Characterizations of surfactant synthesized from Jatropha oil and its application in enhanced oil recovery

Surfactants are frequently used in chemical enhanced oil recovery (EOR) as it reduces the interfacial tension (IFT) to an ultra‐low value and also alter the wettability of oil‐wet rock, which are important mechanisms for EOR. However, most of the commercial surfactants used in chemical EOR are very expensive. In view of that an attempt has been made to synthesis an anionic surfactant from non‐edible Jatropha oil for its application in EOR. Synthesized surfactant was characterized by FTIR, NMR, dynamic light scattering, thermogravimeter analyser, FESEM, and EDX analysis. Thermal degradability study of the surfactant shows no significant loss till the conventional reservoir temperature. The ability of the surfactant for its use in chemical EOR has been tested by measuring its physicochemical properties, viz., reduction of surface tension, IFT and wettability alteration. The surfactant solution shows a surface tension value of 31.6 mN/m at its critical micelle concentration (CMC). An ultra‐low IFT of 0.0917 mN/m is obtained at CMC of surfactant solution, which is further reduced to 0.00108 mN/m at optimum salinity. The synthesized surfactant alters the oil‐wet quartz surface to water‐wet which favors enhanced recovery of oil. Flooding experiments were conducted with surfactant slugs with different concentrations. Encouraging results with additional recovery more than 25% of original oil in place above the conventional water flooding have been observed. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2731–2741, 2017     

Bacillus subtilis-based microbial enhanced oil recovery (MEOR) in polymer microfluidic chip

Microbial enhanced oil recovery (MEOR) is a tertiary oil recovery process that manipulates the microbial environment inside oil reservoirs to modify the physical/chemical properties of the reservoirs to enhance the oil recovery. Up to now, the detailed MEOR mechanism is still not entirely clear due to the multiple influence factors (e.g., pH, nutrients, temperature, porosity, and permeability) on microbial growth and reproduction, as well as the lack of understanding of microbial's influencing mechanism on the oil recovery process. In this study, a Bacillus subtilis-based MEOR process was conducted in a polymethyl methacrylate (PMMA)-based microfluidic device to mimic the MEOR process in the reservoir. The porous microstructure based on real sandstone slice images was fabricated with laser ablation on a PMMA substrate. Two different MEOR approaches were conducted in the PMMA-based microfluidics devices: the direct injection of displacing reagent (biosurfactant produced by bacteria) into the microfluidic chip for the oil recovery (ex-situ), and the incubation of bacteria solution inside the chip followed with brine flooding (in-situ). The result indicates the ex-situ MEOR process with B. subtilis can reach a recovery rate of 38.56%, while the in-situ MEOR process with B. subtilis reached a recovery rate of 40.27%. The proposed study provides a new tool for understanding the MEOR process, with advantages in visibility and accurate fluid control during the MEOR process.     

Rheology and polymer flooding characteristics of partially hydrolyzed polyacrylamide for enhanced heavy oil recovery

Polymer flooding characteristics of partially hydrolyzed polyacrylamide (HPAM) solution with the addition of NaOH were examined in homogeneous glass‐bead packs. The heavy oil recovery in unconsolidated sandstone formations by applying the alkali‐polymer flooding was observed. Experimental results showed that HPAM solution was sensitive to temperature, salinity, and alkali, finding that alkali‐polymer solutions are more effective in improving viscosity than conventional polymer solutions. The solution of 0.5 wt % NaOH mixed with 1500 ppm HPAM (12 mol % hydrolysis degree) was found to be the optimal choice, which gives rise to the highest viscosity on the rheological characterization. Flood tests using the alkali‐polymer solution showed an increase in oil recovery by 30% over water‐flooding when the water‐cut reached 95%, indicating that alkali‐polymer could be more effective in improving sweep efficiency than polymer flood. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

三次采油用表面活性剂结构对油/水界面性能的影响

测定了几种不同分子结构的磺酸盐类阴离子表面活性剂、两性表面活性剂和非离子表面活性剂水溶液与国内某油田原油间的界面张力。结果表明:磺酸盐类表面活性剂降低油水界面张力的能力相对较高,且磺酸盐的烷链长度、芳环种类对界面张力的影响较大,调整磺酸盐的分子结构可以使油水界面张力降低到10~(-2)mN/m数量级;醇/酚醚类非离子表面活性剂以及两性表面活性剂仅能使油水界面张力降低至0.1 mN/m~10 mN/m数量级。     

国内外强化采油用表面活性剂研究进展

中国石油对外依存度持续上升,而采收率持续下降。中国剩余石油储量中大部分为高温高盐、低渗透、稠油油藏等难以开采的苛刻油藏。化学驱强化采油技术目前所使用的石油磺酸盐、烷基苯磺酸盐等常规表面活性剂由于活性低、耐盐性差而导致低效甚至无效。综述了新型表面活性剂,如阴-非离子表面活性剂、双子及寡聚表面活性剂、甜菜碱型两性表面活性剂、高分子表面活性剂、烷基糖苷表面活性剂、黏弹性表面活性剂、生物表面活性剂、阴阳离子混合表面活性剂等的研究进展。讨论了国内外强化采油用表面活性剂评价方法的差异。最后,对采油用表面活性剂的发展方向进行了展望。     

A new zwitterionic surfactant with high interfacial activity and high salt tolerance derived from methyl oleate through an eco-friendly aryl-introducing method

Surfactants, that can reduce the interfacial tension between crude oil and formation water to ultra-low, are needed in tertiary oil recovery. A bio-based zwitterionic surfactant, N-phenylpropanaldehyde epoxy acetal octadecanoicamido propyl-N, N-dimethyl hydroxy sulfonate (PADS), was derived from methyl oleate. In the process of synthesizing PADS, a new reactive site was introduced by epoxidizing methyl oleate and then the benzene ring was introduced by acetalization, which was a greener new method of introducing benzene ring into hydrophobic chains of surfactants. PADS was identified by ESI-MS and NMR, and its interfacial activity was measured by interfacial tensiometer. The results showed that PADS possessed excellent interfacial activity and potential for low-dose application. Under alkali-free conditions, it could reduce the interfacial tension between crude oil and simulated formation water to ultra-low in a wide concentration range (0.005–3 g/L). In addition, although the NaCl concentration was 230 g/L in the system, PADS still had good interfacial activity and could maintain ultra-low oil–water interfacial tension. The protocol of epoxidation and acetalization provides a new feasible path to preparing bio-based surfactants with high interfacial activity.     

The marangoni effect and enhanced oil recovery Part 2. Interfacial tension and drop instability

A computer-based method is described for the determination of the interfacial tension between pendant and sessile drops in a surrounding continuous phase. This has been used to determine the effect on interfacial tension of increasing amounts of aliphatic alcohols, from methanol up to n-octanol, equilibrated between a hydrocarbon solvent (Shellsol) and water. The results indicated large decreases in interfacial tension, with n-butanol, followed by n-propanol giving the greatest reduction. Measurements were also made of the rate of change of interfacial tension during the mass transfer of 2.5% of the alcohols between phases. Changes were observed for all alcohols from ethanol to n-pentanol, the effect being greatest for transfer into water drops and out of solvent drops. Application of the linear stability theory of Sørensen to these results failed to predict the observed instability for transfer into solvent drops.     

为强化石油回采捕集CO2的全周期评估

The development and deployment of Carbon dioxide Capture and Storage （CCS） technology is a cornerstone of the Norwegian government＇s climate strategy. A number of projects are currently evaluated/planned along the Norwegian West Coast, one at Tjeldbergodden. COe from this project will be utilized in part for enhanced oil recovery in the Halten oil field, in the Norwegian Sea. We study a potential design of such a system. A combined cycle power plant with a gross power output of 832 MW is combined with CO2 capture plant based on a post-combustion capture using amines as a solvent. The captured CO2 is used for enhanced oil recovery （EOR）. We employ a hybrid life-cycle assessment （LCA） method to assess the environmental impacts of the system. The study focuses on the modifications and operations of the platform during EOR. We allocate the impacts connected to the capture of CO2 to electricity production, and the impacts connected to the transport and storage of CO2 to the oil produced. Our study shows a substantial reduction of the greenhouse gas emissions from power production by 80% to 75 g·（kW·h）^-1. It also indicates a reduction of the emissions associated with oil production per unit oil produced, mostly due to the increased oil production. Reductions are especially significant if the additional power demand due to EOR leads to power supply from the land.     

Preparation and characterization of nanocomposite hydrogels based on polyacrylamide for enhanced oil recovery applications

In the present work, attempts have been made to prepare nanocomposite type of hydrogels (NC gels) by crosslinking the polyacrylamide/montmorillonite (Na‐MMT) clay aqueous solutions with chromium (III). The X‐ray diffraction patterns of the NC gels exhibited a significant increase in d₀₀₁ spacing between the clay layers, indicating the formation of intercalated as well as exfoliated type of morphology. Exfoliation of the clay layers through out the gel network was found to be predominated, which evidences the high interaction between the polyacrylamide segments and montmorillonite layers. Gelation time as well as variation of viscoelastic parameters such as storage modulus (G′) of the gel network during gelation process at 75°C was studied and followed by rheomechanical spectroscopy (RMS). The NC gels prepared with lower crosslinker concentration showed higher strength and elastic modulus compared with the similar but unfilled polyacrylamide gel. This distinct characteristic of the NC gels yields a gel network structure with high resistance towards syneresis at high temperature in the presence of the oil reservoir formation water. The effects of the composition, such as clay content, crosslinker concentration, and also water salinity upon the gelation rate, gel strength as well as rate of syneresis have been investigated. To optimize the injectivity of the intercalated polyacrylamide solution before the onset of gelation with the gel strength of the final developed gel, sodium lactate was employed as retarder. This was found to be effective to balance these two characteristics of the NC gels, which are aimed to be used for water shut‐off and as profile modifier in enhanced oil recovery (EOR) process during water flooding process. The nanocomposite gels showed much more elasticity and extensibility at low crosslinker concentration compared with the similar but unfilled gel, which makes the NC gels suitable as an in‐depth profile modifier, and also as an oil displacing agent in the heterogeneous oil reservoir in chemical EOR. Effects of the clay content on the thermal stability of the gel network have also been investigated by thermogravimetric analysis (TGA). Scanning electron microscopy (SEM) has been performed upon the NC‐gel samples. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2096–2103, 2006     

The marangoni effect and enhanced oil recovery Part 1. Porous media studies

The use of partitionable solutes, e.g., aliphatic alcohols, to enhance the recovery of trapped oil in reservoir rock, has been simulated using a ballotini-packed column initially flooded with kerosene, and subsequently lowered to an irreducible value by a water drive. Introduction of a “slug” of an alcohol effected an increased recovery, with n-propanol and sec-butanol giving the highest yields. Previous workers attributed such increased recovery to the formation of a “soluble front”, in which both oil and connate water are completely dissolved. However, we obtained similar recoveries using slugs with initial compositions lying on the miscibility boundary, which could not form soluble fronts. It was therefore concluded that Marangoni-induced oscillation of the trapped drops is the more likely explanation of the enhanced recovery.     

The effect of mixed surfactants on enhancing oil recovery

Micelles composed of mixed surfactants with different structures (mixed micelles) are of great theoretical and industrial interest. This work pertains tomaximizing interfacial tension (IFT) reduction via surfactant pairs. In this respect, four types of fatty acid amides based on lauric, myristic, palmitic, and stearic acids were blended with dodecyl benzene sulfonic acid at a molar ratio of 4∶1 and designated as A₁, A₂, A₃, and A₄, respectively. The IFT was measured for each blend at different concentrations using Badri crude oil. The most potent formula (A₄) was evaluated for using in enhanced oil recovery (EOR). The IFT was tested in the presence of different electrolyte concentrations with different crude oils at different temperatures. Finally several runs were devoted to study the displacement of Badri crude oil by A₄ surfactant solution using different slug sizes of 10, 20, and 40% of pore volume (PV). The study reveled that Badri crude oil gave ultra-low IFT at lowest surfactant concentration and 0.5% of NaCl. The recovery factor at a slug size of 20% PV was 83% of original oil in place compared with 59% in case of conventional water flood.     

Emerging applications of nanomaterials in chemical enhanced oil recovery:Progress and perspective

In enhanced oil recovery, different chemical methods utilization improves hydrocarbon recovery due to their fascinating abilities to alter some critical parameters in porous media, such as mobility control, the interaction between fluid to fluid, and fluid to rock surface. For decades the use of surfactant and polymer flooding has been used as tertiary recovery methods. In the current research, the inclusion of nanomaterials in enhanced oil recovery injection fluids solely or in the presence of other chemicals has got colossal interest. The emphasis of this review is on the applicability of nanofluids in the chemical enhanced oil recovery. The responsible mechanisms are an increment in the viscosity of injection fluid, decrement in oil viscosity, reduction in interfacial and surface tension, and alteration of wettability in the rock formation. In this review, important parameters are presented,which may affect the desired behavior of nanoparticles, and the drawbacks of nanofluid and polymer flooding and the need for a combination of nanoparticles with the polymer are discussed. Due to the lack of literature in defining the mechanism of nanofluid in a reservoir, this paper covers majorly all the previous work done on the application of nanoparticles in chemical enhanced oil recovery at home conditions. Finally, the problems associated with the nano-enhanced oil recovery are outlined, and the research gap is identified, which must be addressed to implement polymeric nanofluids in chemical enhanced oil recovery.     

化学驱提高辽河油田原油采收率研究

针对辽河油田区块的油藏条件,在室内进行了无碱二元驱和弱碱三元驱提高原油采收率的研究。对3种表面活性剂SL-YD、HL-1、BH进行了筛选,优选出了对该地层原油具有最佳降低界面张力效果的表面活性剂SLYD和HL-1;然后与聚合物PAM复配,组成二元体系,最佳配方为0.16%PAM+0.20%SL-YD;最后筛选得出了弱碱三元体系0.16%PAM+0.15%SL-YD+0.30%Na2CO3。室内实验表明,无碱二元体系和弱碱三元体系可以使油水界面张力降到10-3mN/m以下,可以大幅度提高原油的采收率,增幅超过10%。     

驱油用表面活性剂AF性能评价及驱油效果研究

评价了脂肪酸烷醇酰胺表面活性剂AF的界面张力和乳化性能,利用岩心驱替实验对其提高采收率效果进行了研究。结果表明,在模拟地层水的矿化度为5 119.63 mg/L时,AF浓度为0.2%～1.2%,其界面张力均能达到超低值;NaCl浓度为0.4%～2%,AF有效浓度为0.3%～0.6%时,体系的界面张力均能达到10-3mN/m数量级。AF具有较好的乳化原油的能力,在浓度为0.5%时,形成的O/W乳状液的稳定性最强,液滴粒径最小。岩心驱替实验表明,AF表面活性剂可在水驱基础上提高原油采收率20%以上,提高采收率效果明显,具有良好的应用前景。     

Polymeric surfactants for enhanced oil recovery. IV—Thermodynamic properties of ethoxylated alkylphenol formaldehyde polymeric surfactants

The thermodynamic properties of some low molecular weight ethoxylated alkylphenol formaldehyde polymeric surfactants have been investigated. Surface tension as a function of concentration of the surfactants in aqueous solutions was measured at 28, 38, 48 and 58°C, using the spinning drop technique. From these measurements, the minimum area per molecule at the aqueous solution/air interface (A_min) was determined. The thermodynamic parameters of micellization (ΔG_mic, ΔH_mic, ΔS_mic) and of adsorption (ΔG_ad, ΔH_ad, ΔS_ad) for these polymeric nonionics were calculated. Micellization is more sensitive to ethylene oxide chain length while adsorption is more dependent on the length of the alkyl chain.     

Stable CO2/water foam stabilized by dilute surface-modified nanoparticles and cationic surfactant at high temperature and salinity

CO₂ enhanced oil recovery and storage could see widespread deployment as decarbonization efforts accelerate to meet climate goals. CO₂ is more efficiently distributed underground as a viscous foam than as pure CO₂; however, most reported CO₂ foams are unstable at harsh reservoir conditions (22 wt% brine, 2200 psi, and 80°C). We hypothesize that silica nanoparticles (NP) grafted with (3-trimethoxysilylpropyl)diethylenetriamine ligands (N3), to improve colloidal stability, and dimethoxydimethylsilane ligands (DM), to improve CO₂-phillicity, combined with the cationic surfactant N¹-alkyl-N³, N³-dimethylpropane-1,3-diamine (RCADA), will develop viscous, stable CO₂ foams at reservoir conditions. We grafted NP with N3 and DM ligands. We verified NP stability at reservoir conditions with measurements of zeta potential, amine titration curves, and NP diameter. We measured NP water contact angles (θ_w) at the water–air and water–liquid CO₂ interfaces. In a high-temperature, high-pressure flow apparatus, we calculated the viscosity of CO₂ foams across a beadpack and determined static foam stability with microscope observations. Modified NP were colloidally stable at reservoir conditions for 4 weeks, and had higher θ_w in liquid CO₂ than in air. Addition of at least 0.5 μmol/m² DM silane (0.5DM) greatly improved foam stability. RCADA-only foam coarsening rates (dD_SM³/dt) decreased 16–17× after adding 1 wt/vol% 8N3 + 1.5DM NP, and 5–10× with a 0.1–1 vol/vol% increase in RCADA concentration (with or without NP). 1 vol/vol% RCADA foam exhibited coarsening rates of 900 and 2400 μm³/min with 1 and 0.2 wt/vol% 8N3 + 1.5DM NP, respectively. These results demonstrate impressive foam stabilities at harsh reservoir conditions.     

Laboratory study of an anti‐temperature and salt‐resistance surfactant‐polymer binary combinational flooding as EOR chemical

Experimental studies were conducted to enhance the oil recovery by a surfactant‐polymer binary combinational flooding system. The surfactant‐polymer binary combinational flooding was obtained by mixing the surfactants with the poly(AM‐NVP‐AS)‐1 which was an anti‐temperature and salt‐resistance tercopolymer and successfully synthesized via free radical polymerization using acrylamide (AM), N‐vinyl pyrrolidone (NVP), allyl sulfonate (AS) as raw materials. The initiator was redox system including water‐soluble azo compound (AIBA·2HCl) and sodium bisulfite (NaHSO₃). Petroleum carboxylate dodecyl dibasic carbonylic acid sodium (C12DAS) and carboxyl betaine dodecyl dimethyl betaine (C12DB) were selected in this article. Compared with the surfactant‐HPAM, the surfactant‐poly(AM‐NVP‐AS)‐1 binary combinational system showed higher apparent viscosity and lower interfacial tension at high temperature and salinity conditions as the result of a better capacity of anti‐temperature, salt‐resistance, and swept volume. The recovery could enhance over 17% based on the core flooding test under the mineralization of 10,000 mg/L at 65°C. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39984.     

Application of microbial enhanced oil recovery technology in water‐based bitumen extraction from weathered oil sands

When using the water‐based extraction processes (WBEPs) to recover bitumen from the weathered oil sands, very low bitumen recovery arisen from the poor liberation of bitumen from sand grains is always obtained. Application of microbial enhanced oil recovery (MEOR) technology in WBEPs to solve the poor processability of the weathered ore was proposed. It was found that processability of the microbial‐treated weathered ore was greatly improved. The improved processability was attributed to the biosurfactants production in the culture solution, alteration of the solids wettability, degradation of the asphaltene component, and the decrease of the bitumen viscosity, which collectively contributed to the bitumen liberation from the surface of sand grains. Although it still has many issues to be solved for an industrial application of the MEOR technology in oil sands separation, it is believed that the findings in this work promote the solution to the poor processability of the weathered ore. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2985–2993, 2014