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Produced water composition analysis provides evidence of what geochemical reactions are taking place in the reservoir. This information can be useful for predicting and managing oilfield mineral scale resulting from brine supersaturation.
This paper presents results of a study of the produced brine compositions from three wells in a field operated in the North Sea, with geochemical modelling complementing the analysis. The findings presented in this work provide evidence of magnesium depletion and sulphate retardation in a sandstone reservoir at 130° C.
This adjusted formation water composition was then used for calculations of the injection water fraction in each of the produced water samples. The Reacting Ions Toolkit was used to plot data in a variety of formats, including ion concentration vs. ion concentration, ion concentration vs. injection water fraction and ion concentration vs. time to identify trends and to examine the extent of involvement of the various ions in geochemical reactions.
The breakthrough of sulphate, a component primarily introduced during seawater flooding, was retarded during injection water breakthrough. Observed sulphate concentrations were lower than predicted for the case of brine/brine interactions only. The implication of this sulphate reduction was lower minimum inhibitor concentration required to control scale formation and longer squeeze treatment lifetimes for the operator.
A brine/rock interaction mechanism was proposed that involves magnesium depletion and is reproduced in the reactive transport model. 1D reactive transport modelling was performed to match possible
The Rajasthan Field has been undergoing waterflood with produced water reinjection (PWRI) using makeup water with a moderate sulfate (≈500 mg/L) and negligible organic content since 2010. Initial analyses of the formation water indicated that the volatile fatty acid (VFA) content was quite low (≈ 20 mg/L), suggesting
The mechanistic reservoir souring model considers H2S biogeneration due to water-soluble VFAs and/or primarily oil-soluble organics such as BTEX components, the effects of H2S-siderite geochemical reactions within the reservoir to scavenge H2S, flow of H2S (and other components) through the reservoir to the surface, and partitioning of H2S into the oil, water and gas phases within the reservoir and in the surface separators. Also included in the Rajasthan model were the use of power water to lift the well production since it affects partitioning at the surface; and, the effect of chemical H2S scavengers added in selected well flowlines to maintain H2S partial pressures at safe levels.
The model determined that the observed H2S production was not possible even with complete consumption of the indigenous VFAs by sulfate-reducing bacteria and that only with the majority of their organic nutrients being provided by the BTEX-type components were the historical H2S production levels able to be matched. The model results have indicated that H2S production rates have already peaked in the field, primarily due to the reduction in makeup water which provides most of the sulfate being injected into the reservoir. Sulfate is the limiting microbial reactant since the oil-soluble organic supply is essentially infinite.
This study has shown even in non-seawater waterfloods and with minimal organic acids in the formation water that reservoir souring can occur, resulting in the need to handle significant levels of H2S on the surface. The significance of oil-soluble organics as a potential SRB nutrient must be considered when planning a waterflood if sulfate is injected.
Jarrahian, Khosro (Heriot-Watt University) | Sorbie, Kenneth (Heriot-Watt University) | Singleton, Michael (Heriot-Watt University) | Boak, Lorraine (Heriot-Watt University) | Graham, Alexander (Heriot-Watt University)
Scale inhibitor (SI) squeeze treatments in carbonate reservoirs are often affected by the chemical reactivity between the SI and the carbonate mineral substrate. This chemical interaction may lead to a controlled precipitation of the SI through the formation of a sparingly soluble Ca/SI complex which can lead to an extended squeeze lifetime. However, the same interaction may in some cases lead to uncontrolled SI precipitation causing near-well formation damage in the treated zone. This paper presents a detailed study of the various retention mechanisms of SI in carbonate formations, considering system variables such as the (carbonate) formation mineralogy, the type of SI and the system conditions. Apparent adsorption experiments, described previously (Kahrwad et al. 2008), are used to show when the SI/substrate interaction is pure adsorption or coupled adsorption /precipitation. Experiments were performed for different SIs at various operational conditions, i.e. initial pH values, minerologies - calcite, limestone and dolomite - and temperatures; the overall results from these coupled experiments are summarised in Table 3. The SI species used in this study included 1 phosphonate (DETPMP), 1 phosphate ester (PAPE) and 3 polymeric scale inhibitors (PPCA, PFC, VS-Co); the full names of these SIs are given in the paper. All precipitates were studied using Environmental Scanning Electron Microscopy/Energy Dispersive X-Ray (ESEM/EDX) and Particle Size Analysis (PSA). These measurements confirmed that when precipitation occurred, it was mainly in the bulk solution and not on the rock surface.
Low steam viscosity during steam injection can cause steam override and channeling issues for heavy oil recovery, resulting in high operating cost and low oil recovery. One of the common methods to increase the viscosity of steam is by co-injecting surfactants that generate stable foams with steam. The objective of this research is to develop structure-property relationships for surfactants in order to identify surfactant candidates as the steam foam additives for heavy oil recovery.
In this study, alkyl propoxy ethoxy ether carboxylate (alkyl PO EO ECA) surfactants were evaluated. Surfactant solutions at 1 wt% prepared in 1 wt% NaCl were aged at up to 250 °C in Parr reactors for up to 2 weeks. The degradation of the surfactants was quantified based on High Performance Liquid Chromatography profiles of the surfactants before and after the aging process. The foaming performance of the surfactants was evaluated at 1 wt% concentration at varied temperatures from 100 to 250 °C in a high temperature high pressure visual cell. Sand-packed columns were performed to evaluate the ability of the surfactant to increase the apparent viscosity of steam.
The results showed that alkyl PO EO ECA surfactants exhibit excellent chemical stability at up to 250 °C. However, the chemical stability of these surfactants are dependent on the hydrophobe structure as well as the numbers of PO and EO units of the surfactants. Among the studied surfactants, only ECA surfactants with specific structures were able to generate stable foam at 250 °C. It was found that the ECA surfactants with both PO and EO units and a long branched hydrophobe demonstrated to be excellent foaming agents that were able to increase the apparent viscosity of steam by three orders of magnitude at 250 °C in sand-pack columns. In the presence of bitumen, these surfactants were able to increase the steam apparent viscosity by two orders of magnitude. This increase in the steam apparent viscosity is sufficient to overcome the steam override and channeling during steam injection.
Past research has randomly identified some sulfonate and ether carboxylate surfactants as foaming agents for steam EOR processes. This work, however, evaluated these surfactants systematically in order to develop the structure-property relationships that can be used to optimize surfactants as steam foaming agents for thermal EOR processes at up to 250 °C.
Wei, Bing (Southwest Petroleum University) | Wang, Yuanyuan (Southwest Petroleum University) | Chen, Shengen (Southwest Petroleum University) | Mao, Runxue (Southwest Petroleum University) | Ning, Jian (Southwest Petroleum University) | Wang, Wanlu (Southwest Petroleum University)
Foams were introduced to enhanced oil recovery (EOR) for the purpose of improving sweep efficiency via mitigating gas breakthrough. In prior works, well-defined nanocellulose-based nanofluids, which can well stabilize foam film as a green alternative to reduce the environmental impact, were successfully prepared in our group. However, due to the costly manufacturing process, its field scale application is restricted. In order to further simply the manufacturing process and minimize the cost, in this study, we proposed another family of functional nanocellulose, in which lignin fraction was remained as well as carboxyl groups. The primary objective of the present work is to investigate the synergism between the lignin-nanocellulose (L-NC) and surfactant in foam film stabilization. Particular attention was placed on the relation between the chemical composition of L-NC and its stabilizing effect. Direct measurements of foamability, drainage halftime, foam morphology, foam decay, etc., were performed. The results showed that after the contents of lignin and carboxyl group were well tailored, the resultant L-NC can significantly improve the stability of foam either in the absence or presence of crude oil. The flooding dynamics observed in core plugs indicated that the L-NC stabilized foams could properly migrate in porous media and generated larger flow resistance accross the cores than surfactant-only foam.
Wang, Xin (Rice University) | Ko, Saebom (Rice University) | Liu, Ya (Rice University) | Lu, AlexYi-Tsung (Rice University) | Zhao, Yue (Rice University) | Harouaka, Khadouja (Rice University) | Deng, Guannan (Rice University) | Paudyal, Samridhdi (Rice University) | Dai, Chong (Rice University) | Kan, Amy T. (Rice University) | Tomson, Mason B. (Rice University)
Iron sulfide scaling is a severe problem in flow assurance and asset integrity in oil and gas and deep-water production. FeS scale control is challenging due to the extremely low solubility, fast precipitation kinetics and complexity of ferrous iron and sulfide chemistry. Despite the ubiquity of FeS, we have limited understanding about the kinetics and thermodynamics of iron sulfide. To address this problem, we have developed a reliable anoxic plug flow reactor using argon gas to remove oxygen and PIPEs or MES buffer to control pH. The FeS (mackinawite) solubility, precipitation kinetics and phase transformation were the focus of this study. The impact of temperature (25 – 90°C), pH (5.92 – 6.91), ionic strength (0.15 – 4.30 M), Fe(II) to S(-II) ratio, dispersant and chelating reagent have been investigated. It was found that mackinawite is always the first FeS precipitated and could be stable for a week. It was suggested that low pH, high temperature and low ionic strength could accelerate the FeS phase transformation. FeS precipitation is under diffusion control at pH lower than 6.1, which could be accelerated by high temperature and high ionic strength. But the precipitation kinetics would be faster at higher pH. Some evidence suggests the importance of neutral FeS(aq) species at pH 6 −7. A polymeric compound containing amide functional group showed a promising effect by controlling the FeS particle size and reducing FeS scale retention rate. EDTA showed satisfactory FeS scale inhibition effect, as well as reducing FeS scale retention and H2S corrosion rate.
Scale inhibitor (SI) analysis is an extremely important part of scale management and, in recent years, much work has been done on the development of specialist scale inhibitor analysis techniques like Liquid Chromatography Mass Spectroscopy (LCMS) to push the boundaries of low level scale inhibitor detection. However, LCMS requires costly and complex instrumentation and there was therefore still a need for the development of other advanced techniques like fluorescence (F) and Time resolved Fluorescence (TRF) that can be used on site to provide near "on line" data.
Fluorescence techniques are particularly suited to tagged polymers and naturally fluorescent molecules like polyamines whereas the operation principle of TRF is based on interactions between lanthanide ions and various functional groups of polymer or phosphonate scale inhibitors.
Both techniques work individually or in combination and this provides a distinct advantage for multiple scale inhibitor analysis in produced brines that enable the design of packages of different products for specific field applications. In addition, TRF and fluorescence techniques offer the capability of on-site detection compared to the majority of scale inhibitor analysis techniques and other advanced methods like LC-MS.
The ability to detect both phosphonate and polymeric scale inhibitors at very low MIC (<1ppm) has the potential for significantly extending scale squeeze lifetimes. This has now also allowed highly efficient, F tagged polymers, to be used in field situations where scale squeezing was either stopped or the lifetime was significantly compromised because of the lack of confidence in the residuals analysis.
Specific field and theoretical examples from both sub-sea and conventional wells will be presented where the application of both advanced fluorescence and TRF techniques has shown significant improvements in scale management.
This paper will compare and contrast the pros, cons and limitations of both fluorescence and TRF techniques for both phosphonate and polymeric scale inhibitors. In addition, it will highlight examples where scale management significantly improves through the application of Fluorescence and/or TRF scale inhibitor analysis techniques in complex production scenarios.
Baghban Salehi, Mahsa (Chemistry & Chemical Engineering Research Center of Iran) | Mousavi Moghadam, Asefe (Chemistry & Chemical Engineering Research Center of Iran) | Jarrahian, Khosro (Heriot-Watt University)
Preformed Particle Gel (PPG) is an appropriate solution for conformance control and managing water production in low permeable reservoirs. Rheological behavior evaluation of these deformable particles is a key factor in designing composition to achieve the best conformance control treatment due to the viscoelastic behavior of these particles along with their swelling. The purpose of this paper is to evaluate the network parameters of PPGs through swelling tests, rheology and determining its role in maintaining their structural strength. Several PPG hydrogels were prepared by varying the concentrations of polyacrylamide and Cr(OAc)3 as copolymer and crosslinker, respectively. The characterization of these hydrogels was performed using Scanning Electron Micrographs (SEM), Electron Dispersion X-ray analysis (EDX), Environmental Scanning Electron Microscopy (ESEM), ThermoGravimetric Analysis (TGA), and Differential ThermoGravimetry (DTG). The correlation between reaction conditions and network parameters of polymer networks such as, molecular weight of the polymer chain between two neighboring crosslinks, crosslink density, and size fraction have been determined. The swelling of the hydrogels was found through the Fickian diffusion mechanism. In this case, the diffusion rate of water in the 3D structure of the hydrogel is less than the relaxation of the polymeric chain, resulting in a significant increase in the PPG particles volume. As PPG was invaded such as in the reservoir by formation water or oil, repeatedly, the sensitivity factor was measured to ensure the swelling in the electrolyte solution. Based on rheological tests, the dynamic modulus of the swelled PPG was strongly dependent on the concentration and consequently network parameters. Also, through the optimization of the network parameters, the appropriate composition from the point of view of strength (complex modulus of 4×104 Pa) and salt sensitivity of 0.5 was presented. In addition, the results of the TGA/DTG test demonstrated the thermal stability of the sample was in temperature range 245 to 340°C. The determination and analysis of the network parameter is the novel technique for predicting the hydrogel performance in porous media and investigating its strength under harsh reservoir conditions. In other words, determination of the network parameter can be a shortcut to ensure the success of the gel performance in porous media.
Hou, Qingfeng (Key Laboratory of Oilfield Chemistry, Research Institute of Petroleum Exploration and Development, CNPC) | Wu, Qi (Key Laboratory for Green Chemical Technology of Ministry of Education. Collaborative Innovation Center of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University) | Xu, Yan (Key Laboratory for Green Chemical Technology of Ministry of Education. Collaborative Innovation Center of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University) | Zheng, Xiaobo (Key Laboratory of Oilfield Chemistry, Research Institute of Petroleum Exploration and Development, CNPC) | Zhao, Yujun (Key Laboratory for Green Chemical Technology of Ministry of Education. Collaborative Innovation Center of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University) | Wang, Yuanyuan (Key Laboratory of Oilfield Chemistry, Research Institute of Petroleum Exploration and Development, CNPC) | Guo, Donghong (Key Laboratory of Oilfield Chemistry, Research Institute of Petroleum Exploration and Development, CNPC) | Xu, Xingguang (Energy Business Unit, CSIRO)
Switchable surfactants can be reversibly converted between surface active and inactive forms by induced triggers including pH, ozone, ultraviolet light, CO2, N2 and heat. Examples of the CO2 triggered switchable surfactants are guanidines, imidazoles and amidines. In a typical process using CO2 triggered switchable surfactants, an emulsion originating from two immiscible phases is stabilized when CO2 is introduced. Afterwards, the emulsion is flushed by N2 or air, resulting in the destabilization and phase separation. These distinctive properties of the switchable surfactants make them appealing chemicals in the transportation and recovery of the crude oil. N'-alkyl-N, N- dimethylacetamidine bicarbonates, as a CO2-triggered switchable surfactant, has been reported in stabilizing the light crude oil (
A new class of permanent clay stabilizers has been developed inorganic based on an aluminum/zirconium-based compound. The increased charge density of the molecule allows it to bind more strongly to swelling clays, while its relatively low molecular weight allows it to stabilize the clay permanently without causing formation damage by blocking the pore throats and reducing permeability.
The most commonly used clay stabilizers are organic and inorganic chloride salts including trimethylammonium chloride, potassium chloride, and choline chloride. These salts have been used for years, are effective in most wells, and are both cheap and abundant. However, their high water solubility and the relatively small size of the cation means that these products are highly mobile and thus are quickly washed away during flowback. Several chemical derivatives were made from a tri-functional amine by reacting it with organic and inorganic acids such HCl, acetic acid, and formic acid; as well as alkylating agents, including chloromethane, benzyl chloride, diethyl sulfate, and paraformaldehyde.
Certain cationic polymers have also proven useful as clay stabilizers. These much larger molecules are not as easily washed away due to steric hindrance and a much higher charge density per molecule. These products have proved useful as long-term clay stabilizers, but their high molecular weights can lead to formation damage by causing them to be filtered out on the rock face.
In this research, several laboratory tests were carried out on the new clay stabilizer. These tests included coreflood experiments conducted on Berea sandstone cores to assess the stabilizer at high temperatures and the influence of different acids on its performance. Coreflood effluent samples were analyzed using inductively coupled plasma optical emission spectrometry (ICP-OES) to measure the concentrations of aluminum and zirconium.
This new permanent clay stabilizer improved productivity from formations that have high clay content by minimizing clay swelling and thus preventing formation damage caused by clogged pore throats and subsequent loss of permeability. It worked well at temperatures up to 250°F and with 15 wt% HCl and regular mud acid (12 wt% HCl, 3 wt% HF).