微生物采油技术及其应用

介绍了微生物采油技术方法、菌种和营养液选择、油藏筛选标准、作用机理及矿场应用。     

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     

Surfactin生物表面活性剂及其驱油研究进展

表面活性素（surfactin）是一类由革兰氏阳性的枯草芽孢杆菌产生的脂肽（lipopeptide）型生物表面活性剂,因其具有优于化学合成表面活性剂的若干优点,如低毒性、高生物降解性、更好的环境相容性,且在极端环境下稳定性好,在提高石油采收率方面有较好的应用潜力,但是目前只有少数的生物表面活性剂可以大规模生产实现工业化应用。本文介绍了surfactin生物表面活性剂的化学结构和生物合成机制,并对其发酵生产过程的影响因素进行分析,为提高其生产经济性探索不同的策略,例如使用更便宜的原材料、优化培养基组分、优化反应器等,系统论述了surfactin生物表面活性剂的驱油机理和其与化学合成表面活性剂的复配研究,同时针对其应用时的不足之处提出研究新思路。     

Purification and characterization of a cold-active protease from psychrotrophic Serratia marcescens AP3801

Protease activity was detected in the culture medium of Serratia marcescens AP3801 grown at 10°C, which was isolated from soil collected from the top of a mountain. The enzyme, designated as CP-58 protease, was purified to homogeneity from the culture broth by ion exchange and gel filtration chromatographies. The molecular mass of the protease was 58 kDa, and its isoelectric point was close to 6.0. Maximal activity toward azocasein was observed at 40°C and from pH 6.5 to 8.0. The activity was strongly inhibited by 1,10-phenanthroline, suggesting that the enzyme is a metalloprotease. The N-terminal amino acid sequence was Ser-Leu-Asn-Gly-Lys-Thr-Asn-Gly-Trp-Asp-Ser-Val-Asn-Asp-Leu-Leu-Asn-Tyr-His-Asn-Arg-Gly-Asn (or Asp)-Gly-Thr-Ile-Asn-Asn-Lys-Pro-Ser-Phe-Asp-Ile-Ala. A search through databases for sequence homology aligned CP-58 protease with metalloprotease. The result of the cleavage pattern of oxidized insulin B-chain suggests that CP-58 protease has a broader specificity than other proteases against the peptide substrate.     

Production of sophorose lipids byTorulopsis bombicola from safflower oil and glucose

The production of sophorose lipids increased with increasing concentrations of both safflower oil and glucose, and was profoundly influenced by the concentration of yeast extract. A high concentration of sophorose lipids (about 135 g/L) was obtained (in a 1-L Bellco stirred reactor) when the medium consisted of 10% glucose, 10.5% safflower oil, 0.1% urea, and 0.25–0.3% yeast extract. A similar yield of sophorose lipids also was obtained in a 20-L bioreactor. About 50% of the apolar sophorose lipid 1′,4″-lactone 6′,6″-diacetate (SL-1) was found in the mixture of sophorose lipids produced under these conditions.     

Novel fluorinated surfactants for enhanced oil recovery in carbonate reservoirs

Novel surfactant‐polymer (SP) formulations containing fluorinated amphoteric surfactant (surfactant‐A) and fluorinated anionic surfactant (surfactant‐B) with partially hydrolyzed polyacrylamide (HPAM) were evaluated for enhanced oil recovery applications in carbonate reservoirs. Thermal stability, rheological properties, interfacial tension, and adsorption on the mineral surface were measured. The effects of the surfactant type, surfactant concentration, temperature, and salinity on the rheological properties of the SP systems were examined. Both surfactants were found to be thermally stable at a high temperature (90 °C). Surfactant‐B decreased the viscosity and the storage modulus of the HPAM. Surfactant‐A had no influence on the rheological properties of the HPAM. Surfactant‐A showed complete solubility and thermal stability in seawater at 90 °C. Only surfactant‐A was used in adsorption, interfacial tension, and core flooding experiments, since surfactant‐B was not completely soluble in seawater and therefore was limited to deionized water. A decrease in oil/water interfacial tension (IFT) of almost one order of magnitude was observed when adding surfactant‐A. However, betaine‐based co‐surfactant reduced the IFT to 10^?3 mN/m. An adsorption isotherm showed that the maximum adsorption of surfactant‐A was 1 mg per g of rock. Core flooding experiments showed 42 % additional oil recovery using 2.5 g/L (2500 ppm) HPAM and 0.001 g/g (0.1 mass%) amphoteric surfactant at 90 °C.     

Polyacrylamide obtained by plasma-induced polymerization for a possible application in enhanced oil recovery

Summary Ultrahigh molecular weight polyacrylamides (PAAM) were obtained by plasma-induced polymerization in water solutions. The influenceof monomer concentration, sealing pressure, initiation time and post polymerization period on polymer yield and molecular weight were investigated. The viscosity and “screen factor” measurements, as well as the thermally stimulated depolarization currents spectroscopic data of the synthesized polymers, indicate good properties as efficient viscosity modifiers in displacement of fluids for enhance oil recovery (EOR). Received: 18 March 1998/Revised version: 21 April 1998/Accepted: 24 April 1998     

Physical and chemical properties of trans-free fats produced by chemical interesterification of vegetable oil blends

Fat blends, formulated by mixing a highly saturated fat (palm stearin or fully hydrogenated soybean oil) with a native vegetable oil (soybean oil) in different ratios from 10:90 to 75:25 (wt%), were subjected to chemical interesterification reactions on laboratory scale (0.2% sodium methoxide catalyst, time=90 min, temperature=90°C). Starting and interesterified blends were investigated for triglyceride composition, solid fat content, free fatty acid content, and trans fatty acid (TFA) levels. Obtained values were compared to those of low- and high-trans commercial food fats. The interesterified blends with 30–50% of hard stock had plasticity curves in the range of commercial shortenings and stick-type margarines, while interesterified blends with 20% hard stock were suitable for use in soft tubtype margarines. Confectionery fat basestocks could be prepared from interesterified fat blends with 40% palm stearin or 25% fully hydrogenated soybean oil. TFA levels of interesterified blends were low (0.1%) compared to 1.3–12.1% in commercial food fats. Presented at the 88th AOCS Annual Meeting and Expo, May 11–14, 1997, Seattle, Washington.     

A review on the application of nanofluids in enhanced oil recovery

Enhanced oil recovery (EOR) has been widely used to recover residual oil after the primary or secondary oil recovery processes. Compared to conventional methods, chemical EOR has demonstrated high oil recovery and low operational costs. Nanofluids have received extensive attention owing to their advantages of low cost, high oil recovery, and wide applicability. In recent years, nanofluids have been widely used in EOR processes. Moreover, several studies have focused on the role of nanofluids in the nanofluid EOR (N-EOR) process. However, the mechanisms related to N-EOR are unclear, and several of the mechanisms established are chaotic and contradictory. This review was conducted by considering heavy oil molecules/particle/surface micromechanics; nanofluid-assisted EOR methods; multiscale, multiphase pore/core displacement experiments; and multiphase flow fluid-solid coupling simulations. Nanofluids can alter the wettability of minerals (particle/surface micromechanics), oil/water interfacial tension (heavy oil molecules/water micromechanics), and structural disjoining pressure (heavy oil molecules/particle/surface micromechanics). They can also cause viscosity reduction (micromechanics of heavy oil molecules). Nanofoam technology, nanoemulsion technology, and injected fluids were used during the EOR process. The mechanism of N-EOR is based on the nanoparticle adsorption effect. Nanoparticles can be adsorbed on mineral surfaces and alter the wettability of minerals from oil-wet to water-wet conditions. Nanoparticles can also be adsorbed on the oil/water surface, which alters the oil/water interfacial tension, resulting in the formation of emulsions. Asphaltenes are also adsorbed on the surface of nanoparticles, which reduces the asphaltene content in heavy oil, resulting in a decrease in the viscosity of oil, which helps in oil recovery. In previous studies, most researchers only focused on the results, and the nanoparticle adsorption properties have been ignored. This review presents the relationship between the adsorption properties of nanoparticles and the N-EOR mechanisms. The nanofluid behaviour during a multiphase core displacement process is also discussed, and the corresponding simulation is analysed. Finally, potential mechanisms and future directions of N-EOR are proposed. The findings of this study can further the understanding of N-EOR mechanisms from the perspective of heavy oil molecules/particle/surface micromechanics, as well as clarify the role of nanofluids in multiphase core displacement experiments and simulations. This review also presents limitations and bottlenecks, guiding researchers to develop methods to synthesise novel nanoparticles and conduct further research.     

Allelochemics produced by the hydrophyteMyriophyllum spicatum affecting mosquitoes and midges

An extract of the hydrophyteMyriophyllum spicatum L. was found to be toxic to first- and fourth-instar larvae of the mosquitoes,Culex quinquefasciatus Say,Culex tarsalis Coquillett,Culiseta incidens (Thomson),Aedes aegypti L., and chironomid midges in the laboratory. When first-stage larvae were exposed to the extract, the lowest concentration (6.4 mg extract/100 ml H₂O) produced 86,60, and 48% mortality inC. incidens, C. quinquefasciatus, andA. aegypti, respectively. Higher concentrations caused 100% mortality in both first and fourth instars (63.75 mg/100 ml H₂O or more). In general, the biocidal activity of the extract was found to be similar when first- and fourth-stage larvae were exposed. Some mortality in the successive pupal and adult stages was observed when fourth-stage larvae were exposed to the extract, but mortality occurred only in the various larval instars when first instars were exposed. Among the chironomids,Tanytarsus spp. was more tolerant to the extract thanChironomus spp. In addition to the biocidal activity against immature mosquitoes, the extract was found to show a unique activity acting as an attractant to both sexes of adultC. quinquefasciatus andA. aegypti. The response elicited inA. aegypti appeared to be somewhat higher than that inC. quinquefasciatus. In general, the percentage of males responding to water treated with the extract was higher than that of the females. The extract at higher concentrations seemed to show some repellency at the outset to both species, but induced positive responses later on.     

Wettability alteration of oil-wet carbonate rocks by chitosan derivatives for application in enhanced oil recovery

The increasing demand for oil and the fast decline of crude oil production from mature fields encourages the development of new enhanced oil recovery (EOR) technologies. In this work, trimethyl chitosan (TMC) and trimethyl chitosan hydrophobized with myristoyl chloride (TMC-C14) are synthesized, and their wettability modification capacity of oil-wet carbonate rocks is evaluated through contact angle measurements, atomic force microscopy, and Raman spectroscopy. Their interaction with asphaltene molecules was evaluated through UV–Vis spectroscopy. Transport behavior and oil displacement capacity were investigated in an unconsolidated porous medium. Results show that they can modify the wettability of oil-wet carbonate rocks, turning them water-wet, promoting oil displacement increases by 25% for TMC, and 16% for TMC-C14.TMC shows a better performance for wettability alteration than TMC-C14, confirming the hypothesis that the higher the positive charge density on the polymeric surfactant structure, the more efficient will be the system as a wettability modifier and as an EOR agent.     

Utilization of molasses for biosurfactant production by two Bacillus strains at thermophilic conditions

Traditionally, biosurfactants have been produced from hydrocarbons. Some possible substitutes for microbial growth and biosurfactant production include urban wastes, peat hydrolysate, and agro-industrial by-products. Molasses, a nonconventional substrate (agro-industrial by-product) can also be used for biosurfactant production. It has been utilized by two strains of Bacillus subtilis (MTCC 2423 and MTCC1427) for biosurfactant production and growth at 45°C. As a result of biosurfactant accumulation, the surface tension of the medium was lowered to 29 and 31 dynes/cm by the two strains, respectively. This is the first report of biosurfactant production by strains of B. subtilis at 45°C. Potential application of the biosurfactant in microbial enhanced oil recovery is also presented.     

Isolation,characterization, and antifungal application of a biosurfactant produced by Enterobacter sp. MS16

Isolate MS16 obtained from diesel contaminated soil, identified as Enterobacter sp. using 16S rRNA gene analysis produced biosurfactant when grown on unconventional substrates like groundnut oil cake, sunflower oil, and molasses. Of these carbon substrates used, sunflower oil cake showed highest biosurfactant production (1.5 g/L) and reduction in surface tension (68%). The biosurfactant produced by MS16 efficiently emulsified various hydrocarbons. The carbohydrates and fatty acids of the biosurfactants were studied using TLC, FTIR, NMR, and GC‐MS. The carbohydrate composition as determined by GC‐MS of their alditol acetate derivatives showed the predominance of glucose, galactose and arabinose, and hydroxyl fatty acids of chain length of C₁₆ and C₁₈ on the basis of FAMEs analysis. Biosurfactant showed antifungal activity and inhibited the fungal spore germination. Practical applications : Enterobacter sp., MS16 produces a biosurfactant composed of carbohydrates and fatty acids which exhibits excellent surface active properties. Use of industrial wastes for biosurfactant production is economical and facilitates the industrial production of this biosurfactant which has potential antifungal activity.     

Ultra-rapid synthesis of syngas by the catalytic reforming of methane enhanced byin-situ heat supply through combustion

Development in highly active catalysts for the reforming of methane with CO₂ and partial oxidation of methane was conducted to produce hydrogen and carbon monoxide with high reaction rates. An Ni-based four-components catalyst, Ni-Ce₂O₃-Pt-Rh, supported on an alumina wash-coated ceramic fiber in a plate shape was suitable for the objective reaction. By combining the catalytic combustion of ethane or propane, methane conversion was markedly enhanced, and a high space-time yield of syngas, 25,000 mol/l·h was obtained at a catalyst temperature of 700 ‡C or furnace temperature of 500 ‡C. The extraordinary high space-time yield of syngas was also confirmed even under the very rapid flow rate conditions as a contact time of 3 m-sec by using a monolithic shape of catalyst bed without back pressure.     

Selective ion-exchange in MAPO-36 and its application in toluene disproportionation

MAPO-36 was synthesized hydrothermally by isomorphic substitution of Mg²⁺ in the framework of AlPO-36 and ion-exchanged with Fe³⁺, Zn²⁺, La³⁺ and Ce³⁺ by wet method. The materials were characterized by XRD, TGA, TPD (ammonia) and SEM-EDX. XRD revealed absence of structural degradation after ion-exchange. TPD (ammonia) showed selective ion-exchange of strong acid sites in ion-exchanged MAPO-36. The weight loss around 550 °C in TGA for Fe, La and CeMAPO-36 suggested conversion of M(OH)₂⁺ to MO⁺. Toluene disproportionation was carried over all catalysts in which diphenyl methane derivative was suggested to be the principle intermediate in the formation of p-xylene and other products. The time on stream study showed exclusive formation of p-xylene after 6 h.     

Corrosion behaviour of AISI 304 stainless steel in presence of a biosurfactant produced by Pseudomonas fluorescens

Under certain conditions, some microorganisms are able to synthesize surface active compounds called biosurfactants (BS), which reduce the surface tension of water. BS characteristics depend on which microorganism produce them and therefore, on the microorganism culture conditions (temperature, pH, C, N-source,…). Numerous applications are known for these biomolecules, such as cleaning, bioremediation, and their use as a detergent, or in cosmetic formulations.Recently, a large amount of literature has been edited on the influence of BS on the interactions between pathogenic bacteria and inert surfaces. It has been shown that the modifications of surface properties by the adsorption of BS can reduce microbial adhesion.Some other studies on chemical surfactants have shown that the adsorption of surface-active compounds plays a major role in corrosion; they are indeed used as an interesting corrosion inhibition tool. Therefore, it seems very interesting to study the impact of BS as environment-friendly (since biological and biodegradable) corrosion inhibitors.In the present work, an attempt was made to study the corrosion behaviour of AISI 304 stainless steel in presence of BS produced by a Gram-negative bacteria, Pseudomonas fluorescens (Pf495). Corrosion tests were achieved on several surface oxidation states. The surface morphology of the corroded specimens was investigated using SEM.     

Application of a novel cationic starch in enhanced oil recovery and its adsorption properties

We report a preparation of water-soluble cationic starch and its application as an oil-displacing agent in chemical enhanced oil recovery. The singular sand-pack core-flood tests provide experimental evidence that the injection of the modified starch after the conventional water flooding can significantly enhance oil recovery and effectively reduce water-cut. To discuss the proposed oil-displacement mechanism of this cationic starch solution, its static and dynamic adsorption properties were also presented in this paper.     

Liquid-phase p-t-butyltoluene autoxidation enhanced by electrochemistry: Activation of the catalytic effect of cobalt acetate

The autoxidation of p-t-butyltoluene (TBT) at 80 °C in the liquid phase is carried out with an initial mixture of cobalt(III) and cobalt(II) acetate in an acetic acid solution. The autoxidation kinetics of TBT is appreciably accelerated by electrolysis with a anodic current density of 62.5 A m^–2. The electrolysis increases the concentration of cobalt(III) acetate, the actual catalyst of the autoxidation reaction. The end product of oxidation is p-t-butylbenzoic acid (TBBA). p-t-Butylbenzaldehyde (TBBZ) is an intermediary whose concentration passes through a maximum. The oxidation experiments with TBT were performed with total cobalt acetate concentrations ranging from 0.0188 to 0.169 mol dm^–3. An increase in total cobalt acetate concentration favours the electrochemical regeneration of Co^III and slightly improves the TBBZ selectivity. The duration of TBT oxidation into TBBA is reduced by a factor of 5 compared with a reaction without electrolysis.