Dow Microbial Control. Delivering Value with an Optimized Microbial Control Program in Oil and Gas Operations

Transcription

1 Dow Microbial Control Delivering Value with an Optimized Microbial Control Program in Oil and Gas Operations

2 Protect Oil and Gas Operations with an Optimized Microbial Control Program Bacteria will grow just about anywhere water can be found. In hydrocarbon production and processes, the large volume of associated water provides an environment in which bacteria will thrive. Their presence impacts the quality and quantity of production, asset integrity and the overall safety of operations. Advanced stimulation techniques like hydraulic fracturing and enhanced oil recovery (EOR) are more water-intensive processes that are susceptible to bacterial contamination if not properly controlled with an advanced and comprehensive biocides treatment program. Left unchecked, the microbes will contribute to reservoir souring, corrosion of pipelines and equipment, and formation plugging. Leaders in Microbial Control for Oil and Gas Operations Dow Microbial Control has over 60 years of experience in developing effective biocides and bringing microbial control solutions to the oil and gas industry. Our leadership position is based on: The broadest portfolio of biocides for advanced sustainable microbial control, including innovative formulations Technical expertise and advanced testing capabilities Regulatory expertise Industry expertise World-class manufacturing capabilities 2

3 Beyond Chemistry: Dow Offers Leading Solutions to Microbial Challenges Dow Microbial Control, a business unit of The Dow Chemical Company (Dow), provides the broadest range of microbial control solutions in the industry. We offer an unmatched combination of chemistries, delivery forms, technical expertise, reliability of supply, and regulatory excellence by leveraging global capabilities with a local presence around the globe. At Dow, we believe that connecting chemistry and innovation can generate innovative ways to solve global challenges at a local level. All of our advanced technologies offer cost-effective and exceptional control of microorganisms to protect the integrity of topside assets, near well area and in the reservoir, with low environmental impact and excellent safety profiles. Over the years, we have successfully introduced new technologies and methodologies that have shaped the use of biocides in the industry 1. We are committed to science and dedicated to educating the market. Dow Microbial Control brings its technology to oil and gas operators through a network of highly trained service companies. Souring Biofilm Control Microbial Influenced Corrosion (MIC) Sustainable Control Working with our customers to develop better solutions and treatment programs to control and protect against reservoir souring. Offering more effective products to help prevent or remove biofilm driven by world-class laboratory test methodology simulating field operating conditions. Helping to prevent microbially influenced corrosion to protect the integrity and service life of assets. Developing solutions that provide sustainable microbial control and meet regulatory needs. Customer Application Centers With an industry-leading breadth of knowledge and more than 60 years of experience in microbial control, our Customer Application Centers offer advanced microbial control solutions both for today and the future. Our ongoing commitment to innovating new products, actives and capabilities is supported by state-of-the-art, fully equipped microbiology, chemistry and analytical laboratories featuring a world-class team of scientists. Dow Microbial Control offers a uniquely focused service to our customers. This includes understanding customers specific application performance requirements, environmental needs and today s stringent regulatory requirements to ensure we develop effective, optimized, sustainable solutions. 1 Recent publications include: Co-authored by Dow Microbial Control and Multi-Chem Production Chemicals: Michael V. Enzien, Bei Yin, Donald Love, Michael Harless, Edward Corrin Improved Microbial Control Programs for Hydraulic Fracturing Fluids used during Unconventional Shale-Gas Exploration and Production, paper no , Society of Petroleum Engineers 2011 Co-authored by Dow Microbial Control and Multi-Chem Production Chemicals: Edward Corrin, Terry M. Williams A Case Study Evaluating a Co-Injection Biocide Treatment of Hydraulic Fracturing Fluids Utilized in Oil and Gas Production, paper no. 5998, Corrosion 2015 Co-authored by Dow Microbial Control, Baker Hughes Inc. and Encana Oil & Gas (USA) Inc.: Jon Raymond, Earl Parnell, Jennifer Fichter Determining Effective Antimicrobial Treatments for Long-Term Protection of Hydrocarbon Reservoirs, paper no. 3879, Corrosion 2014 Co-authored by Dow Microbial Control and FTS International: Stephen N Guessan, Jon Raymond, Reinaldo Navarrete Environmentally-Conscious Biocides for Long-Term Protection of the Fracture, paper no , Society of Petroleum Engineers 2015 Co-authored by Dow Microbial Control and Delft TU: Michael V Enzien, Debora Takahashi, Bei Yin, Simona Bottero Increase Oil and Gas Production Through Improved Microbial Control Programs, paper no. 2740_10, Brazilian Petroleum, Gas and Biofuels Institute 3

4 Protect Oil and Gas Operations with an Optimized Microbial Control Program Registration* Efficacy Water Treatment Microbiocide % Active Ingredient Physical Form CAS Number for Active Ingredient(s) US EPA Canada PMRA Speed of Kill Duration of Protection PREPARE AQUCAR DB 97.6% 2,2-dibromo-3-nitrilopropionamide (DBNPA) Solid AQUCAR DB 20 20% 2,2-dibromo-3-nitrilopropionamide (DBNPA) Liquid AQUCAR DB 5 5% 2,2-dibromo-3-nitrilopropionamide (DBNPA) Liquid AQUCAR 742 AQUCAR % Glutaraldehyde, 7.5% alkyl dimethyl benzyl ammonium chloride (ADBAC) 14% Glutaraldehyde, 2.5% alkyl dimethyl benzyl ammonium chloride (ADBAC) Liquid , AQUCAR % Glutaraldehyde (includes a non ionic surfactant) Liquid AQUCAR GA 50 50% Glutaraldehyde PROTECT DECONTAMINATE AQUCAR GA 30 LT 30% Glutaraldehyde (freeze-protected formulation) AQUCAR GA 25 25% Glutaraldehyde Liquid AQUCAR GA 15 15% Glutaraldehyde AQUCAR GA 4P0 4% Glutaraldehyde AQUCAR PS 75 75% tetrakis(hydroxymethyl)phosphonium sulfate (THPS) Liquid AQUCAR PS 20 20% tetrakis(hydroxymethyl)phosphonium sulfate (THPS) AQUCAR BP 99% 2-bromo-2-nitropropane-1,3-diol (Bronopol) Solid AQUCAR BP 30 30% 2-bromo-2-nitropropane-1,3-diol (Bronopol) Liquid AQUCAR BP 10 10% 2-bromo-2-nitropropane-1,3-diol (Bronopol) Liquid AQUCAR A 78 78% dimethyloxazolidine (DMO) Liquid AQUCAR TA 64 64% 1-(3-chloroallyl)-3,5,7-triaza- 1-azoniaadamantane chloride (CTAC) Solid AQUCAR TN 25 25% tris(hydroxymethyl)nitromethan (THNM) Liquid * Please check the registration details as they apply to your location in the US or Canada to verify the product is approved for your specific use. 4

5 Compatibility Environmental Profile Efficacy on Oilfield Organisms (SRBs, APBs) Friction Reducers/ Anionic Additives Proppant and Formation Low Foaming Non- Corrosive at Uselevel Sour Systems (Sulfide) Performance at High Temp. (>50 C) ph Range of Use Biodegradation Low Aquatic Toxicity No AOX Formation Aboitic Degradation Up to 8.5 Up to 9.5 Up to 9.5 Up to 9.5 Up to 9.5 Up to 8.5 Up to 11 Up to Characterization based on laboratory studies of active ingredients. Generally, higher numbers of represent more favorable characteristics. For speed of kill and duration of protection, please find more detailed information below: Speed of Kill Minutes to about an hour Hours to about a day Multiple days Duration of Protection Lasts weeks to months Lasts a few weeks Lasts for a few hours to few days 5

6 Understanding the Needs of the Different Phases of Oil and Gas Exploration and Production Dow provides the world s broadest range of microbial control actives for oil and gas applications as well as state-of-the-art diagnostic techniques and expertise required for advanced sustainable microbial control. Dow collaborates with multiple stakeholders along the hydrocarbon value chain to design and implement novel applications that can provide specific, yet extended, microbial control, all while minimizing the impact on the environment. Our advanced microbial control solutions are used in a broad range of oil and gas applications including: near wellbore treatment, protection of the reservoir, hydraulic fracturing, water and polymer flooding, topside remediation of produced and recycled waters as well as MIC and asset integrity. Microbial control programs are necessary to optimize conventional as well as unconventional oil and gas production. To maximize microbial control efficacy, the right technologies need to be applied in the different phases of the operation: preparing the water and treating topside, decontaminating the well, as well as protecting the reservoir. Treat topside, prepare the water Decontaminate the well Protect the reservoir Produced water and oilfield waters can contain bacteria that need to be treated. Treating the water with biocides will provide an initial reduction of bacteria, thereby helping to prevent corrosion of the assets, reduce souring, and enhancing the performance of biocides added in later stages of the process. Native downhole populations and microorganisms introduced during water injection leave wells infested with bacteria that survive and thrive in subsurface conditions. Inclusion of an effective biocide in injection water and hydraulic fracturing fluid will provide initial control downhole. Throughout continuous water injection or after the hydraulic fracturing process is complete, it is critical to control microbial growth in the reservoir environment. Biocides that remain effective under elevated temperature, pressure and salinity conditions for longer durations of time are necessary to help prevent souring, corrosion of assets and formation of in situ biofilm over time. TREAT topside PREPARE the water DECONTAMINATE the injection well PROTECT the reservoir / ClO 2/Oxidizers Quats/TTPC DBNPA* Glutaraldehyde* Glutaraldehyde* + Quats THPS* Bronopol* Dazomet DMO* CTAC* THNM* Nitrate (only for water flooding) Duration of Effectiveness *Dow Technology Minutes Hours Days Weeks Months Temperature Ambient Formation Compatibility Poor DBNPA: 2,2-dibromo-3-nitrilopropionamide THPS: tetrakis(hydroxymethyl)phosphonium sulfate DMO: dimethyloxazolidine CTAC: 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride THNM: Tris(hydroxymethyl)nitromethane Downhole Excellent 6

7 Compatibility Hydrocarbon production involves many additives that can interfere with the activity of some biocides. It is critical to understand potential incompatibilities and other properties of biocides that could negatively affect operations. Friction Reducers Many biocides have negative interactions with friction-reducing polymers used for hydraulic fracturing. Those interactions can negatively influence the function of both the biocide and the friction reducer. Figure 1: Glutaraldehyde and Glut-Quat blends retain antimicrobial performance in the presence of friction reducers. Active levels required for 5-log kill of aerobic organisms in frac water with 500 friction reducer a.i Glut* Glut-Quat* DDAC TTPC ADBAC THPS* *Dow Technology Friction Reducer 1 Friction Reducer 2 Foaming A biocide that foams can cause problems during application. Minimum foaming is a desirable parameter for a biocide. Figure 2: Optimized Glut-Quat ratios minimize foaming problems during application. When the ratio is weighted more towards the glut component as compared to the quat, the blends are less likely to have foaming issues. Foam height measured at typical biocide usage levels Foam Height (cm) Exceeded 15 cm maximum measurable height 3 0 TTPC (50 a.i.) ADBAC (20 a.i.) 25.8% Glut* 12.5% Quat* (38 a.i.) 42.5% Glut* Glutaraldehyde* 7.5% Quat* (50 a.i.) (43 a.i.) THPS* (70 a.i.) DBNPA* (50 a.i.) Bronopol* (200 a.i.) *Dow Technology Dazomet (600 a.i.) Dynamic Stable Proppant/Formation Compatibility Surface-acting biocides (like quaternary amines and TTPC) can be adsorbed on high-surface area solids, like some proppants and silt layers in the formation, thus reducing the availability of the biocide to kill microorganisms. Use-Level Corrosion Some biocides in their concentrated forms are corrosive to metals, including stainless steel. However, when diluted to their use concentration (0 or less), most are essentially non-corrosive. The exceptions are oxidizing biocides, including chlorine dioxide, which are strongly corrosive even at diluted use levels (1 or less). 7

8 Efficacy The biocide concentration required to reduce a microbial population by a specific logarithmic level (log kill) is commonly utilized to assess antimicrobial performance in a given system (i.e. injection water, drilling mud, produced water, etc.). The concentration of biocide required for effective microbial kill can vary across different applications and is dependent upon multiple factors including organism type, microbial load, fluid/additive compatibility and system ph/temperature. Furthermore, the concentration and type of biocide required for efficient microbial kill will depend on the particular performance needs such as speed of kill or length of protection. Efficacy against Sulfate Reducing Bacteria A laboratory study was performed in a blended injection water matrix (seawater/ produced water), obtained from an active oil and gas operation, to determine the time-dependent performance of commonly utilized oilfield biocide chemistries. Samples of injection water were inoculated with field-isolated Sulfate Reducing Bacteria (SRB) and then treated with different biocides, at two concentration levels. Viable organisms were measured immediately following, 45 minutes and 4 hours after treatment. Figure 3: All biocides tested provide effective kill against SRBs after four hours. Rapid reduction of SRBs to treat topside/prepare the water and decontaminate the well Log 10 viable SRB Untreated 10 Glutaraldehyde* Glut/ADBAC quat* THPS* DBNPA* 25 0 mins 45 mins 4 hours Efficacy against Acid Producing Bacteria A lab study was performed with Acid Producing Bacteria (APBs) in a synthetic injection water matrix. The samples were inoculated with an isolated APB strain and then treated with different biocides. Viable organism levels were measured immediately following, 45 minutes and 4 hours after treatment. Figure 4: All biocides tested provide effective kill against APBs after four hours. Rapid reduction of APBs to treat topside/prepare the water and decontaminate the well Log 10 viable APB *Dow Technology 0 mins 45 mins 4 hours Untreated Glutaraldehyde* Glut/ADBAC quat* THPS* DBNPA* *Dow Technology 8

9 Efficacy in Heat-Aged Systems Providing protection not only against the organisms in the injection water, but also against organisms native to the formation, helps prevent souring. Extended downhole protection is provided by biocides that are able to retain efficacy in an environment with elevated temperature and salinity. Duration of protection in heat-aged systems High-temperature (75 C) antimicrobial efficacy studies were performed for 64 days in three distinct fracturing fluid systems utilizing CTAC, DMO and THNM preservative chemistries ranging from to 300 active ingredient. The number of days of protection provided by the strongest performing preservative, in each individual fracturing fluid system, following repeated APB/SRB inoculations is represented in Figure 5. Although all three preservative chemistries work well in a variety of fracturing fluids, finding the optimal preservative, dosage, and co-biocide requires customized solutions, which Dow has the technical expertise and capabilities to help develop Results can vary significantly between water samples, dependent on additives used and water composition. Laboratory studies of biocide efficacy are highly recommended for new operations in order to determine the best biocide treatment program. *Dow Technology Figure 5: CTAC, DMO, and THNM provided long-term microbial control of both SRB and APB in three fracturing fluid samples. 9

10 Sustainability Sustainability, in the context of microbial control, is defined as a technology which is able to meet three needs: 1. Firstly, the microbial control solution must do its job effectively, meaning controlling and preventing the growth of microorganisms. 2. Secondly, the biocide treatments disappear after doing their job. They should be designed to be biodegradable, non-persistent, and non-accumulative in the environment. 3. Finally, the biocides should do no harm to society, biodiversity, the environment, people, or processes. Dow is dedicated to developing sustainable microbial control solutions and offers a leading portfolio of such products to the industry today. Hazard-Based Rating vs. Risk-Based Models Individual data points for toxicity based solely upon the hazards of the concentrated product can give an incomplete picture of the risk profile of any given biocide. Riskbased models that take into account all factors (such as toxicity, usage levels, and wastewater treatment processes, biodegradation, etc.) are more accurate and used by regulating authorities. Degradation Biodegradation and chemical degradation are important aspects when considering the overall sustainability of applying a biocide for oilfield applications. These degradation processes are taken into account by risk-based models such as the OSPAR Commissions CHARM (Chemical Hazard and Risk Management) model for assessing chemicals used in offshore oil and gas operations, and other similar tools which assess margin of exposure associated with specific biocide applications. Active Daphnia magna LC 50 () Rainbow Trout LC 50 () DBNPA Glutaraldehyde 5 13 THPS Bronopol DMO CTAC THNM LC 50 : Concentration of a single dose lethal to 50% of laboratory test group. Though each biocide will have a species that is most sensitive, Daphnia magna and Rainbow Trout are common environment model organisms. Active OECD 301 Readily Biodegradable DBNPA OECD 302 Inherently Biodegradable Glutaraldehyde THPS Bronopol DMO CTAC THNM OECD guidelines are intentionally agreed testing methods used by government, industry and independent laboratories to identify and characterize potential hazards of chemicals. OECD guidelines 301 and 302 assess the ability of microorganisms to degrade small doses of biocide. Absorbable Organic Halide (AOX) Formation Most organic biocides do not contribute to AOX levels in water. Certain biocides, most specifically halogenated oxidizers (chlorine, bromine, bleach, chlorine dioxide and stabilized versions thereof), however, can react with residual hydrocarbons found in oilfield waters to produce halogenated hydrocarbons. These products can often be difficult to biodegrade and many are of concern for water discharge. 10

11 Genuine Glutaraldehyde In the more than six decades since glutaraldehyde was introduced to the marketplace, it has become known as a versatile molecule. Today, non-genuine products, mixed with lesseffective aldehydes such as formaldehyde or glyoxal, but labeled deceptively as glutaraldehyde, are available in the marketplace all over the world. Risks are potentially high for workers and the environment when mislabeled chemicals, especially ones containing carcinogens, are unknowingly handled. GENUINE GLUTARALDEHYDE is not a carcinogen, mutagen, nor a reproductive toxicant. It does not bio accumulate and is readily biodegradable. It s critical for companies to ensure they are using GENUINE GLUTARALDEHYDE to comply with approved safe handling guidelines. Non-genuine products may have significantly different toxicological properties that can harm workers and the environment and have been proven to fall short in efficacy and sustainability. The Dow Chemical Company has developed and validated new analytical methods to help customers distinguish GENUINE GLUTARALDEHYDE from non-genuine products that are labeled incorrectly as glutaraldehyde. These methods include an innovative, field-deployable, and easy to use test-kit that provides a rapid detection method. For more information, visit Product Stewardship Dow has a fundamental concern for all who make, distribute, and use its products, and for the environment in which we live. This concern is the basis for our product stewardship philosophy by which we assess the safety, health, and environmental information on our products and then take appropriate steps to protect employee and public health and the environment. The success of our product stewardship program rests with each and every individual involved with Dow products from the initial concept and research, to manufacture, use, sale, disposal, and recycle of each product. Dow strongly encourages its customers to review both their manufacturing processes and their applications of Dow products from the standpoint of human health and environmental quality to ensure that Dow products are not used in ways for which they are not intended or tested. When considering the use of any Dow product in a particular application, review the latest Safety Data Sheet (SDS) and country-specific product label to ensure the intended use is within the scope of approved uses and can be accomplished safely. Dow personnel are available to answer your questions and to provide reasonable technical support. Dow product literature, including SDS s, should be consulted prior to use of Dow products. Current SDS s are available from Dow. Use biocides safely. Always read the label and product information before use. Dow Beyond Microbial Control In addition to the broad portfolio of microbial control technologies, Dow is uniquely positioned to address local and regional hydrocarbon industry challenges worldwide. Familiar with individual company and local needs, Dow s oil and gas experts draw upon global R&D resources and decades of experience for customizing solutions and services tailored to the evolving needs of our customers. And Dow s experts routinely leverage a first-class toolbox of technologies for addressing customer challenges: Dow s branded systems and solutions for cost-effective, sustainable operations relating to exploration, production, enhanced oil recovery, transportation, refining, gas processing and distribution are industry standards. With a broad portfolio of ion exchange resins, reverse osmosis membranes, ultrafiltration membranes and electrode ionization products Dow spearheads the development of sustainable technologies that integrate water and energy requirements to help oil and gas customers optimize all phases of their water usage. 11

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