The Application Of Biocides In The Oil And Gas Industry
NAFTA-GAZluty 2013ROK LXIXAnna Turkiewicz, Joanna Brzeszcz, Piotr KapustaOil & Gas Institute, KrakowThe application of biocides in the oil and gas industryIntroductionCurrently the world uses lots of technology, whereenhanced recovery processes, desulfurization and denitrification of oil are initiated and controlled by microorganisms. Some species of bacteria were also isolated in themicrobial oil survey technique [8]. On the other hand, thepresence of bacteria and other microorganisms in depositsand transmission systems and in stored products is a veryunfavorable phenomenon and often difficult to remove.A necessary condition for the emergence and developmentof micro-organisms is the presence of water and a carbonsource in a given environment (fuel tanks, pipelines, gasstorage, gas supply systems, etc.).The phenomena of microbiological contamination ofthe oil and natural gas environment represent a broad issue. The negative effect of microorganisms is primarilyassociated with the degradation of petroleum hydrocarbons,leading to an increase in oil density, sulfur content andviscosity. These changes cause disruption in oil extraction and processing technology, bringing about significanteconomic losses. Problems also concern the ways crudeoil is stored, products of its processing, drilling fluids, andnatural gas [14, 27]. In addition to lowering the contentof hydrocarbons in crude oil, adverse activity of microorganisms causes corrosion of transmission installations(oil and gas pipelines) and the production of undesirablesubstances (H2S, polymers, organic acids, etc.) that affectthe performance of oil and gas.Attempts to eliminate microorganisms involve usingchemicals, exhibiting biocidal properties, which besidesthe physical method is the most popular and most effectivetechnique of eliminating microbiological contamination.The selection of appropriate antibacterial or antifungalagents requires the consideration of factors affecting theefficiency of the process. Such measures are primarilysought, which show the greatest spectrum of activity. Thepaper aims at the systematization of available literature dataon biocides and their use and their efficiency in industrialenvironments.Microorganisms responsible for the deterioration process of natural gasThe issue of deterioration of natural gas resulting fromthe metabolic activity of microorganisms is related to twomain aspects – gas transmission and storage of this rawmaterial in underground gas storage (UGS), i.e. exploitedgeological structures. Corrosion of metals, in this particularcase of gas pipelines is one of the major problems of thegas industry, causing enormous economic losses. It is estimated that 40% of the corrosion occurring in the interiorof gas pipelines is caused by the action of microorganisms(MIC – microbiologically influenced corrosion), mainlysulfate-reducing bacteria. These bacteria, using energyderived from organic compounds (light hydrocarbonscontained in the gas), reduce sulfates to sulfides or directlyto hydrogen sulfide. Development of microorganisms andtheir metabolic products accumulating in pipelines causemicro-changes on the metal surface, thereby initiatinga complex process of corrosion. Microbiologically inducedcorrosion is involved in chemical and electrochemicalcorrosion of pipelines, facilities and tanks [6, 22, 23, 25].So far, the mechanism of corrosion caused by microorganisms has not been fully elucidated, although there arevarious theories attempting to describe this phenomenon.One of these theories relates to a biofilm forming on themetal surface, consisting of anaerobic bacteria (primarily103
NAFTA-GAZreducing sulfate and iron), which as a result of oxidationreducing processes cause the dissolution of the protectiveoxide layer, covering the metal with forming iron sulfide.Unfavorable activity of microorganisms is associatedwith a manner of storing this raw material – undergroundgas storages. The emergence of biogenic hydrogen sulfide [34], which is a product of sulfate-reducing bacteria(SRB) metabolism, lowers the value of the gas, furthermore there is the possibility of the formation of insolubledeposits of iron sulfides (FexSy) clogging manifolds,gas transmission installations, etc. Measurements of thequantity of produced hydrogen sulfide by Desulfovibriosp. indicate that during the active division the bacteriaare able to produce 10 g H2S/l. One should also take intoaccount the aspect of health risk to personnel working inthe UGS facilities, because of exposure to the resultinghydrogen sulfide which is toxic (its toxicity is comparableto hydrogen cyanide).Tab. 1. The examples of microorganisms responsible for the deterioration processof natural gas isolated from pipelines and UGSMicroorganismsPlace of samples collectionBibliographyArcheMethanobacterium curvum, Methanocalculus halotolerans,Methanoculleus sp., Methanofollis liminatans, Methanofollis sp.,Methanosarcina barkeri, Methanosarcina siciliae,Methanospirillum hungateipipelinesZhu X.Y. et al., 2003 [35]Acinetobacter junii, Acinetobacter sp., E. coli,Pseudomonas aeruginosa, Staphylococcus auricularispipelinesZhu X.Y. et al., 2003 [35]Klebsiella pneumoniapipelinesJan-Roblero et al., 2004 [12]pipelines,underground gas storageLohithesh M. D. et al., 2008 [16]Raczkowski J. et al., 2004 [20]pipelinesJan Roblero et al., 2008 [12]AerobesAnaerobemAnaerobaculum mobile, Thermodesulfovibrio yellowstonii,Desulfovibrio vulgaris, Thermotoga neapaitana, Clostridiumsporogenes, Clostridium bifermentas, Desulfomatoculum kuznetsorii, Thermotoga hypogea, Desulfovibrio sp.,Desulfotomaculum sp.Desulfovibrio desulfuricans, Citrobacter freundii,Clostridium celerecrescens, Cetobacterium someraeMicroorganisms responsible for the deterioration process of crude oil and its processing productsAt each stage of oil processing from its exploitation,transport, processing and ending with the storage, it canbe subjected to the action of microorganisms. They usehydrocarbons contained in crude oil as a source of carbonand modify the properties of this material, thus reducingits value. The complexity of the issue of microbiologicalcontamination of the oil is due to the existence of the possibility of interactions between oil and water. It is extremelydifficult to prevent microbiological contamination of oil,because it is impossible to maintain sterile conditionsduring the extraction, transport and storage of crude oil.An essential and necessary condition for the growth ofmicroorganisms in oil, or products of its processing is thepresence of water in the production well, accumulation ofwater in the pipelines during transmission or at the bottomof the tanks during storage.104nr 2/2013There are several stages during which microbiological contamination of oil and its derivatives may occur[24, 25, 30, 32]: stage of application of drilling fluids, which may becontaminated – in this way allochtonous bacteria areintroduced to the deposit, stage of supply – borehole watering with highly contaminated water, stage of oil transport – presence of microorganisms incontaminated water in transmission systems, petroleum processing stage, stage of storage of crude oil and its processing products.The deterioration of crude oil and petroleum productsunder the influence of microbial activity reduces the hydrocarbon content, because they are being used as a carbon sourcein both aerobic and anaerobic conditions, which immediately
artykułytranslates to changing the physico-chemical parameters of thisraw material. The occurrence and growth of microorganismsat the interface of water-crude oil phases produces a biofilmon the surface of pipelines and tanks, which presents excellent conditions for microbial growth. The effect of metabolicactivity of microorganisms is the appearance of detergents,biosurfactants and hydrogen sulfide in crude oil, affecting thedecrease in the energy value of this resource – acidificationand sulfation. A particularly disadvantageous phenomenonis the secretion of hydrogen sulfide by some of the bacteriaand the creation of a local area with reducing properties,causing corrosion of metals included in the material of tanksand transmission systems [6, 24, 27].Such changes are a major economic problem for themining and refining industry, as well as a huge threat tothe environment. It is impossible to avoid the penetrationof microorganisms into oil fields as a result of drilling, intooil and fuel storage tanks, oil pipelines and transmissionfacilities, which are the perfect place for colonization byboth aerobic and anaerobic microorganisms. Developmentand metabolic activity of micro flora directly leads to thedeterioration of the physico-chemical parameters of oiland fuel. A negative phenomenon is the precipitation ofbiomass (sludge), which are metabolic products of fungi,bacteria, yeast, which forms larger agglomerates. Thiscauses the silting of reservoir rocks, clogging of pipelinesand accumulation of sediments at the bottom of fuel tanks.Bacterial contamination is usually observed in crude oil,whilst fungi usually cause contamination of aviation fuel.The number of microorganisms (bacteria and fungi) inthe aqueous layer contained in crude oil and petroleumproducts, determines the amount of contamination.Tab. 2. The examples of microorganisms responsible for the deterioration processof crude oil and fuels isolated from drilling muds, flooding water and some fuelsMicroorganismsPlace of samples collectionBibliographyFungiPenicillium spp., Fusarium spp., Cladosporium sp.,Rhizopus sp., Aspergillus sp.drilling mud,flooding water,drilling mudBenka-Coker & Olumagin, 1995 [3]Elshafie et al., 2007 [8]YeastCandida tropicalis, Candida albicans,Saccharomyces estuari, Saccharomyces cerevisiaeCandida viswanathiiaviation fuelItah et al., 2009 [11]biodiesel, dieselJunior et al., 2009 [13]Aerobic bacteriadrilling mud,flooding waterBenka-Coker & Olumagin, 1995 [3]Staphylococcus spp.drilling mudBenka-Coker & Olumagin, 1995 [3]Okpokwasili & Nnubia, 1995 [19]Nnubia & Okpokwasili, 1993 [18]Alcaligenes sp.drilling mudBenka-Coker & Olumagin, 1995 [3]Okpokwasili & Nnubia, 1995 [19]stains from drilling wellsAL-Saleh et al., 2009 [2]Das & Mukherjee, 2007 [7]Serratia spp., Acinetobacter spp.Pseudomonas sp.Methods for suppression of biodegradation of crude oil and petroleum productsand an overview of currently used biocidesThe problem of microbiological contamination of natural gas, crude oil and its processing products representsa major problem in economic terms. Among the methodscurrently used, the following can be distinguished: physical and mechanical methods, chemical methods.The article focuses on the second group of these meth-ods – chemical control of microbiological contaminationof natural gas and oil – using chemical agents (biocides).Biocides are compounds used to disinfect, decontaminateand sterilize materials (surfaces, objects) to eliminate microbiological degradation processes. Chemical compounds,exhibiting biocidal properties and used as antibacterial/antifungal preparations have a diverse structure. These arenr 2/2013105
NAFTA-GAZboth inorganic substances (e.g. copper, tin, arsenate) andorganic substances (e.g. aldehydes, hydantoins). Amongbiocides, there are substances with a simple chemicalstructure (e.g. glutaraldehyde) as well as a complex chemical structure (e.g. QUAT’s), of which the mechanism ofinteraction with the microorganism is based on differentmechanisms.The mode of action of biocides is to suspend the currentmetabolic activity of microorganisms, causing changes inthe proper functioning of cells, and consequently death ofthe microorganism [24, 28, 30]. Depending on the subjectaffected by a given biocide, there are antibacterial, antifungal and anti-algae formulations, although the mostpopular are agents which eliminate several types of microorganisms (bacteria, fungi, etc.). A given product mayhave a simultaneous activity against a specific group ofbacteria and fungi, and thus can effectively eliminate onlyone bacterial strain of the species. The main areas of useof biocides are agriculture, forestry, the food industry andcosmetics, also, industrial water and swimming pools alsoundergo antibacterial decontamination.Given the mechanism of chemical action of biocides,biocides can be divided into two groups, i.e., substanceswith oxidizing and non-oxidizing effect. The most commonly used oxidizing biocides are chlorine, bromine,ozone and hydrogen peroxide. However, use of oxidizingbiocides is associated with negative effects: interaction with other chemicals (corrosion inhibitors), the possibility of interaction with non-metallic substances, initiation of corrosion of structural materials.Before each treatment with oxidising preparations, theseeffects should be taken into account when consideringthe potential for oxidation, the dose and type of treatment(intermittent or constant).The group of non-oxidizing biocides includes aldehydes (formaldehyde, glutaraldehyde), acrolein, quaternaryammonium compounds, amines and diamines [29], andisothiazolones.Often used in the industry, quaternary ammoniumcompounds are used as cationic corrosion inhibitors andbiocides. Biocidal activity of these substances is to dissolve the lipid cell membrane, which leads to loss of thecell contents of the microorganism. Additionally, QUATSprevent the formation of polysaccharide secretions duringbacterial colonization, thus showing antibacterial activity.Often, biocides using QUATS have water, alcohol orpotassium base as the dissolving phase, the use of alcoholincreases the antibacterial activity of the preparation, since106nr 2/2013alcohol has biocidal abilities and facilitate penetration ofan entity into the cell. QUATS generally work best in analkaline environment. Inhibition of corrosion using thesesubstances is to create a thin protective layer on the innerparts of the installation, thereby the possibility of interaction of oxidizing agents with steel components of theinstallation is reduced. Furthermore, these compoundswere studied as a control substances, and even as substances preventing biofilm formation. These preparationsare used in closed systems and gas manifolds. However,they are not used during the exploitation of oil becausethey may adversely affect the permeability of the crude oildeposit. Furthermore, they are not compatible with oxidizing agents, especially the chlorates, peroxides, chromatesor permanganates. Most of these compounds are readilybiodegradable.Another type of biocides is isothiazolones. They arefast-acting biocides inhibiting growth, metabolism andbiofilm formation by algae and bacteria. They are used incombination with other biocides or individually, typicallyaqueous solutions of chloride- and methyl-derivatives ofthese compounds are used. Isothiazolones are used only inan alkaline medium, at pH 7 they lose biocidal properties,moreover, these compounds can be used in combinationwith other chemicals without changes in performance. Anexception is environment containing hydrogen sulfide,which causes deactivation of isothiazolones. The mainapplication areas of isothiazolones are coolants and cooling and lubrication fluids.A compound commonly used in biocidal formulationsis methylchloromethyl-isothiazolone (MCMI) and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOI), which causesinhibition of dehydrogenase and thus interferes with metabolic pathways. The following is a formula of this biocide:In addition, commonly used substances with biocidalaction are compounds containing an aldehyde group, whichinclude: formaldehyde, 2-propenal (acrolein), ortho-phthalic aldehyde (OPA), three-seven-carbon (C3-C7) compounds havingaldehyde groups (e.g., pentane-1,5-dial) – formulas ofaldehyde groups are shown:
artykułyAnother discussed compound is glutaraldehyde (pentane-1,5-dial). This is the most common component ofcommercial biocides with powerful antibacterial and antifungal activity. An important advantage of this compoundis the possibility of use in a wide range of temperatures andpH as well as solubility in water. Glutaraldehyde does notreact with strong acids and alkalis, but reacts violently withammonia and amine-containing substances, which causesexothermic polymerization reaction of an aldehyde, andthus its deactivation. It is not sensitive to the presence ofsulfides and tolerates high salinity environments. Aldehyde interacts primarily with the basic amino acid groups(COOH and NH2) and hydroxyl and thiol groups, presentin the cell membrane, wall and cytoplasm. Preparations arecommonly used in which the carrier is water, also products based on alcohols are known, mainly methanol andisopropanol. The use of alcohol increases the possibilityof penetration of the aldehyde into the cell and preventsits solidification during storage. Often biocidal effectiveness is aided with addition of quaternary ammonium salt(2 5%), surfactants or other biocides.Among other non-oxidizing biocidal compounds, worthnoting are biocides with methylene bis(thiocyanate) (MBT),which is effective against algae, fungi and bacteria including SRB. The undoubted disadvantage of this compoundis its instability in alkaline medium, due to hydrolysis.Thus, preparations based on this compound are not used inrefrigeration systems, in which the process water is above8 pH. Optimum pH at which this compound does not loseits activity is 6.5 8.0.Another biocide used in industry is Tetrakis (hydroxymethyl) phosphonium sulfate (THPS), according to thefollowing chemical formula:It is water soluble, ionic biocide destroying bacteria,fungi and algae in industrial cooling installations andprocess water tanks. It is characterized by low toxicity andinteracts with other chemicals used in aqueous environments, a particular advantage of this compound is its abilityto remove residual iron sulfide in pipelines.Biocides discussed in the article are used in many industries. Microbial control in the oil and gas industry isprimarily practiced to prevent the detrimental effects ofmicrobial growth on production equipment, pipelines,and the reservoir. Biocidal products are assigned to one of 23different types. These types are divided into 4 main groups:1) preservatives (e.g. biocides for liquid-cooling andprocessing systems, metalworking-fluids biocides,and biocides for oil and gas industry),2) disinfectants (e.g. drinking water disinfectants),3) pest control,4) other biocidal products.Antimicrobial agents and corrosion inhibitors are widelyused in the oil and gas industry. Treatment chemicals areused in the natural gas industry from well developmentthrough transmission and storage of natural gas. Somepapers [5, 10, 17] describe potential environmental impacts and effectiveness of biocides, corrosion inhibitorsand their use in gas production, storage and transmissionfacilities. Potential environmental impacts were addressedby performing a screening environmental assessment onthe use of glutaraldehyde, a widely used biocide. Scientificand technical biocorrosion and biocidal literature has descriptions and lists of numerous chemical compounds thatexhibit inhibitive properties. Of these, only very few areactually used in practice. Considerations of cost, toxicity,availability and environmental friendliness are of considerable importance. Many of the new formulations tested hada lower environmental aquatic toxicity profile than eitherglutaraldehyde or THPS (tetrakis hydroxymethyl phosphonium sulfate) alone because of the favorable aquatic toxicityprofiles of the complimentary did so with a better environmental footprint. Some papers describe H2S formation andremoval of hydrogen sulfide in Underground Gas Storageconditions. Hydrogen sulfide forms from the activity ofsulfate reducing bacteria. Under anaerobic conditions, thesulfate ion is used as a source of oxygen for respiration bysome bacteria. The main reason for decreased natural gasquality is the b
of natural gas and oil – using chemical agents (biocides). Biocides are compounds used to disinfect, decontaminate and sterilize materials (surfaces, objects) to eliminate mi-crobiological degradation processes. Chemical compounds, exhibiting biocidal properties and used as antibacterial/ antifungal preparations have a diverse structure .
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