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Inhibitor products have been widely used to reduce both steel corrosion and scale deposition on pipelines, tubings and safety valves in critical offshore sites. Their simultaneous injection with brine has gradually increased the lifetime of production wells with incontestable benefits for the oil and gas industry. However, the large use of such additives has not been followed by the development of any efficient technique of dosage that considers the strict requirements of an offshore platform. In this paper, we describe a novel method of chemical dosage that takes into account all the on-site technical and practical parameters, such as the quantification thresholds or molecule specificity, the real-time monitoring, the resistance and compactness of measurement device and a user-friendly interface of measurement. Current techniques of inhibitor monitoring that use elemental analysis (ICP, MS, …) for sub-ppm quantifications appear too complex for a successful long-term on-site industrial exploitation due to the bulky dimensions of apparatus and the delay and complexity of analysis. A long-term collaboration between University of Lyon and Total EP has defined a simple and accurate method for inhibitor monitoring based on the use of lanthanide tracers and the Time-Resolved Fluorescence (TRF) technique. We exploited the fact that inhibitor chemicals (i) are good chelators for lanthanide ions and (ii) amplify the luminescence signal of rare-earths. In this way we are able to collect the photon emission signal by TRF apparatus and dosing the inhibitors. The portability of the TRF device as well as the sensitivity of detection have been engineered in order to obtain a sub-ppm quantification threshold via 1-click task. Several carboxylates, phosphonates and sulphonates additives diluted in brine solutions has been easily measured out even in presence of residual oil. More than 20 commercial inhibitor solution samples were quickly prepared and dosed with an impressive linearity of response (R2 test > 0.996) in the 10 – 100 ppm range. Any further extension of range has been possible. In addition, we were able to quantify two inhibitors (scale – scale, scale – corrosion) in the same brine water. This technique certainly opens a new conception of smart chemicals management in oil and gas production for (i) a dramatic minimization of the injected compounds (ii) a reducing delay in pipelines monitoring, and (iii) a shut down of expenses of pipeline maintenance.
Inhibitor products have been widely used to reduce both steel corrosion and scale deposition on pipelines, tubings and safety valves in critical offshore sites. Their simultaneous injection with brine has gradually increased the lifetime of production wells with incontestable benefits for the oil and gas industry. However, the large use of such additives has not been followed by the development of any efficient technique of dosage that considers the strict requirements of an offshore platform. In this paper, we describe a novel method of chemical dosage that takes into account all the on-site technical and practical parameters, such as the quantification thresholds or molecule specificity, the real-time monitoring, the resistance and compactness of measurement device and a user-friendly interface of measurement. Current techniques of inhibitor monitoring that use elemental analysis (ICP, MS, …) for sub-ppm quantifications appear too complex for a successful long-term on-site industrial exploitation due to the bulky dimensions of apparatus and the delay and complexity of analysis. A long-term collaboration between University of Lyon and Total EP has defined a simple and accurate method for inhibitor monitoring based on the use of lanthanide tracers and the Time-Resolved Fluorescence (TRF) technique. We exploited the fact that inhibitor chemicals (i) are good chelators for lanthanide ions and (ii) amplify the luminescence signal of rare-earths. In this way we are able to collect the photon emission signal by TRF apparatus and dosing the inhibitors. The portability of the TRF device as well as the sensitivity of detection have been engineered in order to obtain a sub-ppm quantification threshold via 1-click task. Several carboxylates, phosphonates and sulphonates additives diluted in brine solutions has been easily measured out even in presence of residual oil. More than 20 commercial inhibitor solution samples were quickly prepared and dosed with an impressive linearity of response (R2 test > 0.996) in the 10 – 100 ppm range. Any further extension of range has been possible. In addition, we were able to quantify two inhibitors (scale – scale, scale – corrosion) in the same brine water. This technique certainly opens a new conception of smart chemicals management in oil and gas production for (i) a dramatic minimization of the injected compounds (ii) a reducing delay in pipelines monitoring, and (iii) a shut down of expenses of pipeline maintenance.
The accurate and precise analysis of scale inhibitors can play an important role in conjunction with other field data like ion analysis, total suspended solids and productivity index in making key decisions on the efficiency of scale squeeze and continuous chemical injection treatments. It is essential to have reliable data on scale inhibitor residuals in produced fluids to prevent wells from scaling and to enable maximum lifetime for scale squeeze treatments especially in complex operating environments. A variety of techniques exist for scale inhibitor analysis including the more simple methods like hyamine, fluorescence and Inductively Coupled Plasma Optical Emission Spectroscopy (ICPOES) to more complex techniques like high pressure liquid chromatography (HPLC) and mass spectroscopy (MS). All of these techniques, including combinations thereof, are currently in use and the advantages and disadvantages of each technique will be compared and contrasted for the different types of scale inhibitor. The impact of phosphorus speciation in phosphorus tagged polymers and for thermal degradation of phosphonates and phosphate esters will also be considered. Examples will be provided of how the analysis results can be misinterpreted if the wrong analysis techniques are used. In addition, specific scenarios in North Sea fields for treating conventional and co-mingled sub-sea wells will be discussed to highlight the use of scale inhibitor analysis techniques to aid chemical selection based upon chemical retention, minimum inhibitor concentration (MIC), detection limits and well production conditions. This paper will present a state of the art review of scale inhibitor analysis techniques and describe how these techniques can be used to provide cost effective scale management in simple to complex production scenarios.
Reliable and accurate analysis of inhibitors is vital for decisions on efficiency and cost-effectiveness of scale inhibitor squeeze treatments. Recent developments have resolved issues for residual sulphonated polymer chemistries which were previously difficult to isolate. Attention now is directed to challenges associated with phosphonate based inhibitors, particularly when assay is required from a multi-component produced water sample containing other P based inhibitor species which currently poses a significant challenge. This paper describes the advantages and limitations of techniques used for phosphorus assay including inductively coupled plasma spectroscopy, ion chromatography and wet chemical methods (e.g. Phospho-molybdenum blue, PMB) approaches. Field examples are discussed to emphasize the analytical challenge with cases whereby speciation is readily achieved and others where this is not the case. To overcome the limitations of these methods, novel approaches for analysis of P – containing inhibitors (in the presence of other –containing additives) include time resolved fluorescence spectroscopy (TRF) and mass spectrometry (MS) detection (which also require development) are considered with potential benefits and limitations / interferences highlighted. These are discussed with highlights of TRF development presented. This technique shows significant scope and potential with promising results showing speciation and discrimination of both polymeric and phosphonate based scale inhibitors as well as a phosphate ester based corrosion inhibitor. This paper highlights the concept that for residual scale inhibitor assay, one analytical approach does not fit all environments and applications. However the availability of a range of techniques, some of which are still in development, allows for effective monitoring in complex, multi-component environments. The paper highlights development opportunities for some of the newer approaches such as TRF and MS as well as discussing their limitations in complex produced fluids.
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