Achieve More Effective & Economical
Frac Water Treatment with Chlorine Dioxide

Chlorine Dioxide (ClO2) is the most effective and economical biocide for frac water treatment. It’s more effective because it provides greater microbial control; it is fast acting, yet far more selective than other oxidizers used in the frac water treatment process. It’s more economical because it requires lower doses to kill bacteria and because it eliminates iron, hydrogen sulfide and biofilms, which reduces produced water treatment cost.

Chlorine dioxide also has less corrosivity than chlorine, peroxide and ozone, and has proven to have no significant corrosion impact on frac equipment.

For more than 70 years, International Dioxcide has been a leading provider of chlorine dioxide equipment and technical expertise to the oilfield for frac water treatment. Our partnership with leading field service companies forms the largest network of ClO2 frac water treatment companies in the oil and gas industry.

Benefits of Chlorine Dioxide on Treating Frac Water

The benefits of using chlorine dioxide in the frac water treatment process include:

  • Addresses a wide range of treatment conditions due to its fast acting nature at lower doses
  • Does not require a low pH level to be effective, which lowers corrosivity
  • Easily monitored in the field with simple analytical methods and equipment for mobile frac water treatment needs
  • Minimizes undesired reactions with organics, which also reduces cost
  • Readily oxidizes sulfide that stabilize oil/water emulsions in produced water disposal systems
  • Safe and reliable oxidizing biocide that also removes iron, sulfide and biofilms
  • Domestically-sourced precursors offer regulatory compliance and fast, reliable supply

The following demonstration video provides an in-depth explanation of why chlorine dioxide is effective in the frac water treatment process:

Chlorine dioxide is an innovative oxidizing biocide for oil and gas frac water disinfection, produced water treatment or other oxidative emulsion breaking treatments. There is a need for multifunctional oxidative biocides in oil and gas water treatment, which provide better microbial control in top side operations and address iron, sulfide and biofilm problems that increase cost.

Downhole conditions strongly impact the performance of non-oxidizing biocides, increasing required concentrations and their disinfection byproducts. Chlorine dioxide at typical dose levels not only oxidizes iron, sulfide and biofilm but ultimately reacts to form sodium chloride at levels that are insignificant when compared to the natural salt levels found downhole. Therefore, for hydraulic fracturing well completion and workover stimulation, it is desirable to use a rapid-acting, broad spectrum, sustainable, oxidizing biocide such as chlorine dioxide.

Oxidizers that hit multiple targets are very rapid and effective microbial control agents. With chlorine dioxide, the metabolic rate of the microbial species is vastly less important, and the rate of effectiveness is considerably more uniform.

Chlorine dioxide is different from traditional oxidizers such as hypochlorite and other oxidizers that are ionized molecules in solution. Chlorine dioxide is a dissolved gas in solution. Therefore, it easily penetrates polysaccharide biofilms and the microbial cell wall via diffusion and performs its oxidative function on the metabolic biochemical components of the microbe.

Inadequate microbial control can have a significant impact on downhole corrosion rates and can create both economic cost and sustainability concerns. SRBs (sulfate-reducing bacteria) are the primary cause of microbial-induced corrosion. Chlorine dioxide quickly and effectively kills SRBs and oxidizes the hydrogen sulfide (H2S) they produce, reducing the sour in the formation water that further reduces the corrosion rates. Chlorine dioxide at typical dose levels ultimately reacts to form sodium chloride at levels that are insignificant when compared to the natural salt levels found downhole. Because its oxidation potential is much lower than chlorine, peroxide, or ozone, and it does not need an extreme pH level to be an effective oxidant, use of chlorine dioxide results in lower corrosivity. It is clear the benefits of using ClO2 as a topside disinfectant in oil and gas applications are significant.

Recently published studies continue to show that ClO2, when properly generated and used at typical 1-5 ppm residual concentrations for disinfection of frac water, has minimal impact on the corrosive erosive nature of fracturing operations. With the increase in produced water recycle for fracturing, frac iron systems are seeing higher salt concentrations and just like sea water systems, they will experience wet dry cycles that allow concentration of salts which significantly increase general corrosion and pitting. Proper use of inhibitors can minimize corrosion from low pH and salts, but not eliminate it. It can be concluded from these studies that acidic solutions are the main contributor to corrosion in frac systems followed by salt from produced water.

Most oil/water emulsions are stabilized by FeS and/or biomass. Chlorine dioxide efficiently eliminates both, thus destabilizing the emulsion and breaking it up. It has been demonstrated that asphaltenes, inorganic fines, clays, and (especially) iron sulfide particulates will stabilize oil water emulsion layers. Particularly where SRB’s are active producing hydrogen sulfide, iron in the water will combine with sulfide to form very fine iron sulfide.

To improve emulsion breaking one must address both the stabilizing sulfides and the source of the sulfides. ClO2 acts as a direct oxidizer for metal sulfides, hydrogen sulfide and other inorganic fines. Oxidation allow formation of floc both soluble sulfates and floc that will settle, removing the stabilizing effect of the sulfide fines. In addition, ClO2 will act as a dissolved gas easily penetrating the emulsion, biofilm and other phases to kill the SRB’s and prevent further generation of sulfide stabilizing fines. These attributes are valuable in surface tank collection systems, salt water disposal wells, water floods, and other systems where oil water emulsions exist including resolving near well bore blockage in production and injection wells.

Chlorine dioxide destroys H2S by oxidizing it to sulfate. This permanently eliminates the compound, rather than simply adsorbing it into amine as most other H2S treatment chemistries do. These amine based chemistries will also release the H2S again if the pH varies from its operating range.

In addition, most H2S is generated from sulfate reducing bacteria (SRB’s). ClO2 is especially effective at killing these bacteria and eliminating the source of additional H2S.

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