Industry biocides

Biocides are often misapplied in the industry. Many of the misapplications occur because the characteristics of the biocides are not considered before use. In this article we review the major biocide types and summarize their properties. Some of the guidelines for biocide selection are outlined. Biocides are the most underused, misunderstood, and misapplied chemical products in the industry for many reasons. Biocides are used to combat a problem that is subtle and difficult to detect. Very few simple and reliable means of monitoring are available to the supplier or the end user, and the benefits of biocide used take a long time to become evident. Finally once bacteria are well established in a system, their eradication is nearly impossible without drastic measures. Early detection of microbiological problems is imperative, and remedial measures must be taken as soon as possible. These measures should include changes in operating methods to prevent degradation of the operating environment. This might include rejection of untreated waters or cleaning of deposits in vessels and lines. In general, biocides are needed to control the activity of the bacteria in a system. However biocides alone usually will not solve a microbiological problem. Types of Biocides Biocides can be classified broadly into two groups: oxidizing biocides and non-oxidizing biocides. In general, oxidizing biocides are used only in freshwater systems because their activity is rapidly consumed by organic matter in produced waters. The non-oxidizing biocides cover a wide spectrum of chemical compounds that can be used in many different types of environments.

Oxidizing biocides
Chlorine Chlorine (Cl2) reacts with water to form hypochlorous acid. Hypochlorous acid dissociates to hypochlorite ion (OCl-), which is the biologically active species. Chlorine functions best when pH is between 6 and 8. Chlorine is used widely in freshwater systems; it is often injected at the water source to maintain control of microbiological populations throughout the system. Chlorine is effective against many micro-organisms. However decades of chlorination have caused the effect of resistance building and the reactivity of chlorine is a disadvantage when attempting to disinfect biofilms. The chlorine consumed in reactions with organic matter and iron in the biofilm and it thus is unavailable for killing bacteria. Chlorine production involves the use of mercury a very polluting substance and negative by products e.g. TriHaloMethans. These THMs trigger the production of free radicals in the human body, causing cell damage and are considered to be carcinogen. The reactor required for chlorine production is a hazard factor involving special security measures and policies. Last but not least chlorine is a carcinogen. The general attitude towards chlorine is to decrease the use. E.g. governments in the EC have a tendency to move to other biocides to avoid all the use, health and environmental risks.

TwinOxide Canada Corp. Suite 26, 100 - 6 Ave. SW Calgary, AB, Canada T2P 0P5 Phone: + 1 403 938 5272 E-mail: [email protected] Web: www.twinoxide.ca

Chlorinating Compounds Chlorinating Compounds include bleach (sodium hypochlorite solution [NaOCl] and calcium hypochlorite (dry chlorine [Ca(OCl)2]). The use of these materials avoids the dangers and inconvenience of handling chlorine gas, but the materials are bulkier. The addition of large amounts of calcium might also create the scaling problems in some systems. Monographs are available to calculate the amounts of chlorinating compounds required to produce the hypochlorite ion in concentrations equivalent to those produced by chlorine. Chlorinating compounds are as effective as chlorine require larger quantities than when using chlorine but are suspected to be carcinogen. The general attitude is equal to chlorine. Chlorine Dioxide Chlorine Dioxide (ClO2) is a very effective oxidizing agent that can be used to remove organic materials, biomass and iron sulfide deposits from a system. This makes its use in down attractive. Chlorine Dioxide is effective in a wider pH range than hypochlorite and is less affected by organic material and ammonia. Traditionally Chlorine Dioxide must be generated on site. Three precursors are generally used to produce chlorine dioxide: sodium hypochlorite (NaOCl), hydrochloric acid (HCl), and sodium chlorite. A two-stage reaction process is required. The first stage involves reacting 15% Hcl and 10% NaOCl to produce 6% aqueous chlorine: 2HCl + NaOCl Cl(aq) +H2O + NaCl The 6wt% chlorine is then reacted with sodium chlorite: Cl (aq) + 2NaClO2 2ClO2 + 2NaCl Chlorine Dioxide is a very fast biocide. Within a flash of a second it destroys micro organism leaving no deposits. (Chlorine takes roughly 7 seconds to crush a micro organism leaving sporidical deposits). TwinOxide Where the patented TwinOxide concept delivers a 0.3% Chlorine Dioxide solution the fundaments are completely different from classical chlorine dioxide. Apart from being a twopowder component concept it delivers a +99 % yield of ClO2. Further it is not explosive, has a shelf life in powder form which is guaranteed for 5 years and in the activated 0.3% solution a chemical halftime of 30-60 days is applicable (depending on storage conditions).

TwinOxide Canada Corp. Suite 26, 100 - 6 Ave. SW Calgary, AB, Canada T2P 0P5 Phone: + 1 403 938 5272 E-mail: [email protected] Web: www.twinoxide.ca

TwinOxide has all the positive characteristics from Chlorine Dioxide with extra features amongst which are: No reactor required for generation of ClO2 Non gaseous but a ClO2 solution Non-explosive Applicable in pH levels between 4 10 Effective against biofilm and all in water common bacteria No resistance building Non corrosive Shelf life characteristics Easy to transport, simple to handle No HMs, No free chlorine, chlorite, chlorate or chloride Easy application by standard dosing equipment No hazard to health or the environment Pure, clean and approved for application in drinking water 260% more biocidal power than chlorine At least 10 times more oxidizing power than chlorine Chloramines Chloramines (e.g. ammonium chloride or monochloramine [NH2Cl] are a reaction product of hypochlorous acid and ammonia. Ammonia is added at a 3-to-1 ratio to injected chlorine, and 1 ppm of monochloramine is formed per each ppm of chlorine Monochloramine has less than 5% of the disinfecting power of chlorine (!!) on a time/concentration basis. However, mono-chloramine is more effective than chlorine for penetrating biofilms and killing bacteria because it is not reactive enough to be consumed by other biofilm constituents, and thus is available for disinfection. Once bacteria are well established in a system, their eradication is nearly impossible without drastic measures. Chloramines are relatively corrosive and require the injection of ammonia and considered carcinogen. Bromine Bromine (Br2) is analogous to chlorine. Generally it is used in the form of a solid compound (1-bromo-3-chloro-5,5-dimthylhydantoin), which releases bromine hydroxide and chlorine hydroxide into the water. Bromine is more effective than chlorine at a higher pH level but has the negative side effects of chlorine and in addition to that bromate is a side product that is considered a carcinogen.

TwinOxide Canada Corp. Suite 26, 100 - 6 Ave. SW Calgary, AB, Canada T2P 0P5 Phone: + 1 403 938 5272 E-mail: [email protected] Web: www.twinoxide.ca

Peracetic Acid Acetic Acid is a reaction product of peracetic acid. The Acetic Acids are a very useful nourishment for micro organisms - therefore bacteria grow/enlarge more after using peracetic acids. Peracetic Acids belong to the group of organic peroxides: Class 5.2/5b these are extremely dangerous classes. Peracetic Acids are a derivate of hydrogen peroxide and the disinfection spectrum is very limited. Peracetic Acid is disrupted very fast by catalysts (e.g. rust, dust, metals) and accidents will happen when a piece of metal (nail, screws, coin, pen etc) drop into a vessel with peracetic acid. In such case the vessel will explode spontaneously as the peracetic acid immediately reacts. Therefore the water to be disinfected should contain very few iron and manganese.

Non oxidizing biocides

Formaldehyde Formaldehyde (HCHO) is used generally as an aqueous solution (37%). It has restricted applications because high doses are required for it to be effective. It reacts with ammonia, hydrogen sulfide and oxygen scavengers. Further it is highly carcinogen and forbidden in many countries. Glytarealdehyde Glytarealdehyde (pentanedial, OCH[CH2]3CHO) is used widely in the petroleum industry. It is sometimes used in a blend with other biocides or surfactants to increase effectiveness. It is insensitive to sulfide, non-ionic (compatible with other chemicals) and tolerates salts and hardness. It is de-activated by ammonia, primary amines and oxygen scavengers. Acrolein Acrolein (H2C=CHCHO;2-propenal) is a highly reactive material that is an effective biocide and sulfide scavenger. It is a gas at ambient temperature and extremely irritating to eyes and mucous membranes and requires careful handling. Injection takes place by pumping or displacement using oxygen-free nitrogen. Acrolein is a broad-spectrum biocide and penetrates deposits and dissolves sulfide constituents. It is difficult to handle reacts with polymers, scavengers, etc. and is highly toxic.

Amine type compounds

Quaternary amine compounds Quaternary amine compounds ([R1 R2 R3 R4 N] + X~) have been used for many years in the industry. The products are generally used in low- total dissolved solids water. Generally these compounds function best at alkaline pH levels. Quaternary amine compounds have persistence and have low reactivity with other chemicals. They are inactivated in brines, are foaming and have a slow acting. Amine and diamine biocides The most commonly used amine/diamine (R-NH2, R- NH-R-NH2) is the cocodiamine. These materials usually are neutralized with an acid, such as acetic acid, to form a water soluble
TwinOxide Canada Corp. Suite 26, 100 - 6 Ave. SW Calgary, AB, Canada T2P 0P5 Phone: + 1 403 938 5272 E-mail: [email protected] Web: www.twinoxide.ca

salt. They have some inhibition properties, are effective in sulfide-bearing waters but react with other chemicals, particularly anionics and they are less effective in water with high levels of suspended solids.

Halogenated compounds
Bronopol (C3H6BrNO4, 2-brono-2- nitropropane-1,3dioV) is a dry product sold as a powder or compressed into a solid stick. It has been used in drilling and completion fluids as well as produced fluids in the oil industry. It has the ability to degrade is low toxic to humans and it breaks down in high pH. Another compound, DBNPA (2-2-dibromo-3nitrolo propionamide CHBr2CNCONH2), also has been used. DBNPAs are fast acting and effective but are affected by sulfides.

Sulfur compounds
Isothiazolone (C4H4NOClS) has been used for several yearsto kill bacteria. It is inactivated by sulfide, so it is considered to be not effective in killing sulfate-reducing bacteria (SRB) in mature biofilms. It is compatible with brines and it is degradable but cannot be used in acid pH. Carbamates (alkyl thiocarbamates) may be a better choice than isothiazolone in some circumstances as they are effective against sulfate-reducing bacteria (SRB) and spore formers, are effective in alkaline pH and are useful for polymer solutions. It is required in high concentrations and reacts with metal ions and other compounds. Metronidazole (2-methyl-5 nitroimidazole-1- ethanol) is only effective against anaerobic organisms and it is effective against sulfate-reducing bacteria (SRB) and compatible with other chemicals

Biocides selection
Biocides must be selected according to several criteria amongst which are: Effectiveness: Ability to kill planktonic bacteria, ability to kill bacteria, minimum concentration and contact time. Safety: personnel risk assessment (for insurance, toxic gases or physical contact) neutralization requirements registration, discharge to environment and persistence. Compatibility with system fluids: solubility, partition coefficient, pH, presence of hydrogen sulfide, temperature hardness, presence of metalions or sulfates, level of total dissolved solids. Handling: Easy of use corrosiveness to metals and elastomers, freeze point, thermal stability, separation of components, shelf life, storage requirements

TwinOxide Canada Corp. Suite 26, 100 - 6 Ave. SW Calgary, AB, Canada T2P 0P5 Phone: + 1 403 938 5272 E-mail: [email protected] Web: www.twinoxide.ca

Conclusion
A wide range of products is available to control microbiological activity in systems. The specific product application must be carefully considered and all the relevant factors evaluated before designing the chemical program. Laboratory screening and field monitoring are necessary to ensure the level of success of the biocide program.

References
S.D. Faust, O.M. Aly, Chemistry of Water Treatment (Stoneham, MA: Butterworth Publishes) J.F. McCafferty, et al.,Field Performance in the Practical Application of Chlorine Dioxide as Stiumlation Enhancement Fluid, paper no. SPE 20626 (Dallas, TX: Society of Petroleum Engineers) J. Boivin, R. Shapka, A.E. Khoury, S. Blenkingsopp, I.W. Costerton, An Old and A New Method of Control for Biofilm Bacteria,CORROSION/92, paper no. 171 (Houston, TX: NACE, 1992) R.G. Eager, et al., The Use of Glutaraldehyde for Miaobiological Control in Waterflood Systems, Corrosion/88, paper no. 84 (Houston, TX: NACE)

Contact
For further information we cordially invite you to contact us: e-Mail : [email protected] Office : +1 403 938 5272 Fax : +1 403 938 5275

Mobile : +1 403 612 1005 (Wim ten Kate)

Or write us at: TwinOxide Canada Corp. Suite 26, 100 - 6 AVE. SW Calgary, AB T2P 0P5 Canada

TwinOxide Canada Corp. Suite 26, 100 - 6 Ave. SW Calgary, AB, Canada T2P 0P5 Phone: + 1 403 938 5272 E-mail: [email protected] Web: www.twinoxide.ca