fracturing fluids fracturing fluids (or frac water) can be contaminated with; eg; bacteria; organics; natural organics; 0 appearing in composition; organic treatment chemicals; (such as viscosifiers, emulsifiers, stabilizers 60151017..;..etc.); production chemicals (such as scale reducers, reducers, 110000 anti-corrosion chemicals | anti -corrosive “chemicals (pH modifiers” etc.) and/or other contaminants where YO leads to a high percentage of total dissolved solids.The presence of these contaminants can interfere with the

e (sale) the subsequent use of the water; Storage and/or discharge (eg, injection into disposal wells or dispatch to municipal treatment facilities). Domestic treatment facilities face a regular increase in waste water requirements associated with hydraulic fracturing and meeting these requirements is costly. Similarly, to the extent that fracking water and Jin 5 water store contaminated oil in oil field drilling, open ponds or lagoons, high levels of residual polymer and stagnant solids in drilling can aid in hydrogen sulfide production. High, which causes safety and environmental issues.More recently, producers are converting to closed cycle systems as the preferred method for circulation of return flow water and product water (ie, reuse of that water in subsequent processes). The water used for hydraulic fracturing operations is often a combination of product water and/or coiled water, surface water, and/or local water (also known as 'mixed water'). Successful treatment allows For polluted water produced in pits and storage tanks with the formation of mixed water from a greater percentage of the water produced than what could be in another way; And in turn; provide low disposal costs; Low VO fresh water costs; Use/sale problems Use less water. Simple, low-cost technologies are required so that small producers or separate production areas can easily use the processing processes. The process disclosed herein is an unexpectedly low-cost efficient process that performs well under difficult process conditions associated with water from drilling/0 oil and gas production (JB) as it contains high levels of One or more calcium (Ca) magnesium (Mg) magnesium barium iron yaa (Ba) barium (Fe? (Ferrous) or ferric oxide) (Fe (Ferric) manganese (Mn) plus chydrocarbons sulfates (504); total organic carbon (TOC) total dissolved solids; YO volatile organic compounds; and bacterial contamination. The

The methods and system disclosed herein will reduce and/or effectively reduce bacterial contamination; chydrocarbon metals inorganic pollutants or metal ions phosphates volatile organic compounds; ass (TSS) total dissolved solids and other contaminants from oil and gas from waste water for the ultimate reduction of water footprints associated with oil production The new highly effective treatment method and system disclosed herein are unexpectedly very effective in treating the highly produced water pollutant by removal and / or reduction of certain inorganic pollutants such as calcium; magnesium; sodium (8L); iron (Fe) 1200 | 0 chlorine (Cl) chlorine; manganese; dissolved solids (CaClO; (dla) sulfate compounds barium as well as hydrocarbons biological contamination and other colloidal material furthermore by modifying Ailes physical process variables some contaminants can be selectively targeted at higher removal rates chemical performance Chlorine dioxide's unique properties and physical properties to VO make it ideal for use in fracturing fluids 7801017109. For oxidant 1; It is possible to penetrate the hydrocarbon and crack the emulsions allowing the separation and extraction of the hydrocarbons; Plus reduced and/or removed biocontamination. Because of its fineness, its ability to oxidize Jie contaminants can be directed to sulfides and polymer residues without the formation of undesirable by-products; In contrast to bleach Gaull sale or chlorine, chlorine dioxide does not form chlorine by-products that could cause operational or environmental problems. Chlorine dioxide and/or chlorite ¢ is however regulated in wad form and caution is necessary in its generation, handling and storage. Furthermore, it can be very expensive to order chlorine dioxide from wastewater and/or source water Various embodiments of the Yo invention utilize the oxidative power of chlorine dioxide in conjugation with oxygen

(or air) to achieve unexpected results; unexpected increase in effectiveness; And unexpected processing ability

for these types of water; which were not achieved prior to disclosure herein.

add to that; According to some different embodiments of the invention; A combination of cleanse is used

and oxidation of chlorine dioxide to provide fast-acting waste water treatment. These methods and systems lead

To an excessive chlorine dioxide capacity and an excessive efficiency in relation to the volumes of water

processing; that provide low chemical use; low energy; low effluent; where

In turn, it results in a low burden on the environment and a low cost.

according to one or more of these embodiments; The use of chlorine dioxide is in a closed cycle system

“oilfield wastewater to treat oil field waste water storage tanks closed loop system: Unexpected possibility of bacterial contaminant production; calcium; Magnesium sodium lll or water 0

+iron; chlorine; manganese total dissolved solids; (CaClO; sulfate compounds; barium; oil;

fat; terminator combinations; thus providing low processing costs; Fluid discharge and formation costs

Water purchases (by allowing significant reuse of oil field waste water as a fluid

hydraulic fracturing fluid, low environmental and safety problems. In alternative Vo embodiments; chlorine dioxide may also be used for pretreatment and purging of fracturing fluids prior to

use in crude oil production processes and/or hydraulic fracturing; Includes but not limited to water

surface water output; mixed water; Return effluent or any combination thereof.

Accordingly, it is desirable to provide methods and systems for treating waste water associated with DHS

pumping and the production of crude oil (ie, the resulting water) to mitigate problems associated with current treatments. 0 to be exact; It is desirable to provide improved methods and systems for treating the produced water for reuse

In the form of fracturing fluids

While certain features of traditional techniques to simplify disclosure of the invention have been discussed; did not protect

applicants in no way those technical features; It is believed that the protected invention can include:

One or more traditional technical features discussed in this document.

in that description» where a document is indicated; or a procedure or item of knowledge or discussion; Such reference or discussion shall not be taken as an acknowledgment that the Document; procedure or item of knowledge or any combination thereof; on the priority date; available to the public; publicly known part of familiar general knowledge; or otherwise be prior art under applicable legal provisions; or is known to be 0 related to an attempt to resolve any issue to which that description relates.

ua olf is the general form of the invention in a feature; The invention relates to a method that includes the following steps Step 1. The produced fluids are transported in a vessel that allows a holding time between 0 ? Minute and Toe min.

Ye Step LY The fluid is withdrawn from the first vessel by means of a pump passing through a venturi sprayer and returned to the first treatment vessel. Air is introduced into the atomizer to provide for fine atomization and/or atomization of the air stream returning to the first container. A solution of sodium chlorite or a combination of sodium chlorite and sodium hydroxide or these two chemicals is also fed into the return.

1 separate. alternatively Another feedstock may be added to simplify precipitation of a target compound. The SUPPly stream is drawn from approximately 0 level up from the bottom of the vessel. The water is discharged through a distribution line at the center line of the bowl. The first vessel has preference for degreasing hydrocarbons or other low specific gravity sales; and AY preference for high-density solids.

0 Step LY The fluid is discharged from the first vessel to the center line of a second vessel. Jay Chlorine dioxide gas and transfer line Chlorine dioxide dosage sufficient to achieve residue in second vessel.

A — — step ;?. The second vessel has a retention time of approximately +3 to Te min. The second bowl has a downward flow into the third bowl. The second bowl has preference for degreasing from sale flocculant 106001816 material where JE is low specification. Step Lo The third bowl has a holding time of approximately 10 to 00 minutes. That vessel has an overflow to the third vessel or clear well. This vessel has a preference for removal of the high density of solids remaining in the vessel. The following expressions used in this document have the following meanings: Chlorine Dioxide - the amount of chlorine dioxide (or sale of another oxidant) consumed by SUS from non- 0 organic and organic) in a given sample of wastewater (i.e., oilfield water, fracturing fluid, process fluids, or other target fluids. Chlorine dioxide demand is determined by By subtracting the amount of chlorine dioxide remaining after a given period from the amount of chlorine dioxide initially added to the system Free residue or residue - the amount of chlorine dioxide (or other oxidant) present at a given time Yo to interact with the biospecies after conversion of the previous pollutants (or "request"). in pal the amount of chlorine dioxide (or other antioxidant) available for bacterial control. Biocide - chemical agent capable of killing living microorganisms, often in a selective manner ( Also referred to as bactericides or antimicrobials bials Yo Biological Contamination - i.e. microorganisms living a J microorganism A by-product of a living micro-organism present in waste water (ie; water Jia oil); fracturing fluids; Treatment fluids dalled source water or fluids for another purpose. the

— q —

Effective Biocidal Amount - An amount that will fight; or kill or otherwise reduce the content

bacterial or microbial waste water (ie, oil field water); fracturing fluids; process fluids; water

The source or fluids for another purpose under study.

Well Fluid Fracture Fluid—Frac Fluid—meaning the fluid used

0 in any drilling operation; complete Maintenance and production of subterranean oil and gas from

Gas wells and generally includes Le & source (or raw; or primary) feed (eg

example; fracturing water) plus any additives 8001017/85.

Frac Water - Raw water feed used in the fracturing process

hydraulic fracturing from any source; Surface water includes, but is not limited to, surface water, municipal water, process water, or produced water.

Produced water - Naturally occurring water within a subterranean formation is being produced

to the surface, whether as part of a hydraulic fracturing process or as crude oil.

Flowback Water - fracturing fluids extracted from

It flows back to the surface after being pumped down into a subterranean formation as part of the 1 hydraulic fracturing process or crude oil.

oil field water - as used herein; Includes production water; flowing water

yield water 101/0801 and other fluids that Jia are by-products of crude oil production;

hydraulic fracturing; Or other petroleum production processes.

Further as Wel 2 in this document of All 58 have the words Pl] | by "has" yo and "includes" and all grammatically variable forms of each of them have the non-exclusive comprehensive meaning that does not exclude

Additional elements, parts of an assembly, or a structural element

The features of the present invention will be readily apparent to those skilled in the art by reading a description

the following incarnations.

the

=« \ _ BRIEF EXPLANATION OF GRAPHICS The subject matter to be specifically considered and patented is presented distinctively in the claims when the description is inferred. The foregoing and other features and advantages of the invention will be easily understood from the following detailed description of the preferred embodiments together with their accompanying drawings: © Fig. 1 is a schematic typical water treatment system according to an exemplary embodiment of the invention. Figure ¥ is a schematic diagram illustrating an embodiment of the AT of the invention. Figure 3 is a schematic diagram showing an embodiment of the AT also of the invention. the shape ; is a schematic diagram showing an embodiment of the AT also of the invention. 0 Figure © is a schematic diagram showing an embodiment of AT also of the invention. Figure 7 is a schematic diagram showing an embodiment of the AT also of the invention. Figure 1 is a schematic diagram showing another embodiment of the invention. Figure A is a schematic diagram showing an embodiment of the AT also of the invention. Figure 4 is a drawing illustrating one embodiment of the invention. 0 Detailed Description: For purposes of furthering understanding of the principles of the invention” embodiments shown in the drawings will now be indicated and special language will be used to describe them. It will be understood, however, that it is not intended therefore to present the limitations of the field of the invention; And any other substitutions and modifications in the embodiments Raum sell and any other applications of the principles of the invention as set forth herein as would normally appear 0 anyone skilled in the art to which the invention relates has been completed.

-11- The expressions used in this document are for the purpose of describing specific embodiments only and are not intended to limit the invention. As used in this document. singular means "8"; 80" and 67 that unless the context clearly indicates otherwise. will be of the plural forms of clad include (and any form of include; such as 'include' and 'include'); 'by' dell It is also understood that the expressions 'include' (and any form of include; such as 'include' (le) (and any form of baha such as 'has' and 'contain © 'contain' and 'include') are Have the verbs Jie on); and 'contain' (and any form of containing; Ja is a broad conjugation. As a consequence; a method or device where 'includes' or 'has'; or 'includes' or 'contains' contains one or more steps or elements that have one or more of those steps (Jal) or elements but are not limited to having only one or more of those steps or elements. or 'contain' one or dest' A step of a method or element of a device that "has" or has 0 or more attributes that have one or more of those attributes; Or an installation that is designed in a certain way at least in that way; but it can also be designed in ways that are not listed. hydraulic fracturing and large water drilling; turn Produces large quantities of waste water. additionally; 0 Many other types of industrial or commercial operations depend on large quantities of water and produce large amounts of waste; Each of them requires treatment. These industries include; without limitation; The industry is primarily agricultural; chemical; pharmaceutical; mining » metal plating; fabric; fermentation » food processing leads to the presence of biological contamination, semiconductor pollutants and beverages; and other organic semiconductors have low activity and can cause damage (ie, corrosion, blockage, growth of harmful bacteria). likewise; The types of water that have high organic or biological pollution residues are unsuitable and need to be treated before injecting them under the oilfield operations. Chlorine used to treat oil field water and surface flow—back water (including production water; oilfield water Yo

-117-

(surface water) to produce both a biocontainment and to assist in breaking down residual organic contamination in the water. For example, though not exclusively, one or more embodiments of the invention may be used to treat the produced water or return effluent prior to discharge or reuse. Both tend to of produced water and returning effluent to have significant biopollution, as well as a high load of organic pollutants (those petroleum hydrocarbons, oil and grease6, and diesel-related organics 1818180-A01658”; 176 8); Jie polymers iron polyacrylamides volatile organic compounds inorganic transition metals or metal ions

suspended solids and other contaminants.

I in a typical embodiment of the invention; The methods disclosed herein can be used in a closed continuous cycle system to treat the produced water or return effluent (before sale) using the water in a subsequent hydraulic fracturing process. however; Also according to the protected invention; The methods can also be used as a pretreatment of the fracturing water; Includes but is not limited to 'on the fly' pretreatment; prior to water deposition in 18900105 storage pits/tanks; or as part of a variable

oilfield production systems Jia Wide Oil for Vo production systems. One embodiment is a process for treating waste water that provides a significant reduction in contaminants other than chydrocarbon metals (JED). inorganic contaminants volatile organic compounds; total dissolved solids and other contaminants from oil and waste water gas

gas wastewater | 0 compared to conventional treatment methods; The treated resultant water is allowed to achieve a final chlorine dioxide residue in the range of about +0 mg/l and 0 fame 50 l thus making the treated resultant water suitable for reuse; For example (JU in the form of hydraulic fracturing fluid without the need for additional processing techniques (Jie reverse osmosis systems). (SIS customizes) performs the processing system and method disclosed in this

the

Q1 document to the unavailable Lad and unexpected decrease of metal ions that include Fe; calcium; manganese; Magnesium and barium. in certain embodiments; The amount of chlorine dioxide required to treat the resulting water is considerably less than what would be expected by those of ordinary skill in the art and is considerably less in comparison to what would be required if chlorine dioxide separation was used thus also providing financial and economic benefits to Great scope for commercial use. Figure 1 shows an embodiment of a closed cycle process system 151 according to the specified embodiments of the invention. in operation; As represented in Figure 1; Y raw produced fluid is transported in; or enter; first treatment vessel 011 through treatment inlet VV system inlet 0 via NA pump though not restricted; As shown in Figure 0 the first process vessel 011 is a hydraulic frac tank placed on site at an oil and gas production site. Prior to transfer in the first vessel Vo the Y fluid may be stored in one or more storage frac tanks (LS 001) shown in Figure 1 in embodiments. dha The fluid ¥ rile Vo can be transported from eg jd truck pipe or well using various transport methods and equipment known in the art in the first vessel AN In typical embodiments, although not required, the crude product fluid is a highly contaminated wastewater stream from an oil and gas application that includes high levels of contaminants selected from the group consisting of bacterial contamination; calcium; magnesium yo; sodium; iron; chlorine; manganese; total dissolved solids; “CaCl; sulfate compounds; barium”; oil; grease; and combinations thereof. First 011 using techniques known in the art.Before entering the vessel 011 the fluid ?(eg; ore; untreated product water) has an initial first order Yoo where it can be identified as Using tests known in the art.

ve

For the purposes of that disclosure; Referring to Figure 1, the waste water to be treated is indicated; For example, (Ja) the resulting water; Contained in vessel 011 herein as fluid OY The first treatment vessel 011 provides fluid IY with a retention time of approximately 11 minutes to +0 minutes. The total retention time required for Fluid IY will vary and is dependent on the properties of Fluid 0 and other environmental factors. For example Jd in some embodiments the retention time will be this sd y kk decoding < 1 (£0 (fh) TO (Fu (YY) 5 e or 01 min; lay in any and all ranges and subranges has Je) sabil 15 (Jd) to 010 minutes; 8 to 55 minutes; 0 to 50 minutes; 10 to 1 minute; 11 to 10 minutes; 01 to * ?minute; Yo AYA

minute; Yo to 00 minutes;..etc.).

0 Once Jal is in vessel 011 the fluid IY is then withdrawn from the first vessel 011 by means of a circulation pump (YF circulation pump) passing through venturi 4; and returning to treatment vessel . 011 Jf The supply stream of fluid IY is drawn from a level of approximately 7708 up from the bottom of the first treatment vessel 011 for transport or distribution through line #.As fluid ?a passes through the atomizer of oxidizer 0760801 is introduced 560; which in the embodiment shown herein is air; in

Vo sprayer; To provide for fine partitioning or a dissolved stream of air in return fluid A with its return to the first vessel .011 air (or oxidizer £1) is introduced at a rate to avoid scavenging air so that volatile reductants (i.e.; Hydrogen sulfide (sulfide) by oxidation; Yay from physical purging or scavenging. By selecting an air flow rate that prevents or avoids gas separation of the hydrogen sulfide or other volatile compounds present

0 In fluid JY the reducers are oxidized in situ Vay from the purging by allowing the oxidant to come into contact with the sulfide compounds and allow oxidation to occur. In the embodiment disclosed in Figure 1 the £0 oxidant is air. however; In embodiments of Alay the oxidized sald can be Sle 5 0 from oxygen—enriched air cair or any chemical oxygen source or combination that is stable

Yo using chlorite 00103. Although not preferred; If ozone is used, it must not be used

AC \ — Use it in combination with chlorine dioxide in the first step because ozone consumes chlorine dioxide. Furthermore it; in alternate incarnations; The oxidant fe can be introduced into fluid ?a by means other than spray 4; Such as injection boom 11667 pressure source pressurized source aerator mechanical agitation © air sparger cair sparger diffuser or sprayer or other common air injection and distribution means In Art. the amount of oxidant 0; the dose required will depend on the properties of the fluid ¥ (eg (JE Preliminary Order 107); the treatment system and the specific use or application; together with other considerations known to those of ordinary skill In Art. Total volume of fluid IY to be treated, using a more preferable dose of about 01 mg/kg to about 1 kg [Se] of oxidant 4 to a total volume of fluid 1 to be treated. a Embodiments Dosage includes You (Yer (00) Vo (Yo 0 Yo) Nifaq (YO) Yll Nk Lt Bl (YOu L One P Ave Al cen mg/ kg oxidant to the total volume of L fluid to be treated; including any and all ranges and their sub-ranges (eg 010 (JED) to 0056000 mg/kg; 001 to 0001 mg/kg 6 * * 9" to Y"ue mg/Ov ¢ PRESS to + Y * 1 mg/kg 1 “ee og to Y * + 0 mg/Y * 4 PENS to J ee * 1 mg/o * 4 PENS to 0 ee * 1 mg/kg * * 1 to 0 ee * 1 mg/PENS 4 [Ore Ye to You mg/kg; A) to Ou mg/kg;..etc.) When the fluid iy is withdrawn from the first s vessel 011 by means of a circulating pump Y and passes through a 1% sprayer and before returning to the first treatment vessel 110; A solution of sodium chlorite (chlorite (Ys) is introduced either at the same time as oxidized sald 0; or to a large extent simultaneously with it. Like Jan a combination of sodium chlorite ( Chlorite (Fr) and sodium hydroxide (caustic +4) as a single feed or as LEAR vi “b) and sodium hydroxide (caustic 30) as 0 approx. Alternative; sodium chlorite (chlorite) two separate feeds (not shown); at the same time as air; or to a large extent baltz safe with him In the “sodium chlorite solution preferred embodiment” 775 sodium chlorite solution is used as DiKlor® Saber Oxidation Technologies, Inc. Commercially available as B available and known to those 0 chlorite #0 B. however; The other available sources of chlorite are 0'b at an appropriate dose 0 of those of ordinary skill in the art. in embodiments of the invention; Chlorite 5000 mg/L is added to about 01 and an appropriate period of time to reach a dose of about in some embodiments; Include the dose (JU) to be treated. For example IY in the fluid Ni YOu nikat kak AY kat nef nak YY YY Ye 001 on af chlorite

00 470 060 mg/L including any and all ranges and ranges (dpe dl) in it (eg 0 to 000 mg/L 15 to 001 mg/L 15 to 7000 mg / L 01 to Yoo 01 to 01 mg/L © to 001 mg/L 00 to 001 mg/L don £0 mg/L 77 to $Y 717 to 10 mg/L; 7 to 70,000 mg/L 71 to 0 mg/L (YY to 770 mg/L etc.).

1 Referring to Figure 1; after the dose has been administered using a mixture of air; sodium chlorite; and caustic (optional) »; The returning fluid IY is drained back into vessel 011 through the distribution line © and/or other distribution means known in the art for uniform distribution of fluid IY into the first vessel 011. In that particular embodiment » is Drain returned fluid ?a back into vessel 011 at center line or centerline TA (halfway through the vertical rise

Yo is the volume of the fluid contained in the container); or to a great extent about the midline; From the first vessel .01 a number of different means of dispensing the fluid ?a may be used during this step; Including but not limited to a 19 submergible boom (fixed or movable) with openings for fluid discharge ?a as shown in Figure 1 or similar types of uniform spraying or dispensing mechanisms known in the art of waste water treatment.

yy through the nebulizer; After 0101 of pot IY continuous rotation is allowed; or recycling; of the fluid through the distribution line © by diffusing the fluid 'A sufficiently with the oxidant 011 that returns in the vessel in the form of 011 ensuring finally that the fluid ?A diffuses into the first treatment vessel eT and chlorite 0 *b, where evenly distributed to 0 and chlorite © 0 complete with and exposure to the oxidant which shall significantly; and unexpectedly; lead stage 1; or .011 substantially through vessel 5 B (and optionally caustic) to a significant reduction in demand 0 and chlorite 6 0 combines oxidizing agent or a high percentage of reduction in contaminants; compared to oxidation / 001 initial demand Ventilation using only air / oxygen For example, the drop in demand from Process 1 during Phase 780-1700 can be as much as 011 in the Initial 7000 Processing Pot detected. Shown in Figure 1; the 0

IY so that chlorine dioxide (170) can be introduced into the fluid (101 treatment system dalled) 1. chlorite 07b during phase cae of; or in combination with Ya skimming 011 degreasers in one or more embodiments; A first treatment vessel or other low specific gravity material whose hydrocarbons to remove hydrocarbons 1 means rises to the top of the fluid?a. Degreasers 6 are well known in the art of treating Vo paddle waste water; The means for degreasing oil include; A paddle type dissolved air flotation or other equipment known in the art to remove conveying belt (type treatment tank) hydrocarbons or flocculants from the surface of a treatment tank (aay) removed solids at the same phase hydrocarbon in certain embodiments; the amount of hydrocarbon from the fluid ?a.77-1 may be in the range of about 0 also a separation system 011 in one or more embodiments; the treatment vessel is The first is to remove solids High Vv (removal means dll) Separation system. ov separation; or means of removal may include waste water treatment that can remove solids deposited at the bottom of a YO tank

AA

in embodiment .SCraper or scavenging auger processing; It may include; For example; Activating mechanism draws up precipitated solids 1011 Other agitating or scavenging mechanism rests on the bottom of the vessel (ada

Baal through 011 and the solids are pumped out of the BEAD to the center of the tank; Where ;1 is in the second phase of the embodiments of the invention protected herein; And shown as in Figure 011, the treated fluid is withdrawn or discharged from a first treatment vessel (YY) using the pump © transfer line Jit via line 0101 from a second treatment vessel centerline For Ya injection port, chlorine dioxide gas is introduced into fluid A at injection port 4. Fluid B. A second dose of dia is on 017 through a conveyor line 9 and before distribution in the second container, a container Jala Chlorine oxide incorporated into fluid A? is sufficient to achieve residual chlorine dioxide in fluid B and depends on the amount of biocontaminant in the fluid. In some embodiments the dose of 011 includes a Ys dioxide treatment

JB mg/L; For example, 0000 mg/l to about 10 TP of chlorine dioxide yeah / liter including any and all ranges and their sub-ranges (eg; 15 mg/l to 375 mg/l AY 001 to 775 mg/l 01 mg/l 001 to TY 47 il mg/litre 0.5 to 770 mg/litre £0 to 775 mg/litre £0 to 0 to 100 to 7; mg/litre 10 mg/litre YY to 01 mg/l fe to ∼00 mg/l fe (mg/l..etc..) 0 In certain embodiments, the amount of biocontamination may be determined or monitored prior to introduction of the raw fluid? eg 011 from process vessel IY immediately while withdrawing fluid 011 process vessel and testing one or more samples from hydraulic fracturing storage tanks A) eg; YS or some combination may terminate co distribution line (V+) vessel VY inlet 5 to determine microbial contamination. in alternate incarnations; In the same line, monitoring equipment can be paired at different locations along the treatment system to allow continuous monitoring of biological contamination. The test may be performed by assayers known to those skilled in the art to determine microbial demand and/or microbial killing

-14- The concentration of the target residual chlorine dioxide in treated fluid B depends on the storage period specified before re-use as, for example, a hydraulic fluid. For example, chydraulic fluid for immediate use is Fracturing water composition in a hydraulic fracturing system of about 1.0 mg/L and approx. 1.1 chlorine oxide is desirable from fluid B between about SB residues preferably between about +0 mg/L and about © mg/l. If on the other hand; 0 Fluid B was to be stored for several days or before reuse as hydraulic fluid; The remaining 00 mg/l target chlorine dioxide is between about (© mg/l) and about (sald) concentration of mg/l. A person skilled at 00 mg/l and preferably about 10 between about ef time on the properties of the ordinary fluid in the art can calculate and determine the dose required

0 Estimated storage, intended use, and other factors. for example » in some embodiments; Target residue includes 11 mg/L 0.7 mg/L 17 mg/L 1.5 mg/L 01 mg/L 1.5 mg/L ? mg/“il © mg/litre 0 mg/litre VO mg/litre Yo mg/litre YO mg/litre 0? mg/L or 0 mg/SA Ly including any and all ranges and ranges Rue dl) in it (eg 11 to 500 mg/L 1.1 YO to 01 mg/l 1.1 to 10 mg/l 1.1 to 1.1 mg/l to ?mg/cA 5 to 10 mg/l 1.5 to 10 mg/L © 5 to 10 mg/L 01 to 10 mg/L 0 to 10 mg/L © to 10 mg/L © to tr mg/L © to on mg/liter 01

to 00 mg/l, 700 to 00 mg/l, etc.). Any suitable chlorine dioxide production method known in the art may be used to generate 0 chlorine dioxide suitable for use in the present invention. in general; Chlorine dioxide solutions can be produced by treating chlorite salt solutions (for example; (NaClO) using an acid solution to produce acidic solutions containing (ClO). This scavenges it as a gas in water to produce ClO, aqueous. Other precursors such as sodium chlorate may also be used. For example YO; in an embodiment (unde) the present invention provides a process involving the production of SB chlorine oxide using

1. For example; The “chlorine dioxide generator prepared as chlorine dioxide” was disclosed and protected in US Patent No. 1,577,519, the contents of which are included in this document for reference. Chlorine dioxide is generated either directly as a gas or as a carrier (or a carrier, preferably in the form of another suitable chlorine dioxide mixture). The generator is preferably operated with an excess amount of liquid carrier ©

Ampurity contaminated sale sodium chlorite to produce chlorine gas generation potential in the form of in line with the treatment system; 175 with reference to Figure 1; The chlorine dioxide precursors, sodium chlorine dioxide precursors and sodium chlorite chydrochloric acid are stored in the YA flow stream respectively. The sprayer is VAS YY VT tanks in hypochlorit 0 generator tanks. Chlorine oxide from the generator reaction column SB drains a stream and draws ADA water that forms aqueous chlorine dioxide in the water stream to form aqueous chlorine dioxide for the fluid. residence time 017 in the typical embodiment; The second processing pan has a minute; Although the retention time will vary depending on the nature of the fluid from To to approximately 10"b

VO AY 001 ?b. For example; In some embodiments the retention time will be VO min; Including any and all bands and sub-bands with 1 or YY (Yo (YY 1E) 01 to 10 minutes; 10 to 11 minutes; 00 to 11 to 50 minutes; 01 JE sabil Je) minutes;...etc..). The second vessel shall have Yo to 11 minutes; Yo to 10 minutes; Underflow 0 “pipe” or other means conduit on VY underflow means 0 is well known in 017 to flow into a vessel 011 to allow fluid B to be placed at the bottom of a vessel On Art 017 means of waste water treatment systems. In a typical embodiment; The second vessel includes the light flocculate material (sale shown) for degreasing pe) VE on other VY of low specific gravity; outside the surface or top of the second processing vessel well known in the art and can VE as used herein; Examples of degreasing methods are YO L

-1?- to include; For example on oil skimmers (eg, paddle type, conveying belt, dissolved air flotation) or other equipment known in the art to remove lighter solids; hydrocarbons or flocculants. From the surface of the treatment tank © The third treatment vessel 017 contains fluid 7 C. Vessel 017 has a retention time of approximately 10 to 10 minutes; however the retention time will vary depending on the nature of fluid 1 "c. eg Jd) Some embodiments the retention time will be OY 000 lm 01 yy (Yo 7 or 1 minute; including any and all domains and their subdomains (eg 01 (JE to ve min; 11 to ve min; 115 to 510 min; 01 to 50 01 ARE to 71 0 min; 01 to © ?min; clear well as used herein; ad overflow means 11 are well known in the art and may include, for example, for example; A conduit, line (Jas) or other means to allow fluid oY to flow from Ad vessel 01 into vessel 01 of which VO is well known in the art of wastewater treatment systems The third vessel 01 shall also have means for removing high-density solids from the treated fluid?d from the bottom of vessels 0017 examples of which are well known in the art and may include, for example, JED scrapers or augers In the embodiment shown in Figure 1, the process vessels 011-015 are hydraulic fracturing Yo tanks located on site at an oil and gas production site The disclosed protected product water treatment system is combined with a cycle system already closed in situ. In alternative embodiments the foregoing method and system may be modified to remain within and consistent with the invention disclosed herein. For example and more generally; dallas with a closed loop Yo. closed loop treatment system Yo in accordance with the claims of the invention. The closed cycle treatment system 151 includes:

1 to be treated; (Vo) (eg waste water 001 fluid stream Ve 560 and oxidant 0; chlorine oxide 0 vessel and treatment/storage system slo For example; Vo stream on waste water 001 Fluid stream The fluid stream includes a check from an oil and gas site.

Yoo A mixture of chlorine oxide LY is introduced into the raw produced water le Vo The waste water is 1 0 preferably chlorite 1 comprising .001 chlorine oxide in a fluid stream fr and an oxidant ?a); or a combination of chlorite (1) but which cannot also include chlorine dioxide (FY) for example; as is introduced into the stream .001 (Ir) and chlorine dioxide (YY) for SFr (disclosed in association with Fig. 1; sodium chlorite (ie, chlorite if Fig. 1 is indicated) may be included; where of is (or aerosol 31 by elicitation with aerosol 0 that is processed; or other well known means 001 about a portion of the fluid stream Ble Yo sprayer A person of ordinary skill in the art may use techniques known Alay in the art. in embodiments in the art to introduce; mixing and / or dissipation of chemicals into a process system; either directly in the tank or inductor pumps ls pas pumps including without fluid flow line in a fluid flow line pumps 0110105; chigh pressure injectors flow lines pressure dle Vo injectors or a combination thereof spargers mixers mixers conduits channels lines is air; ‎ chemical oxygen source rich in oxygen; or any chemical oxygen source stabilized with chlorine dioxide (0?a) and/or chlorite (1b); or some combination thereof. And the; in one or more embodiments of the invention; Oxidant 0 is introduced; By direct injection 0 (ie; air spray; compressed source; aerator; fine bubbles into waste water in fine bubbles)

Oil) (A cf) Yo or extraction via aerosol (os) diffuser mechanical agitation » diffuser must not be oxidized if ozone is used in the form of 1-1 for example. ; It is recommended to use it in combination with chlorine dioxide in the first step because ozone consumes chlorine dioxide.

AA Chlorine. On the contrary; Only chlorine dioxide should be used in the second phase; or step; and only after depletion or near depletion of ozone residue in the waste water; or water volume. In accordance with typical embodiments of the invention as applicable to the oil field and hydraulic fracturing industry; The storage/treatment vessel (or system) 00 contains the waste water Vo which is supplied by © source 01. Source 01 includes a source of the produced water. In dha embodiments the source 0 includes the return flowing water; surface water mixed water; fracturing water; waste water; or any combination thereof. One of ordinary skill in the art will also recognize that waste water Vo can be any target water or aqueous fluid that is contaminated (eg; with organics and/or microorganisms) and is sale) recrystallization or processing reuse storage and/or discharge back into the environment; regardless of industry. In one or more embodiments the demand for sale is the oxidation of contaminants in waste water Vo before Processing: from about 1 mg/L to about 800 000 mg/L preferably from about 0.000 mg/L to about 0000 mg/L The oxidant demand includes reducing agents including without limitation reduced sulfur compounds biomass and other biological by-products 1 and reduced minerals including but not limited to iron 11 eg in some embodiments Canadian sales calls include 1 TNF 00 You Bik Bug Avs (YOu Bank You evan Tvil Yarns Bank Tech and 0000 mg/l including any and all domains and sub-domains thereof (eg 36 to 500800 mg/001 pil) to 00 0010 mg/L 060 to 0001 mg/L 50 860 to 0 700 000 mg/L 0001 to 00001 mg/L 00 to 0001 mg/L 560 to 0001 fans vomit 001 to 001 mg/l (Hove 5000 mg/l 50 to 5060 mg/l etc.) - in certain embodiments; Nebulizer 01 is used for both generation and introduction of chlorine oxide 0 (i.e. chlorine dioxide oF) and/or a combination of chlorine(IV) dioxide and chlorite (SF) fluid YO stream 001 and »; additionally; thereafter to insert sald) oxidized 0 4. in other embodiments; the

Separate sprays 76010115 (eg Spray 4; YA Fig. 1) are used in a preferred embodiment; The TY-derived fluid for the Sale Vo aerosol comes from a storage vessel 50. Vessel 50 contains waste water Vo i.e. waste water to be treated; or a combination of slo treated waste (or other target fluid) and waste water to be treated. One of ordinary skill will grasp the art; With ella the steering fluid YY drive fluid can come from any available water dae placed in the same line with the system Now as shown in the figures AY The store/handling system 50 includes Single tank or container. However according to the invention” the storage vessel 0 * is a tank, cesspool or pond; or any other storage means (eg JUL reservoir tank container 0 | ©001806; or lagoon) that stores, transports, or contains waste water 11 from source 01. The Vessel System 50 may include one or LAST treatment tanks, vessels, containers, or other waste water treatment systems suitable for waste water treatment (0) (2) JU as described in association with Figure 1; Vessel 50 actually comprises four treatment vessels 011-014 and storage tanks 10 ... In embodiments of the invention “0 chlorine oxide ? and oxidant 0 at that rate where it removes volatile reductants (i.e., hydrogen sulfide) by oxidation rather than physical purging or scavenging, and by choosing an air flow rate that prevents or avoids gas separation from Hydrogen sulfide (or other 0 volatile reductants) present in the waste water (Vo) reductants are oxidized on site rather than purified. The goal is to add water The oxidized 0© is added to the fluid at a flow rate that brings it into contact with the sulfide compounds to allow oxidation to occur. Therefore, the flow rate that leads to the addition of volatile air must be avoided. Thus scavenging sulfide compounds before oxidation. The volume of fluid to be treated in the Vessel 00 system will directly affect the range of flow rates that Yo can be used to avoid gas separation/purge; And therefore; The appropriate range is diffuse. For example; maybe

(d) A small tank requires a much lower air flow rate than a deep basin. However, one of ordinary skill in the art will be able to determine the flow rate constrained to avoid purging, or scavenging, of volatile matter, based on size, depth, and/or ana Vessel system 50 (or fluid to be treated); Process system as a whole and oxidant ordering In fig. oF a spreader 71 is used to enter oxidant sald 0 ; in an embodiment; and as shown In Figure f the oxidant Hale 5 0 is added to the waste water 15 via a pressurized source Av near the bottom of vessel 0 and thus the mechanical effect can be used to promote mixing of the waste water Yo within vessel 0 If a single point insertion method is used, it is preferable that the injector be movable across the horizontal plane of the 50 container (not shown).

Yoo sl in one or more embodiments disclosed herein; 0 oxide is introduced for an amount of 00 “chlorine oxide as follows. 15 00 ase is introduced into the waste water and the oxidant of chlorine dioxide water for a sufficient period of time and in a dose sufficient to produce the demand for chlorine dioxide percent; including all ranges 710 percent to about 01 within the range of about 11 percent waste...etc.) the amount of 115 percent; eg 0 time and dose required on waste water Vo characteristics (eg, chlorine dioxide demand); treatment system; specific use or demand; in one or more embodiments; during the initial (or first) stage of Processing chlorine oxide Ye comprises only chlorite (oF) In embodiments where chlorine oxide 31 comprises chlorite ca (Fr) the introduction step of the oxidant 560 can be performed (and ; in many cases; is preferred) cam Sali at the same time as 0; substantially at the same time; or substantially concurrent with it (see for example Fig. 01 the description of Fig. 1 and the examples in this document). Embodiments of the invention; chlorite is added 0 0b with an identical dose and a corresponding time period to reach a dose ranging from about 10 mg/L to about 010 mg/L in the fluid ?A that will be treated. For example; in some embodiments; Chlorite dose 1a*b includes 1 netkat yy nat mvl VAC d1 Yo .2k (YOu a 7 06 fame liter including any and all bands yi

Yo mg/L 500 mg/L 15 to 00 to 01 and its sub-ranges (eg AYO 001 mg/L 001 to 10 mg/L Ten to 10 to 700 mg/L £0 mg/L 77 to 71 to 10 mg/L 77 to 00 mg/L ©081 to 00 mg/L reflux..etc..) 771 mg/l 7 to 001 to 717 mg/l 001 mg/l 7 to ?a); 1) chlorite is chlorine dioxide 0 in this step; it can be chlorine oxide © and free radical chlorine oxide reacting as free radicals SB or a combination thereof. Since (7 ) therefore; react at the same time mostly; chlorine dioxide cannot be added at high rates or, therefore; if 5.0 high concentrations at the same time with the addition of a large amount of oxidant during that step ) A71(chlorine dioxide includes chlorine dioxide A70 and chlorine dioxide (0?a)); Substance (QV) from the initial chlorite dads (or 0?a) cannot be added to chlorite 1) at the same time until all oxidized chlorine dioxide 0o has been converted or if performed in At the same time, the oxidant 0 at a low rate (QT) before the 11 chlorine oxide of the SB waste water should be added sufficiently to ensure that no fluid body dispersed through the fluid body is flushed or purified. (not shown) whether before 900 Furthermore; in certain embodiments; caustic 5 may be added

Vo or in conjunction with it to raise the pH of waste water 91 treated with chlorine oxide for example; In the embodiment described with Fig. 1; Vem is added to approx. by introducing AS sodium hydroxide (caustic 30) to achieve a pH of approx. contaminant metals contaminant metals will be avoided 05 higher pH of waste water iron will be distilled) of solution and form certain mineral complexes which (JU) (for example 00 expected within the (AY) range) tend to form at a lower pH. In the same embodiments upon request 310 sec of that invention” Skip the first step of adding chlorine oxide chlorine oxide and the order/system in place. Either prior to treatment with chlorine oxide 0 7; Vo?; in the waste water 0 oxidant is introduced or afterwards in conjunction with it The oxidant £0 is added at an appropriate dose and period of time YO yy mg/kg of substance 0000000 mg/kg to about Yoo of about AS to achieve a dose range in that every Lay to be treated; Vo to a total volume of oxidant waste water 0 mg/kg to 01 pH ranges and pH ranges using a more preferable dose of about to a total volume of fluid that is 50 oxidant m g/kg of oxidant 0001 about ele will be treated. once again; The amount of time and dose required will depend on the characteristics (© (request chlorine dioxide); treatment system; the intended use or (JB) way of Je) Vo waste the request; together with mechanical considerations known to those of ordinary skill in the art. in one 10 percent of the total; from about cf + or more embodiments; The application of the oxidant consumes

To percentage of total chlorine dioxide demand; Preferably from about 900 to about 0 percent to about 90 percent of the demand for chlorine dioxide. For example; In some embodiments the oxidant YO (Yo ov) will consume NF Nectfit LaVe or 01 percent of the demand for chlorine dioxide including any and all of its ranges and subscales (eg 01 (JU to ye percent; 01 to 710 percent; 15 to 0 percent; 01 to Av 50 sll to Ae percent; Te to 80 percent; Te to 90 percent...etc.) VO The introduction step of sale oxidation 500 can largely be carried out in conjunction with, simultaneously with, or immediately after the first step of adding Fe precisely when the chlorine oxide 00 is dad chlorite (Fh) during the first treatment step.As discussed lla The synergistic effect of sald oxidation and chlorine oxide can reduce the initial demand by as much as -1760 (0) or 0 in the next step (or second treatment); chlorine oxide 00 is introduced at a dose sufficient to achieve the target CIO residue in the fluid as it depends on the demand for redox sale in the fluid. For example, after introducing sodium chlorite, air, and caustic in step 1 of the Dall process ed in the 011 treatment vessel for a period of time (ie; about 11 to about 0 minutes); Chlorine dioxide is introduced in the second step into the second treatment vessel 017 until YO reach target residue of chlorine dioxide (Yo) however; In embodiments of Aly through vy A- on one or more chlorine dioxide 70 this second step may include chlorine oxide

Vo to be the same Ways chlorine oxide or a combination thereof. maybe; but not the (G0) chlorite oi) that was used in the initial first step. For chlorine dioxide in treated fluid or waste water 700 Target residue concentration depends on Hydraulic fluid (Jia) 58 specified storage prior to re-use; for immediate use as water (eg A-V) and as shown in Figures 0 001. Fracking in a hydraulic fracturing system; required chlorine dioxide residue from the fluid Preferably between about Gil mg/01 exiting the system between about (+ mg/l) and about mg/l and about © mg/l including any and all ranges and sub-ranges thereof (see 5

SL for example; Figures 1-7); if ltl (eg also 00 residual (14-19 sald) . it should be concentration of IT days or sae sad 00 the treater will be stored in the vat mg/l; Preferably 050 chlorine dioxide targets between about 050 mg/l and approx 50 mg/l including any and all bands and sub-bands of 50 mg/l and about 10% between approx (see 74-15 ). As discussed previously; in typical embodiments; Chlorine oxide contains chlorine dioxide (0?a) only during the last stage of the treatment process. During step 0 Vo 7a)) and Article 1 (in the form of chlorine dioxide 70) of this treatment, chlorine oxide cannot be added at the same time. 001 stream to the oxidizing stream 500 Total treatment time required for waste water (oe RAY) in one or more embodiments is hours; if A hours; preferably less than YE to achieve oxidation and/or disinfection is less than 0 or pond Pond (pit dank on 50 tank Jas) Ye In the same other embodiments, the total treatment time required for the water of a lagoon is min; preferably less than 1 to achieve oxidation and/or disinfection of less than approx 11 waste or combination pipeline is 5 0 min pipeline; if system/vessel Vo is approx use it for “on the fly” operations “Outside the field (see, for example, Key Ma Jie pipes and tanks;

—v4— will be 0010 when there is a restricted holding time and the process fluid (AT 6) is the example; The figures show its use directly. The different embodiments of the =F system are shown with reference to the embodiments shown in the figures

Ov In a vessel fv an air injection is used to introduce the oxidizing agent oF in Fig. 150 dalled A chemical tank of and a pressurized source 1 no. In figure Ve by means of a diffusing tool © co is used to introduce the oxidant 46. In figure Av a pressurized source chemical tank and pressurized source 17; placed in the same line; to insert the oxidizer £0 into the 710 spreader .47 mechanical agitator in certain embodiments; A mechanical vibrator is used. Current 001 Embodiments of ( ) and also figure A= are shown with reference to the embodiments shown in the figures

Vou in particular; in those embodiments; Yoo's different treatment system includes treatment system 0 for example; The Hydraulic Fracturing Treatment System on the 750 is a 'live' Al industrial water treatment system on the fly or any industrial water treatment system placed in the same line for immediate use. In Figure 6 the oxidant 00 is introduced; In the same is done ov? no. In the figure chemical source from the chemical source Yo the line by spraying in 2001 in the stream 0 in the same line to introduce the oxidizing substance Ay using a chemical tank 1 via a spreading tool 001 ; In stream 0 an air injection is used to introduce the oxidant (Fig. A You vo. Although not shown, the treatment system may include YY and a pressurized Ve source as well as waste water treatment methods 00 Caustic (JAY) is also on source; mechanical shaking overflow systems; shal Jie overflow systems; electronic sensors and cdefoaming agents; defoaming agents; monitoring devices. and Monitoring Devices As discussed above, any suitable chlorine dioxide production method known in the art may be used to generate chlorine dioxide suitable for use in the present invention. Treatment of chlorite salt solutions (eg where they can be washed on ClO, using an acid solution to produce acid solutions containing Yo

to

Gas-in-water form to produce ClO, aqueous. Other production materials such as sodium chlorate may be used

sodium chlorate too.

They are multiple chemical means of generating chlorine dioxide and chlorine dioxide producing chemicals

The interview is known in art; The selection of suitable media and chemicals shall be within the possibilities of those skilled in the art. Typical chemical means of generating chlorine dioxide are disclosed in the patent

American Patent No. 184,114 (Saffala met him) and «(:-Mason et al) o,Y.¢,.AY

and 5,177,776 “(Eltomi et al) and “(Eltomi et al) o0,YOoA VY and 5,115, .50?

et al) No. 00/8.); and 1,145,487 (\Mason et al) whose contents are included in this

document for reference.

0 in preferred embodiments; Chlorine dioxide shall be of the best available purity. more customized; Chlorine gas 985 00101106 must be present in the inlet chlorine dioxide gas at a level less than about 75; Preferably less than about 70.0 eg (JE) in the (unde) embodiment The present invention provides a process involving the production of SB chlorine oxide using equipment such as eg chlorine dioxide alse; as disclosed and protected in innocence

1 US Patent No. TEA EVA whose contents are included in this document for reference. Chlorine dioxide is generated either Hale as a gas or preferably as an aqueous chlorine dioxide mixture (or other suitable liquid carrier). The generator is preferably operated with an excessive amount of sodium chlorite to produce the potential to generate chlorine gas as a pollutant. Generally accepted methods for generating SB chlorine oxide can be obtained at; For example;

Yo US Patent Publication No. 74/7005 00180 (US Patent Application No. 1/1001 ); The contents of which are included in this document for reference. Furthermore it; The generator preferably uses the waste water 11 in the form of steering fluid to generate chlorine dioxide and brings the chlorine dioxide gas into contact with the waste water V0 under vacuum pressure so that the chlorine dioxide gas is drawn into the waste water 11 To form an aqueous solution of carbon dioxide

chlorine dioxide aqueous solution Yo

and in certain embodiments; The fluid to be treated is circulated through a closed-loop dalled system; System on site in accordance with the methods and systems disclosed herein; USES until the contaminants are oxidized and the appropriate residue of chlorine dioxide is collected before being discharged from the system. In the same embodiments (AY) after treatment with chlorine oxide “0” and a second oxidant 0 50; the treated fluids are left to settle in vessel 0 for an appropriate length of time to allow settling of solids and to drain off the oil to be degreased prior to reuse or discharge using industry-known waste water treatment methods In the same as other embodiments The treated fluid is used (or “sale use”) immediately after treatment for crude oil, hydraulic fracturing, or other industrial applications Figure 9 is a schematic illustration For another embodiment of 0 - the invention. aed the treatment system and method disclosed herein shall be coupled; prior to or can be associated with existing treatment units or systems for treating or transporting the resulting water. (eg Jd) The treatment system protected herein may be added to a system already in place at an oil and gas production site. Additionally, in exemplary embodiments and with reference to Figure 1 as an example, the concentration of biological contaminants can be monitored Molecular size; volatile compounds compounds total dissolved solids; and inorganic materials with the exit of the second treated fluid leaving vessel 014 and/or process system. Monitoring can be continuous or periodic. If the fluid leaving the treatment system does not enter a specified lire range, the fluid can be recycled back into the treatment system and/or the amount of oxidant and/or 0 chlorine dioxide entering the treatment system can be adjusted. Balmtl; in some embodiments; All or part of the stream flowing out of the treatment system can be recycled through the treatment system via one or more sale recycle lines (not shown). Recirculating the fluid stream through the system several times can allow for a significant reduction in the concentration of the contaminants. Referring again to Figure 1 as a GARY in some embodiments; Part of the stream leaving the system can be mixed with part of the Yo stream entering the VY treatment system inlet.

Although the examples and description above discuss a substantially dale” Alia cycle treatment system, the systems and methods disclosed and protected in this document can also be used for an “on the fly” cracking system and method, where the treated water can be used immediately and/or directly After being treated for fracturing (see Figures = A) for typical embodiments, the fracturing water to be injected into the subterranean formation may be treated using the methods disclosed herein in the oil field; prior to the blister head. For that system; You shall continuously fill the vessel (eg at fracturing tanks site; located at fracturing site/oil field) with required source water which will be treated prior to introduction into the well Water may include surface water mixed water produced water furthermore; in embodiments of the invention Abad) the system or process disclosed herein may be aggregated with one or more from one or more conventional or unconventional biocides, whether oxidizing or not oxidized; To achieve a synergistic biocide effect | synergistic .51001021 additionally; In embodiments of Aly a person of ordinary skill in Gall VO will readily realize that additional processing operations known in cl) may be included in the same line or elsewhere in the system (whether prior to processing according to that invention; or thereafter) in a process whether in batches or continuously. eg dah without restriction; Treatments to remove oil and/or solids can be included in the system; or if formation occurs; One of which can include a compatible SB chlorine oxide defoamer. Balmtl; in certain embodiments; The method and system that 01 disclosed in this document can be added to; or recycled in; Ulla existing recycling or processing system and can be carried out continuously in the same line or in selected quantities in a batch process. One of ordinary skill in the art will also easily recognize that in one or more embodiments; Appropriate equipment and/or measuring and fitting may be included in the method and system disclosed herein.

In the embodiments disclosed in this AAS a person of ordinary skill in the art will realize that residual chlorine dioxide may be determined and/or calculated using method E 02 4500-0

Standard Methods the Analysis of described in Amperometric Method 11

Standard Method or modified versions where the Wastewater ; Water E Amperometric Method 1 © 4500-0102 uses the following calculations: Yoo A Y,89¢ X Atm X (D - B) xX yy, Yo — ( A (mg/ClO, Chilorite (mg/L) = xD for khem ? Yeo [AT 0 [¢ OF (YO X +, va 07g X [¢ /(D) - B) - A] - chlorine (mg/L) where calibration A is chlorine and one-fifth of available chlorine dioxide; calibration calibration 8 four 0-fifths of chlorine dioxide and chlorite; calibration calibration © Non-volatile chlorine non-volatilized (le) chlorine (nitrogen cleans up the chlorine dioxide sample); however, it is not used in any calculation; the calibration is 00 chlorine. In the same embodiments (AY) the chlorine dioxide residue can be determined by spectrophotometry or by measurement of the oxidation reduction ((ORP) potential each of which is included in this document. or by modified versions thereof. ve Examples For simplicity of understanding of the present invention, the following examples of embodiments according to the invention are given. realizing cad] However, the scope of the invention is not to be restricted.” The following examples should not be read to restrict or limit the scope of the invention. In the following examples; The effect of chlorine dioxide on oil field waste water is being studied; With and without yo oxygen treatment. :1 JE

The following experiment was carried out to substantially determine how the addition of air/oxygen affects the treatment of chlorine dioxide (and/or chlorite) to an oil field waste water sample. The experimental results show that the air/oxygen combination using chlorine dioxide or chlorite has An unexpectedly beneficial consequence of greatly reducing the required dose of oxidant for the oxidation of sulphide compounds © in oil field waste water.In addition, the air/oxygen combination using chlorine dioxide unexpectedly achieves bacterial killing at considerably lower doses. In contrast, the addition of air/oxygen alone cannot affect a reasonable period of time for the removal of sulfides from waste water or for the killing of bacteria present in this document; and the addition of alternative oxidants (i.e. nitrogen) does not have the same synergistic effect.

0 for all experiments 1 - (A) 1 (6) below; A sample of water containing 10 percent solids with 101 mg/L of sulfide is used in the aqueous phase and has a pH of AY The solids consist of biomass; Inorganic (Material) hydrocarbon; sulfide compounds at a concentration of 87.5 mg/kg. Reducing sulfide and general @erobic bacteria were cultured from the sample to determine growth above 101 units.

V0 culture formation/ml. The sample (solution and solids) shall be black. First a series of test comparison samples are performed as follows: Comparator sample WA A 001 ml portion of the sample is treated with 75 mg/L chlorine dioxide over 11 minutes while stirring to obtain a minor residue (< 01 mg/L) of chlorine dioxide in the solution. The sample quickly turns black to brown/orange with the solids

0 insoluble solids precipitate rapidly and form an iron-type wafer. There is also a slight hydrocarbon sheen on the surface of the treated sample. No further change in the appearance of the treated fluid was observed over the course of minutes. The solids (slime) and fluid were analyzed for sulfide content using Gas Train 681161. No ALE detectable sulfide compounds were detected in the solids or fluids. Reducing sulfur and general aerobic bacteria were cultured from the sample; do not explain

Yo no bacterial growth.

o£

—yvo- mg/l chlorine dioxide YY ml of sample using 001 comparator 8. A portion was treated over five minutes while stirring. The sample quickly turns black to grey-brown/orange with the insoluble solids rapidly precipitating and forming an iron-type wafer. No further change in the appearance of the treated fluid was observed over the course of minutes. Materials on the Garret Gas Train were analyzed using sulfide solid (slime) and fluid to determine the sulphide content (0) mg/L (5 mg/kg) in the fluid and slurry; respectively. There is no residual 1 reductant dioxide and general aerobic bacteria from the sample; Shows the growth of sulfur chlorine. Sulfur was cultured culture forming unit/ml. 101 bacteria over mg/l of chlorite 401 ml of the sample using Yor. The C fraction of the comparison sample was treated as mg/l in the form of chlorite sodium) while stirring. The sample turns from black to brown/0 (010) orange with insoluble solids precipitating and forming an iron-type flake over a slight hydrocarbon sheen on the surface of the treated sample. Load not observed ten minutes. Minutes Solids and fluids are analyzed 01 There is an additional change in the appearance of the treated fluid after No sulphide compounds have been detected 68061 685 Train To determine the sulphide content using mg/l Vo detection in fluids; however The solids contain approximately 1 ALE sulfides

Jae sulfide. Reducing sulfur and general aerobic bacteria were cultured from the sample; Shows growth on a culture forming unit/ml. 0 fine ml of sample using air through a fine-dispersed stone Yor comparison sample Na. Part sprayed? minute; The sample changes color in 0 minutes. Over the course of 01 SLPM, the diffuser stone is black to gray in colour. The solids (slime) and fluid were analyzed for sulfide content using 0

Vo mg/l sulfide and the solids contain 1 mg/l sulfide (Garret Gas Train). Reducing sulfur and general aerobic bacteria were cultured from the sample; showing the growth of culture forming unit/ml. 011 Jae On the implementation of spraying experiments in three systems (air - chlorine dioxide, nitrogen - chlorine dioxide, and air - chlorite) as follows:

© Experiment E. A Yoo ml portion of the sample was sprayed with air through a Y Jara SLPM microdiffusion stone for four (£) minutes. At the same time a dose of 771 mg/d was cline l Chlorine dioxide is added over five (°) minutes, with the addition of al min to administer the dose without air spraying. In this example, ClO is added at low AK using volume and flow rate © of air which does not scavenge chlorine dioxide prior to its reaction.The sample rapidly turns from black to brown/orange with insoluble solids precipitating rapidly and forming an iron-type flake during spray stop.No further change in appearance of the treated fluid was observed over five (5) years. The solids (sludge) and the fluid were analyzed for sulfide content using a Garret Gas Train. There were no detectable sulfides in the solids or the fluid. Reducing sulfur and general aerobic bacteria were cultured from the sample; Experiment A. A 0.10 mL portion of the sample was sprayed with nitrogen through a microdiffusion stone at VO SLPM for four (£) minutes. At the same time, cline a dose of 771 mg / liter of chlorine dioxide is added over a period of five (°) minutes, with the addition of the last minute to give s the dose without nitrogen. Yo sparging 01009©80. The sample rapidly changed from black to brown/orange in color using insoluble solids that precipitated rapidly and formed an iron-type flake while stopping spraying.No further change in the appearance of the treated fluid was observed over ¾ minutes.The solids (sludge) were analyzed and fluid for determination of sulfide content using the Garret Gas Train There are 1 mg/L and 1161 mg/L of residual sulphide compounds in the fluid and solid compounds, respectively.0 Reducing sulfur and general aerobic bacteria were cultured from the sample; to 01 bacterial growth.Experiment G.Yoo ml part of the sample was sprayed with a air through a Y Jara SLPM fine diffusion stone for 115 minutes.At the same time linge A dose of 100 mg/L of chlorite (507 mg/L as sodium chlorite) was added over the course of five (*) YO minutes. The sample turns from black to brown/orange using insoluble solids

It will quickly settle and form an iron flake while stopping spraying. No further change in the appearance of the treated fluid was observed over the course of 115 minutes. The solids (slime) and fluid were analyzed for sulfide content using Gas Train 681161. There are no detectable sulfide compounds in the solids or fluid. Reducing sulfur and general aerobic bacteria were cultured from the sample; © shows bacterial growth over 10 culture-forming units/mL.

In the following examples; The unexpected synergistic effect of treating a storage tank with oil field waste water using chlorine dioxide and oxygen treatment in a closed cycle system is studied. Spraying experiments are carried out on two systems (air - chlorine dioxide (chai) and air - chlorite - chlorine dioxide) as follows:

0 Example?: A tank containing about 0,008,000 barrels (barrels) of fresh water and the resulting return effluent is analyzed and found to contain 000,010 mg/l total dissolved solids; Above 601 culture forming units/mL of bacteria and 56 mg/L of sulfide compounds in the homogenate at pH 7.8. The demand for chlorine dioxide from the fluid to be treated is specified as VAL mg/L. Specifies the amount of 0 75 sodium hydroxide required to memorize the number

The pH to be 10 gallons. The tank is equipped with a chlorine dioxide generator (see; for example JU US Patent No. (ETA, EV) although without limitation; an example of a generator al se could be the Saber system BB series portable DiKIor® als with maximum capacity os ?Jay per day of continuous production.This system is self-continuing and has distribution system

0 is allowed to circulate fluids in the tank. with more customization; A pilot fluid stream is drawn from the tank and circulated through also chlorine dioxide by a centrifugal pump at a rate of YY gallons per minute. The generator is arranged so that the suction for the stirring fluid stream is drawn from the lower end of the tank; The vacuum solution containing chlorine dioxide and/or air is returned to the tank and discharged to the bottom of the tank via an ALE movable injection boom.

Ad A —_ _ boom (see Fig. © L(A) The injection boom was moved continuously around the tank at a rate of 0*5 ft per minute. Sodium hydroxide is added to the tank using enough sodium chlorite to absorb approx. 0 percent of the theoretical demand for chlorine dioxide. In that particular example” ag© calculations readily known in the art, the amount of sodium chlorite required to absorb 700 demand of chlorine dioxide was a dose of approximately YY mg/L Chlorite Sodium hydroxide and chlorite are added over a period of six minutes with air at a rate of SCFM 11 In that embodiment air is introduced by means of a sprayer At the end of the Te minute period the injection of air 'se' is stopped and the dioxide demand is retested Chlorine and found to be YY mg/L Chlorine dioxide is then introduced by means of a nebulizer at an appropriate rate to achieve a dose of £V mg/L over the course of 0?min No air is introduced during the CO2 step Chlorine The resulting fluid is clear with an orange/brown sediment and has a thin layer 1110 of floc on top which is determined to be 7156 of inorganic sale and VAT hydrocarbons. Then A mg/L chlorine dioxide was detected as residue in the fluid. fluid has been analyzed; slime and flocculanted by Vo Garrett's gas train and determined that it does not contain any sulfide compounds. Bacterial growth was detected by culture analysis. The fluid was analyzed to determine the suitability of "crystallization" for fracturing use. The crystallized fluid and crosslinked without difficulty. This method results in a 775% reduction in the amount of chlorine dioxide required to achieve the target chlorine dioxide residue and without bacterial growth. Example: A tank containing about 11 barrels of fresh water with a flow yield of 0 product is analyzed and it is discovered to contain 00001 mg/l total dissolved solids; Above 101 culture forming units/mL of bacteria £05 mg/L of sulfide compounds in the homogenate at pH K the demand for chlorine dioxide from the fluid is determined as YA mg/L. The tank shall be equipped asa chlorine dioxide in which suction is drawn for a stream of stirring fluid from the lower end of the tank; The vacuum solution containing chlorine dioxide and/or air is returned to the tank and discharged to the bottom of the tank via a removable injection boom. The injection boom is continuously moved around

And the tank at a rate of 00 feet per minute. The liquid is withdrawn from the tank and calculated through the chlorine dioxide generator by means of a centrifugal pump with a rate of 01? gallons per minute. in that example; Chlorite is not added directly to the system as sodium chlorite. instead of © that; Chlorine dioxide is added to the tank initially (Sun (converts to chlorite); Followed by air and then a second dose of chlorine dioxide as shown below. by assigning more than 1 (1) of time zero (1) and on Jae the first 10 minutes; chlorine dioxide is added to provide 771 of the total dose; 7) from the 01 minute to the minute oF is swirling the solution; 9) From minute ye to minute 0 air is added; (Fy from minute 1 to minute Av) BL JAY 77860 of SU 0 chlorine oxide is in the tank. In total, the tank is treated with 011 mg/l chlorine dioxide during build-up (but; non-consecutive) 00 min. Concerning step oY someone of ordinary skill in the art of when using a large tank; one has to be careful to put blood into "HALL spots" and allow a scattering slightly chlorine dioxide.In the oF step the air is added in the separation through a nebulizer at a rate of SCFM 001 to a You tank 1 - min Fe to min 10. In alternative embodiments low doses of ClO may be added , with air Depending on vessel size and depth as well as flow rate Sodium hydroxide is added at the same time to maintain a constant pH The fluid was analyzed after treatment The resulting fluid is shown with an orange/brown precipitate and has a thin layer of floc on top determined to be 2 inorganic material 1710198016 and 77 hydrocarbons -hydrocarbons 0 VY mg/L chlorine dioxide was detected on residue in the fluid.The fluid was analyzed; slime flocculants with a Garrett gas train and determined that they did not contain any sulfide compounds. Bacterial growth was detected by culture analysis. The fluid was analyzed to determine the suitability of “crystallization” for fracking use. The fluid crystallized and crosslinked without difficulty. This method results in approximately 7400 reduction in the amount of chlorine dioxide required to achieve the target chlorine dioxide residue and with no bacterial growth.

2 m (JU): a tank containing 70,000 gallons of water produced. The homogeneity is analyzed and found to contain 770,000 mg/L total dissolved solids; Above 014 culture forming units/ml of bacteria and 7511 mg/L of sulfides with a pH of VLA, the demand for chlorine dioxide from the fluid was determined to be 2860 mg/L. The tank shall be equipped with 0% chlorine dioxide in which suction for the steering fluid stream is drawn from the lower end of the tank; and the discharge solution containing chlorine dioxide and/or air by means of a perforated tube along the length of the tank bottom. The fluid is withdrawn from the tank and circulated through the chlorine dioxide generator by means of a centrifugal pump at a rate of 701? gallons per minute. As in Example 3; Chlorine dioxide is added to the tank initially by spray + FY followed by 0 air and then a second dose of chlorine dioxide as shown below. Assigning VSS of time zero (+) and over the course of the first minute, chlorine dioxide is added to provide 771 of the total dose; thereafter an FV of six minutes A(T) ten minutes (10); The remaining 77868 chlorine dioxide is introduced into the tank. In total; the tank is treated with 701 mg/l chlorine dioxide during the build-up (Sly non-consecutively) for 0 minutes. Air is added through the Vo spray At a rate of 04 SCFM into the tank from the first minute (1) to six minutes (1). Sodium hydroxide is added at the same time to maintain a constant pH. The fluid was analyzed after treatment. The fluid is clear with an orange precipitate / Brown with a thin layer of flocculant on top which was determined to be 797 inorganic matter and 7 hydrocarbons.1 mg/L chlorine dioxide was detected as residue in the fluid.The fluid was analyzed: sludge; and flakeYe by Garrett gas train and determined that it does not contain any sulfide compounds.Bacterial sail was detected by culture analysis 010076a0. This method results in an approximately 7% reduction in the amount of chlorine dioxide required to achieve the target chlorine dioxide residue and without bacterial growth. Al-Mathal ©: The tank contains 47,090 gallons of produced water. The homogenous fluid © is analyzed and found to contain 77006800 mg/l 105 over 014 culture forming units/ml CLAS

mg/l of sulfide compounds with a pH of 7.8. The demand for chlorine dioxide from the fluid 15W was determined to be 880© mg/L. The tank shall be fitted with a chlorine dioxide generator where suction is drawn from the lower end of the tank; and the drive fluid stream vacuum solution

Lie containing chlorine dioxide and/or air by pipe discharge solution along the length of the tank bottom. The fluid is withdrawn from the tank and circulated through a CO2 generator © YY + chlorine by a centrifugal pump at a rate of

Jae mg/L on VY chlorite is introduced directly at a rate to achieve a dose (JU in that L fame 701 buildup 1st min. Chlorine dioxide is also added at a rate to achieve a dose of (+) five) 0 In particular, chlorine dioxide is added from time zero Jae (01) to the first minute (1); and then again from six minutes (1) to ten minutes 0 (0). To the tank from minute zero to minute nine SCFM 50 Adding air through a sprayer at a rate Sodium hydroxide is added at the same time to maintain a constant pH The fluid was analyzed after treatment The treated fluid is clear with an orange/brown precipitate It has a thin layer of flocculant on top of which 17 mg/l sec has been determined to be 797 inorganic matter and 7 hydrocarbons. By gas train and determined that it does not contain any sulfide compounds Bacterial growth was detected by Garrett culture analysis This method leads to approximately 767 reductions in the amounts of chlorine oxide required to achieve the target residue M n chlorine dioxide and without bacterial growth. The following test results show that the combination of an oxidant £0 (air/oxygen) with chlorite 0 followed by the introduction of chlorine dioxide (1a); It has the unexpected beneficial consequence of significant (TY) reduction of unwanted contaminants in oil field waste water (or product water); include calcium; manganese; total dissolved solids»; and 08010; Compounds (Cl, magnesium, sodium, iron, sulfate, barium, oil, grease, in addition to bacterial contamination, so that the fracturing fluids are suitable for reuse in the form of fracturing fluids Yo

Example 7: A processing train is being prepared for the produced fluid (Y) typical of North Texas production. Approximately six barrels per minute of fluid is transferred via a circulation pump (©) to a 0 barrel frac tank (1st hydraulic fracturing tank) 01 at a ready flow rate. Approximately four barrels per minute of fluid is withdrawn from the ? feet above the bottom of the first hydraulic fracturing tank (V0) that fluid (IY) passes through a sprayer (8) where air (0) sodium chlorite (QF) and sodium hydroxide (10) are added to the fluid stream. The fluid stream (IY) entering another ye into the first hydraulic fracturing tank (010) includes air (£), chlorite (V+), and caustic (19) along the center line (10) of the tank ( V0) through a dispensing rod (V9) passing through the length of the tank (0101). For example, 0 chlorite (WF) is introduced to achieve a dose of 00 mg/L and an oxidant (£) is added. 0) to achieve a dose of 400 mg/L. A degreaser (1) is placed at the top of the first hydraulic fracturing tank (010) to extract the floating material The fluid (IY) is drawn into a second hydraulic fracturing tank (017) by emptying approximately ft from the bottom of the first hydraulic fracturing tank (010). Fluid (IV) is introduced into the second hydraulic fracturing tank (Vo) at approximately the level of ?ft. Chlorine dioxide injection (IF) into the fluid stream between the first and second hydraulic fracturing tanks (YoY OY) on For example; Chlorine dioxide (170) is added to achieve a dosage of Yo mg/L. Fluid (VF) from second hydraulic fracturing tank (017) flows down to third hydraulic fracturing tank (VF) Fluid flows (7C) From the third hydraulic fracturing tank (001) to the clear well 0 (?10). In it (JU) contains the resulting fluid (7) that flows into the first hydraulic fracturing tank (01) Originally on approximately 71 by volume of a petroleum hydrocarbon. In the first fracking tank (011) the free hydrocarbon was extracted mostly at the surface. In the second fracturing tank (o) + Y) the iron sulfide (FeS) reacts iron sulfide which has been oxidized by Yo chlorine dioxide to form iron three hydroxide 1[00].

Ad—the low-density solid formed by that reaction and the additional hydrocarbons liberated also of density formed as part of that process to the bottom of the combined second and third tanks.

01 for extra storage. The treated fluid has a chlorine dioxide residue of 0 mg/l in the clear well. Tables 1a-1c refer to the results obtained by the above method and system. Table 1a

fimo | | phone | [oe| | mg | red | mg/sample Description 0 pH - red Air treatment | 1 mL jar (YA) of | TAN AK | by obtaining | lah | VV chlorine treatment | Flow line using Aad Rakhat 1 to Tam | GAY [TAY EY av] 16 from CIO Bowl | to "after

—¢¢— Y 1.90 cistern fencing [TAY] ke sen kd [ZAC] Afd X cistern fencing | a pot ? Veg TAA Protect | AYO ZAY 1 No GIA 7 Fence cistern cle ¢ 1,4¢ VENUE Za] for cut AYA [AY When 7 Flow Line Separate FLOW LINE to AcYoY Jay Y.v ay Yer VY 1,AY mm Processor | STORAGE Table 1b CO; | 0 0" and p ohm field A Cl| SO, "| HCO, 0 OH Sr | Mn. mg | mg |mg/ |mg/ | mg | mg |mg/ | mg/l a liter a liter a liter water line ALYTE | YYA, +» av, v1 18 sag) 417 only, raw 727 from

—¢0— IN TANK FACILITY FARM TREATMENT USING AIR VAN 1717 kcal YoY. T | ovo Amir Y, As 3 Waldichlor treatment flow line | from using a JAS container «,0¢ 7154 Vo, 0 YAV,YA| YT, 0 1 0 , Yo clo, to vy after 0102 cia d a cle To, Ye cistern | 108 0 LMMA AA YY [ZYa 249 Y 1" Y SIA + & TANK YTOYAY | TAY | YET, NT UA | KNM | Y Ro Y Machines Sia .. © to pure |

Flow Separation Line Water 8" Met | Za TA [AVA [IVA YE] TE YY to oe Processor ie 1 Table 1c TDS 1 Total |7 Flow Line from Raw Water Facility at 7 0 0 AYO, vv 4 oY 0, ARS TEY, vv oY ass AYE oY \ clog and dichloro Flow Line from le, c 1 y ZYY | You (YA) ClO2, q AA what to?

7c Example 7: Processing train of typically produced fluid from Permian Basin Approximately six barrels per minute of fluid is conveyed by pump to a 060-barrel hydraulic fracturing treatment tank (V0) at a ready flow rate by six fracturing storage tanks Hydraulic © (200). The six (+0) hydraulic frac storage tanks are filled by truck from the field. Approximately four barrels per minute of fluid is withdrawn from a level of ? feet above the bottom of the first frac storage tank (010). That fluid passes (010). ?a) through a spray of o£) where air (£4) sodium chlorite (V+) and sodium hydroxide (30) is added to the fluid stream. The fluid stream reentering the first 0 cracking treatment is introduced tank; which contains air (£0) chlorite (Fr) and caustic (90); along the center line of the first cracking tank (0101) through the distribution rod (V9) passing along the length of the tank (V+ ) for that example, chlorite (0?b) is introduced to reach a dose of ov mg/l and oxidant (40) is added to reach a dose of 5000 mg/l (eg 0 ? Jana liters of air). A degreaser (1) is placed on top of the tank (V0) to extract the supernatant Yo. The fluid is drawn into a second frac tank (VY) by vacuuming approximately Y feet from the bottom of the first tank (V0) and inserted into the L Second tank (017) at approximately 7ft level. Chlorine dioxide (1?a) is injected into the fluid stream between the first and second tanks (10 – 4 L(V) for this example; chlorine dioxide (1?a) is added to reach the dosage of Yo Yo mg/L Under fluid flows (B) from second tank (VY) Under flows into tank L (V) YF) cult Fluid (21) overflows from third tank (VF ) to the clear well (?10). In tank one (1010); mostly free hydrocarbon recovered at surface. In tank two (710); iron sulphide oxidized by chlorine dioxide reacting to form Yo trioxide iron three hydroxide The low-density solids were extracted by lard

A — ¢ — reaction and hydrocarbon precipitated by surface grease from that tank. The formed high density solids fall to the bottom of the second and third cells/tanks. The third cell/tank (00”) overflows into a cementitious blister (;10). The fluid (oY) is pumped out of the well (Veg) GALI for storage thereafter. The treated fluid has residual chlorine dioxide 71 mg/L.0 in that (JU) the inlet fluid Te measures ppm by volume of petroleum hydrocarbon in extract samples. This measurement is imprecise, however, due to the nature of the transport truck. It is not Some incoming trucks have visible hydrocarbon" while others contain multiple ratio due to hydrocarbon sludge going into the system. A large amount of hydrocarbon is extracted from the first and second tanks by degreasing; representing 71.77 grab samples in the 1 0 discharge from the last tank Which shows an average of 5 4 ppm of total hydrocarbon Tables ?a-7c refer to the results produced by this treatment Table ?ait | fas . | mg/red | mg/l l l l FLOW line Alma & Raw 1 ¢ VY Yor YY, oof LINE

—¢4— processing slat Lb and m came to arla 7m /sY | Via pain | AAA oY ANY 1 AIR DIKLOR FLOW LINE Cure TA VYo 1 | than Ya nick m | AY Al ClO, to 1 after 06002 mig pot Ye vot TAA | YT 71 cistern 1 |" 77 mm container 77 | A: A | Ya Y YY AYA] You 114 m container 114 m | Yoo (A 11 ET) to the water separation line | Flow 011" | 77 YYY 111 |41 A GYT[ 211 You A Processor to] Table B A

Qo = _ (tot)Fe CO3 - yi 4 Cl| SO4-2 | —HCO2 -OH Sr'| Mn" 2 0.0 in the treatment tank facility using Ley & air p [Ye bert AY] marked | oV 1 d for YAY YVYV, Ye A Lamkla 06 8 m 7 co, to 0102 1 container Y 7 tank

_— \ g sia gat Leg ZY Yao tank] 14,74 | “0” AA | AY Y Y out of X Le what a Ley 4 cistern IY, Ne | FY A TA for mold ‎Zao | Yu | 71 $ 11" Y Flow Separation Line Water and 0 Zao | 6 77 177 ONY of 96.00 | 0 to MCP Stored Table 1c TDS 7 Ad |7 Flow Line Water Crude in a mash | 0.6 mL 0 Fe LEAR

_— \ g treatment using 1 container 12661 - e bitter oo L 1 1 m air and dichlorine flow line treatment using 11 & Leg 78 ha 8 LAY 4 ClO, to ah” After ClO, flow line Separation of treated water ARE 80.0 ZY A 73 0 No to storage The process of the present invention Ad is unexpectedly effective and economical when removing pollutants from the resulting water streams carrying hydrocarbons hydrocarbon is highly polluting. Most pollutants are low in the range of Vo - 7958 as shown in Tables 1 and . As such the treated water is acceptable for use on a Loa hydraulic fracturing fluid without additional dallas; in most cases; Or in the form of a feed stream that can also be treated (if necessary) for discharge to the environment. The removal of a high level of contaminants » Jia Calcium Magnesium ¢ Sodium 1 Iron 1 Cl; manganese total dissolved solids; “CaClO, 1-barium sulfate compounds; hydrocarbons and biopollution; As achieved by the protected process, Ye in the form of Je is a required process for the treatment of large quantities of polluted waste water streams formed by Jia oil applications. avoid process; Also cade and to a large extent; separation of gas from harmful components; Volatile in an organized manner such as hydrogen sulfide

I hope although the modified application of the method and system disclosed herein is in oil field applications; Such as petroleum wells, downhole formations 08105 and industrial and petroleum process water; Additional industrial applications include; without limitation on cooling the process water; mineral process water © geothermal wells digester paper mill 65 m. materials Jue washers bleaching plants cbleach plants ore bins stock 015 water White water systems black liquid evaporators in the pulp industry continuous casting processes in the metallurgical industry and water reclamation refrigeration systems 060050806 food processing streams 060050806 filtration systems (meat, vegetables, sugarcane, poultry, fruit, soybeans); waste treatment systems municipal wastewater treatment clarifiers in addition to clarifiers

sewage treatment 01 Municipal water systems Drinking water treatment Potable water systems Ground water Caquifers and water tanks Water tanks Moreover; For the purposes of that disclosure; water volume is considered; waste water stream; waste water; aqueous fluid volume; The aqueous fluid stream all represent the fluid that will be treated by the method and system that have been detected.

0 Various embodiments and modifications of that invention are described in the foregoing description. Such embodiments and modifications are illustrative only and shall not be taken to limit in any way the scope of the invention; which is determined by the following safeguards. Other variations of what have been described also fall within the scope of the invention; The present invention could be modified and practiced in different but equal ways evident to those skilled in the art who would benefit from the studies presented herein. Furthermore it; did not

Yo any limitations on the construction or design details described in this document are determined; Other than that as is

the

_G is described in the claims below. All numbers and ranges disclosed above can change by some amount. (lim) Expressions in the claims must have their plain, plain meanings unless otherwise expressly and clearly indicated by the patent applicant. The subject matter included by reference has not been deemed to substitute for any limitation of a claim, unless otherwise expressly indicated. lo } Sequence list: The volume of water to be treated (pond/lake/pit/cistern; reservoir)

Cl oO,” “b and c air py air inlet l.” and “and” materials “a and” stage 1 irrigation stage 7 sd Id fluid circulating through a sprayer “i” generating and treatment using chlorine oxide (eg: (CIO), 'Z' phase Ag phase 'Sy' phase; continuity of chlorine oxide replacement / air treatment until residual chlorine oxide (b) and stopping chlorine oxide treatment and introducing air through the nebulizer

Claims (1)

Here are the elements of Hamaba - 1 way to reduce » disable; destroy » remove; Or dispose of aqueous fluid Sle pollution selected from the group that includes calcium ccaleium magnesium 01880865700 sodium ¢sodium iron and cchloride manganese manganese calcium chlorate calcium chlorate csulfate barium barium hydrocarbons chydrocarbons total dissolved solids | total “dissolved solids© biological contamination and their terminated combinations The method comprises introduction into the aqueous fluid (Sl) of an oxidant selected from the group comprising oxygen air” oxygen-enriched air coxygen—enriched air and combinations terminated and introduced into the fluid chlorine oxide first selected from the group comprising 0 cchlorine dioxide chlorite cchlorite and combinations terminated and introduced chlorine dioxide into the aqueous fluid after introducing the oxidant and the first chiorine oxide, where it includes chlorine oxide | The second mentioned chlorine oxide is chlorine dioxide or a combination thereof. Vo "- method of claim 1; wherein the oxidant is introduced at a rate where outgassing of hydrogen sulfide or other volatile reductants is avoided. 0 * - The method according to Claim 1 or oF where the oxidant is introduced by extraction via a venturi spray; - The method according to any of the previous claims, where the first chlorine oxide includes chlorite chlorite and is introduced into the aqueous fluid before or largely concurrent to Yo with the introduction of sale .oxidant h — g — o method according to any of the claims AL where the oxidant is added to achieve a total dose ranging from 01 mg/kg to 0001 mg/kg in -aqueous fluid (All) 1—the method under any of the foregoing claims; Also include JAY sodium hydroxide© before or in conjunction with chlorine oxide your first opacity to raise the pH to .01-17 -1 method according to any of the claims Ala where chlorine oxide is included The first chlorine oxide is based on chlorite “chlorite A”—A method according to the oF claim where chlorite is added to achieve a dose ranging from 0 mg/l to 600 © mg/l In an aqueous fluid, it is smooth. 9— The method according to Claim 7 or cA where the chlorite is a VO solution sodium chlorite solution -0 The method according to any of the previous claims where it includes chlorine oxide The second is based on chlorine dioxide -11 YL, the method according to the element of protection Ve, where the second chlorine oxide is added in a dose sufficient to achieve the remaining chlorine dioxide in the aqueous liquid as a strong suspension. - The method according to claim OY, where the method also includes measuring and keeping chlorine dioxide residues from 11 mg/L to 50 mg/L in the treated aqueous fluid Yo 3. — 7 g-0” method according to claim oY in which chlorine dioxide is introduced to achieve a dose of 01 mg/L to 0 5 mg/L in the -aqueous fluid 64 - The method according to any of the previous protection elements, where before treatment according to edi all the demand for the oxidant of pollutants in the aqueous fluid is 01 mg / liter to 550000 -10 the method according to any Among the elements of the previous protection, where the step of introducing the first oxidant and chlorine oxide leads to a decrease in the demand of the aqueous fluid by 001 AAV compared to the demand for the previous treatment built from the German fluid 2. - The method according to any of the protection elements (BLL), where the source of the aqueous fluid (Damato) is chosen from the group that includes a vessel, ctank, a pit, a lagoon, or a pond for storing water. waste twist water treatment plant water treatment slo plant VO hydraulic fracturing tank ¢hydrauc fracturing tank or piece of equipment pipeline or vessel used For hydraulic fracturing or crude oil production. oxidant in the aqueous volume, where the said oxidant includes oxygen; coxygen—enriched air or a combination terminator at a flow rate where outgassing of volatile reductants is avoided from the water volume; Introduce sodium chlorite into the water volume; Yo water volume aggregation; oxidant and sodium chlorite; thus lowering the initial oxidant demand to calla a low oxidant; -Eh- Introducing a separate feed of chlorine dioxide into the water volume in an amount sufficient to eliminate the low oxidant demand and provide residual chlorine dioxide | chlorine dioxide ranges from 1.1 mg/L to 50 mg/L in the methylated volume. —VA © Ady fluid treatment system pile dallas method according to any of the claims previous. 4- A fluid treatment system for direct use at the hydrocarbon producing well site, which includes: treatment and treatment cell, a first treatment cell, treatment cell, treatment cell, 0 treatment cell, third; cell with material request, wastewater stream, first for fluid flow, Tine, fluid flow line, cell treatment 0 first treatment cell in the treatment cell initial oxidant As the first oxidant mentioned has an entry in fluid contact with it; treatment cell Vo SU fluid flow line for circulating waste water from the first treatment cell The treatment cell for the first treatment mentioned has an outlet and an inlet in fluid contact with it; Venturi tube “Jf venturi arranged in fluid connection with the second fluid flow Tine and the cooxidant source to introduce the oxidant into the fluid pila” SEY flow line Ye in controlled amounts and at a controlled flow rate; a second venturi; regulator in fluid contact with the second fluid flow line and chlorine oxide source to introduce the first chlorine oxide into the second fluid flow line in controlled amounts; A third fluid flow line to transport the treated waste water from the treatment cell second fluid flow; Where the first treatment cell fluid flow line to the treatment cell is cel Yo said third line in fluid communication with an outlet from said (AY) treatment cell and an inlet from said second treatment cell; Third venturi tube arranged in fluid connection with third fluid flow fine line and chlorine dioxide source to introduce chlorine dioxide into SBN fluid flow fine line © in controlled quantities controlled flow rate; Whereas, the first treatment cell includes a skimming apparatus, a separation apparatus, to remove precipitated contaminants from the first treatment cell, and our detention time ranges from 1 to 10 minutes; Where the aforementioned Aull treatment cell includes a skimming apparatus + an underflow outlet (£54 in the third treatment cell ¢) and a residence time of 01 minutes to 0 ? minute; Whereas, the aforementioned third “Dasada” cell includes a separation device Separation apparatus to remove residual contaminants from the ASIEN treatment cell Overflow outlet Coverflow outlet And a holding time from 01 minutes to 0? minute. Vo-0 fluid treatment system according to Claim 09 wherein the first venturi tube and the second venturi tube are a single venturi tube designed to introduce a Jad oxidant or At the same time with the introduction of the first chlorine oxide. -71 0 0 fluid treatment system according to Claim 01, where the mentioned oxidant is selected from the group that includes oxygen (p “air” air rich in oxygen ‎coxygen-enriched air and combinations thereof. Sodium chlorite -aqueous solution of sodium chlorite h “= _—YY A fluid treatment system according to any of the claims 19 to YY where the controlled flow rate of the oxidant avoids the release of volatile reductants gas From waste water p1, p7, p7/8:1. 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PRS | pel A they c 1 ha Tt et i 7, 0 | Pata ply BEES a, i KC Ln = = =A LTC 20 A #5 ¢ fi @ 0 7 & and a * J » and “1” Fig. 4 (continued). The validity period of this patent is twenty years from the date of filing the application, provided that the annual financial fee is paid for the patent and that it is not invalid or forfeited for violating any of the provisions of the patent system, layout designs of integrated circuits, plant varieties, and industrial designs, or its executive regulations issued by King Abdulaziz City for Science and Technology; Saudi Patent Office P.O. Box TAT Riyadh 57??11 ¢ Kingdom of Saudi Arabia Email: Patents @kacst.edu.sa