Scale inhibitors are commonly used for mitigating scale deposition risks in many oil and gas wells worldwide. Of the various chemistries used for scale inhibition, much research has gone into the various conditions in which each chemistry performs best (i.e. temperature, brine solubility, salinity, etc.)4-6. Furthermore, it is known that dissolved iron (Fe2+ and Fe3+) can hinder the performance of scale inhibitors, some more than others3. Thus, applying this knowledge we can extrapolate which inhibitor chemistries might perform best under a given set of conditions. This knowledge can then be applied regionally where most production comes from the same or similar reservoirs and production conditions. However, less research has been conducted on the effects of pre-existing iron sulfide deposits on the performance of scale inhibitors. Iron sulfide solids are becoming increasingly problematic in the oil field. The combination of iron sulfide with more conventional scaling deposits and the fact that scale inhibitors are surface active and tend to adsorb onto surfaces can yield very challenging situations. This paper discusses testing conducted on various scale inhibitor chemistries and evaluates how exposure to pre-existing FeS solids may impact performance. The various scale inhibitors were evaluated for inhibition performance against a set of controls (no FeS exposure) utilizing the NACE Standard TM0137-2007 "Laboratory Screening Tests to Determine the Ability of Scale Inhibitors to Prevent the Precipitation of Calcium Sulfate and Calcium Carbonate from Solution (for Oil and Gas Production Systems)" with an additional pre-test procedure to expose scale inhibitors in stock solution to a set weight of reagent grade ferrous sulfide (FeS). Scale inhibitor chemistries evaluated include two polymers (scale inhibitor A and B) and five phosphorous based scale inhibitors (scale inhibitors C through F). The various configurations tested included: scale inhibitors alone, scale inhibitor plus FeS solids, scale inhibitor without FeS plus crude oil, scale inhibitor plus FeS and crude oil. The inclusion of the crude oil allowed an interface for potential micelle interactions. The results indicate scale inhibitors A, C and G were least affected by the presence of FeS with no regard to the presence of crude oil. With this study a scale inhibitor that worked best in the presence of FeS solids for the customer's field in the Permian Basin, where FeS has become an increasing issue, was recommended. This also allowed the customer to treat the FeS solids issue via the method that works best for them.
Accurate bicarbonate measurement is crucial in carbonate scales prediction. A common method for bicarbonate determination is through subtracting total alkalinity with carboxylates, but the measurement of carboxylates is time consuming and not applicable in the field. Since bicarbonate is hard to preserve in field brines, a field applicable method for bicarbonate detection was developed in a previous study. It was named the "head space method". The method is based on the head space pressure change due to carbon dioxide (CO2) releasing from test brine by adding strong acid to convert bicarbonate to CO2. This study is to further validate the method with synthetic and field brines and to investigate potential limitations. Based on the the tests of this study, the head space method can measure bicarbonate accurately without interference by the presence of carboxylates. In both synthetic and field brine analysis, the bicarbonates measured by head space method generally matched with the calculated bicarbonates through total alkalinity and total carboxylates. A case study further validated the accuracy of the head space method on bicarbonate determination. Moreover, this method is fast with low costs. Each sample analysis takes about 5 minutes. The capital cost of head space method equipment is less than 1,000 dollars. A limitation of the head space method identified that it is not applicable for high sulfide brines or brines with < 100 mg/L bicarbonate. Desipite the limitation, this low-cost bicarbonate detection method is fast, accurate, and applicable in the field, and able to provide instant bicarbonate monitoring in produced water in many cases.
In the Rocky Mountain region of the United States, high-salinity brines (total dissolved solids > 250, 000 mg/L) present during oil and gas production cause severe scale problems in the Williston Basin. The scales include not only calcium carbonate, calcium sulfate, barium sulfate, strontium sulfate, but also sodium chloride (halite). This paper presents the development of test methods and their corresponding testing results for scale inhibitor evaluations in the laboratory and their applications in the field for high-salinity brines. It is well known that there is no effective test method for halite scale inhibitor laboratory testing due to the difficulty of controlling the amount of halite precipitation and reproducibility in the test. The evaluation of scale inhibitor performance was conducted by using a tube-blocking test and a static bottle test with synthetic high-salinity brines from the Williston Basin. Two sets of brines were designed, based on the field brine, and were tested with two methods. One set of brine was for halite scale inhibitor evaluation by mixing near-saturated NaCl synthetic brine with a highly concentrated brine of CaCl2·2H2O + NaCl. The second set of brine was designed to evaluate scale inhibitor performance on calcium carbonate, calcium sulfate, barium sulfate, and strontium sulfate by modified brines. Three types of scale inhibitors were used for the performance evaluations, including halite scale inhibitors, general scale inhibitors, and a multifunctional scale inhibitor. The lab test results showed the multifuntinal scale inhibitor exhibited good scale inhibition performance for both sets of scale testing. Successful scale inhibitor implementations in the field applications and case history are also presented in this paper.
Fluorescence tagged (F-tagged) scale inhibitors are drawing more interest in the oil industry and are being applied in the field. One main reason is being easily detectable and differentiable from other scale inhibitors. However, when applied to a new oilfield, it is necessary to evaluate their thermal stability, limit of detection (LOD), and fluorescence measurement interference from other chemicals. Two F-tagged scale inhibitors were tested in this study. They are the same polymeric inhibitors with different and differentiable fluorescent tags. Both F-tagged inhibitors were able to be detected in synthetic brine and field brine from a Gulf of Mexico (GoM) field, with LOD of 1ppm. A coreflood test was also conducted for inhibitor squeeze treatment evaluation. The residual scale inhibitor in core flooding samples was measured by both fluorescence method and high performance liquid chromatography (HPLC). The results from two methods generally match with each other. This strongly indicates that the F-tag is stable on scale inhibitors and fluorescence measurement is a reliable method for scale inhibitor detection. Thermal aging test and long storage test were conducted. For both F-tagged scale inhibitors, the thermal aged samples and samples with different storage lifetime did not show significant difference on scale inhibition performance and fluorescence measurement. The two F-tagged inhibitors tested can tolerate high temperature up to at least 130°C (266°F). With proper storage, F-tagged inhibitors after long shelf storage were still as effective as fresh inhibitors. Based on all the test results in this paper, these two scale inhibitors are ready for squeeze application in GoM.
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