Summary A systematic study was made of phase behavior of alkoxyglycidylether sulfonates (AGESs). These surfactants were screened with either NaCl-only brines or NaCl-only brines and n-octane at water/ oil ratio (WOR) ~1 for temperatures between approximately 85 and 120°C. All test cases were free of alcohols and other cosolvents. Classical Winsor phase behavior was observed in most scans, with optimal salinities ranging from less than 1% NaCl to more than 20% NaCl for AGESs with suitable combinations of hydrophobe and alkoxy chain type [ethylene oxide (EO) or propylene oxide (PO)] and chain length. Oil solubilization was high, indicating that ultralow interfacial tensions existed near optimal conditions. The test results for 120°C at WOR~1 have been summarized in a map, which might provide a useful guide for initial selection of such surfactants for EOR processes. Saline solutions of AGESs separate at elevated temperatures into two liquid phases (the cloud-point phenomenon), which may be problematic when they are injected into high-temperature reservoirs. An example is provided that indicates that this situation can be alleviated by blending suitable AGES and internal olefin sulfonate (IOS) surfactants. Synergy between the two types of surfactant resulted in transparent, single-phase aqueous solutions for some blends, but not for the individual surfactants, over a range of conditions including in synthetic seawater. Such blends are promising because both AGES and IOS surfactants have structural features that can be adjusted during manufacture to give a range of properties to suit reservoir conditions (temperature, salinity, and crude-oil type).

The production and properties of two families of anionic surfactants (internal olefin sulfonates and branched C16, 17 alcohol-based alkoxy sulfonates) are described for chemical flooding of oil reservoirs at high temperatures and/or high salinities. Surfactant properties measured include oil/water micro-emulsion phase behaviour obtained using new glassware-based procedures appropriate for higher reservoir temperatures. The results obtained relate to oil/water interfacial tension behaviour and give the "operating window" of the surfactants in terms of their optimal salinity and ability to solubilise oil in the micro-emulsion. The phase tests also give information on the quality of the micro-emulsions obtained where low viscosity and absence of gels is desirable. The surfactants described are promising for EOR and can be produced in commercial quantities. Different IOS products are available with different carbon chain cuts (with range C15 to C28) allowing matching of the IOS to the temperature, salinity and crude oil type of reservoirs. In addition, both IO carbon chain (degree of branching) and the degree of sulfonation influence the surfactant properties of the IOS mixture formed which provides a means for tailoring an IOS surfactant for optimal performance. 1. Introduction In chemically enhanced oil recovery (EOR) the mobilisation of residual oil saturation is achieved through surfactants that generate a sufficiently (ultra) low crude oil/water interfacial tension (IFT) to give a capillary number large enough to overcome capillary forces and allow the oil to flow1. However, reservoirs have different characteristics (crude oil type, temperature and water composition), and the structures of added surfactant(s) have to be tailored to these conditions to achieve an ultra low IFT. In addition, a promising surfactant must satisfy other important criteria including low rock retention, compatibility with the polymer to be used, compatibility with hard water (if present), thermal and hydrolytic stability, acceptable cost/performance balance and commercial availability in sufficient quantities. Because of the well-established relationship between the micro-emulsion phase behaviour and IFT2 it is common in the industry to screen surfactants and their formulations for low IFT through laboratory-based oil / water phase behaviour tests3, 4. This approach works well for tests carried out at room temperature and slightly higher, but at higher temperatures there may be safety issues. Specifically, conventional sealed glass tube test methods may be problematic from a laboratory safety standpoint at higher temperatures due to the vapour pressures from water and crude oil. This paper presents the results of the evaluation of surfactants using improved phase behaviour experimental methods for higher temperatures (up to 150°C). Optimal salinities and solubility parameters have been measured. Two surfactant families have been evaluated, both produced by Shell Chemicals: Internal olefin sulfonates (IOS) which are part of the ENORDET™ O series and proprietary, branched C16, 17 alcohol-based anionic surfactants which are part of the ENORDET™ A series. Both families are suitable for EOR because they have a reduced tendency to form ordered structures/liquid crystals that are undesirable in reservoirs4, IOS products because they are a complex mixture of surfactants of differing chain lengths and the branched C16, 17 alcohol based surfactants because of their randomly branched structures.

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A systematic study was made of phase behavior of alkoxyglycidylether sulfonates (AGESs). These surfactants were screened with either NaCl-only brines or NaCl-only brines and n-octane at water/ oil ratio (WOR) ~1 for temperatures between approximately 85 and 120°C. All test cases were free of alcohols and other cosolvents. Classical Winsor phase behavior was observed in most scans, with optimal salinities ranging from less than 1% NaCl to more than 20% NaCl for AGESs with suitable combinations of hydrophobe and alkoxy chain type [ethylene oxide (EO) or propylene oxide (PO)] and chain length. Oil solubilization was high, indicating that ultralow interfacial tensions existed near optimal conditions. The test results for 120°C at WOR~1 have been summarized in a map, which might provide a useful guide for initial selection of such surfactants for EOR processes. Saline solutions of AGESs separate at elevated temperatures into two liquid phases (the cloudpoint phenomenon), which may be problematic when they are injected into high-temperature reservoirs. An example is provided that indicates that this situation can be alleviated by blending suitable AGES and internal olefin sulfonate (IOS) surfactants. Synergy between the two types of surfactant resulted in transparent, single-phase aqueous solutions for some blends, but not for the individual surfactants, over a range of conditions including in synthetic seawater. Such blends are promising because both AGES and IOS surfactants have structural features that can be adjusted during manufacture to give a range of properties to suit reservoir conditions (temperature, salinity, and crude-oil type).

The development of structure – property relationships are described for new commercial grade internal olefin sulfonates (marketed as the ENORDET™ O series) and laboratory scale alcohol-alkoxy-sulfate surfactants for use in chemical flooding. Surfactant structure was characterised by an in-house developed liquid chromatography mass spectrometry (LC-MS) technique and properties focused on oil/water microemulsion phase behaviour. Such relationships are important to match the surfactant formulation to particular reservoir conditions (temperature, salinity and crude oil). The relationship between IOS structure (by LC-MS) and optimal salinity (by phase tests) has been modeled by the empirical HLB number and by a semi-empirical molecular model. An IOS 24-28 based surfactant system gave excellent microemulsion performance with several, regionally different crude oils and an initial correlation of performance with the composition crude oils has been made. The IOS surfactants described have been produced on a pilot scale and with consistent quality. This commercially available family, and the commercially available alcohol-alkoxy-sulfate family, cover most of the salinity and temperature reservoir conditions expected, though for high temperature and high salinity reservoirs, alcohol based sulfonates will most likely be required. Finally, the chemistry of production of the IOS surfactants and their handling properties are summarised. Part 2 of this paper (SPE-129769-PP) describes work to formulate an IOS mixture that was subsequently used in a successful ASP field test.

This paper discusses the design and application of an alkaline-surfactant-polymer (ASP) system for the West Salym field in West Siberia. The discussion in the paper focuses on surfactant selection, and less on polymer selection. The optimum surfactant system for the West Salym crude is a combination of IOS 24-28 (internal olefin sulfonate with a tail length of 24-28 C-atoms) and IOS 15-18 and also includes an alcohol as co-solvent. The IOS surfactants are manufactured commercially by Shell Chemicals as the ENORDET™ O series. In an accompanying paper1 the properties of the IOS family of surfactants are discussed in more detail. For optimum performance, the surfactant needs to be tailored to the crude oil. Although the oil is not too heavy (API density is 30), and has a near-zero TAN, it contains a significant fraction of heavier components such as asphaltenes and resins, which are surface active and can interfere with the surfactant in the oil-brine interfacial layer. It is discussed in the paper how the crude oil composition affects the surfactant selection process. From test results and theoretical considerations, it was concluded that these types of crude require a surfactant with a long alkyl tail, such as an IOS 24-28. Further optimisation of the surfactant formulation was based on phase behaviour, surfactant solubility and core flow tests. To adjust optimal salinity, and to improve solubilisation, a co-surfactant (IOS 15-18) and an alcohol (2-butanol) were also added. Polymer tests were performed as part of the ASP design program. The purpose was to optimise the ASP/oil mobility ratio. Based on filtration and rheology tests, a hydrolysed poly-acrylamide polymer with a molecular weight in the range 5-8 million was selected. The optimised ASP system was tested in the field in a single well chemical tracer (SWCT) test. The test design, execution and result will be discussed in the paper. The goal of the SWCT test was to measure -under field conditions- the ability of the ASP system to reduce the residual oil saturation. A tracer test was performed, to measure remaining oil saturation (ROS), before and after ASP injection. The test was executed successfully. Analysis of tracer response indicated that 90% of the ROS after waterflood was mobilized by the ASP flood.

In this paper an innovative structure/property approach is used to evaluate several commercially available surfactants in tests relevant to both alkaline-surfactant-polymer (ASP) and surfactant-polymer (SP) floods, in order to gain an understanding of how hydrophobe structure is related to surfactant performance and crude oil composition. The surfactant structural elements considered here include relative branching level and carbon chain length. This has application to chemical EOR implementation in fields over a range of reservoir temperatures and salinity. Phase behavior (giving interfacial tension), and micro-emulsion viscosity tests were carried out for internal olefin sulfonates and mixtures with alcohol propoxy sulfates to identify those that perform well while minimizing or eliminating the use of costly co-solvents. Hydrophobe branching and carbon chain length, characterized by gas chromatography, were used to match surfactants to certain crude oil properties such as natural surfactants, including total acid number (TAN) and asphaltenes, and the ratio of saturates/aromatics. The paper also examines how crude oil sampling influences crude properties and surfactant performance. The approach used and associated data contribute to cost reduction of formulations through a) better matching of commercially produced surfactants to the reservoir and crude oil properties to improve oil recovery efficiency, and b) minimizing or eliminating the use of co-solvents to reduce formulation and logistics costs. In addition, the study demonstrates how binary blends from a few core surfactants can match formulations across regionally different crude oils thereby simplifying formulation selection, and reducing uncertainty and cost.

Accurate laboratory screening of surfactants for their ability to give ultra-low interfacial tensions in oil/brine systems is important as a pre-cursor to laboratory core flow tests and surfactant flooding processes in the field. Screening is usually judged by visualisation of middle-phase micro-emulsions in oil/brine systems. Three laboratory methods are described which enable the phase behaviour of oil/water systems containing surfactants to be more safely visualised and measured in glassware at higher temperatures. Higher temperature test conditions result in significant vapour pressures from crude oil and water, and some glass tube test methods currently used in the industry may not be appropriate from a laboratory safety standpoint. The new methods have been verified in our laboratories for higher temperature use and provide useful screening methods for higher temperature reservoirs (up to 150°C).