脂肪醇/烷基酚聚氧乙烯醚磺酸盐的合成工艺

实验以脂肪醇/烷基酚聚氧乙烯醚(AEO/APEO)为起始剂,经过卤代、磺化反应得到脂肪醇/烷基酚聚氧乙烯醚磺酸盐。以不同结构中心碳原子的反应规律分析确定了磺化反应为S_N2过程,以L_(27)(3~(13))正交实验得到较佳合成条件为:AEO为起始剂,磺化反应2 h,反应温度70℃,最终产物收率89.67%。界面活性测试结果表明,在单剂质量浓度0.2%,矿化度80 g/L时,Ca~(2+)/Mg~(2-)总量在0.4～1.1 g/L范围内变化,2 h油水界面张力稳定值达到10~(-3)mN/m数量级。     

脂肪醇聚氧乙烯醚磺酸盐的合成与性能评价

为开发适用于高温高盐油藏驱油剂,探讨了以脂肪醇聚氧乙烯醚硫酸钠(AES)为原料,亚硫酸钠等无机盐为磺化剂,合成脂肪醇聚氧乙烯醚磺酸盐的可行性。测试结果表明,少量添加抑制剂硫酸氢钠能抑制副反应进行,磺化剂亚硫酸钠、亚硫酸氢钠和抑制剂硫酸氢钠按质量比5∶1∶0.1比例配置,反应釜搅拌速率为600r/min,产物收率达到53.8%。反应时间4h、反应温度150℃时,混合产物具有较好的耐盐性能和协同效应,油水界面张力值可达到10~(-3) mN/m超低水平。以尕斯原油配制模拟油,脂肪醇聚氧乙烯醚磺酸盐驱油表面活性剂的驱油效率可达到11%以上,具有较好的驱油效果。     

脂肪醇聚氧乙烯醚磺酸盐合成方法的改进

以脂肪醇、环氧乙烷、氯化亚砜和亚硫酸钾等为原料,依次通过阴离子聚合、氯代、磺化等反应合成了脂肪醇聚氧乙烯醚磺酸盐(AESO)。通过IR,13 C NMR,ESI-MS等手段对产物进行了结构表征。利用单因素法对各步反应的工艺条件进行了优化。各步反应的最佳条件为:阴离子聚合反应中,采用环氧乙烷间断式进样法,n(脂肪醇)∶n(环氧乙烷)=1∶4,催化剂氢氧化钠的用量为脂肪醇质量的0.1%,反应温度为115~125℃,反应压力为0.4 MPa,收率为44.2%;氯代反应中,以吡啶为催化剂,氯化亚砜为氯代剂,n(脂肪醇聚氧乙烯醚)∶n(氯化亚砜)∶n(吡啶)=1∶1.6∶0.8,70℃反应10h,收率为92.4%;磺化反应中,以水为溶剂,正己醇为稀释剂,质量均为氯代物质量的20%,亚硫酸钾为磺化剂,n(亚硫酸钾)∶n(氯代物)=1.5∶1,反应压力为1.0 MPa,155℃反应6h,经两相滴定法测得收率为91.3%。     

系列脂肪醇聚氧乙烯醚磺酸盐的合成及其性能

以C14~18脂肪醇、环氧乙烷和丙烷磺内酯为原料合成了系列脂肪醇聚氧乙烯醚磺酸盐表面活性剂,测试了表面活性剂的溶解性及其溶液的表面性质,讨论了临盘油田地层水和CaCl2溶液对其表面性质的影响。实验结果表明,环氧乙烷数为3的脂肪醇聚氧乙烯醚(3)磺酸盐表面活性剂中的脂肪醇碳原子数越少,在盐溶液中的溶解性越好。C14脂肪醇聚氧乙烯醚(3)磺酸盐表面活性剂在蒸馏水中的临界胶束浓度(cmc)略高于其在模拟临盘油田地层水中的cmc。当疏水基链长相同时,随环氧乙烷数的增加,脂肪醇聚氧乙烯醚磺酸盐表面活性剂的cmc和其所对应的表面张力均呈增大的趋势。C16脂肪醇聚氧乙烯醚(3)磺酸盐表面活性剂在CaCl2溶液中具有良好的活性,抗盐能力较强。环氧乙烷数为6的脂肪醇聚氧乙烯醚(6)磺酸盐表面活性剂的界面活性明显低于环氧乙烷数为3的脂肪醇聚氧乙烯醚(3)磺酸盐。     

脂肪醇聚氧乙烯醚磺酸盐NNA系列高温高盐条件下界面活性研究

实验考察了作为驱油表面活性剂合成的氧乙基数n为7,8,9,12,15的十二烷醇聚氧乙烯醚磺酸盐NNA-n在高温高盐条件下的界面张力性质.实验中使用华北油田晋45断块脱水脱气原油,实验温度70℃.用含钙镁离子0.6g/L的模拟水配制的NNA溶液,随矿化度增大(20～120g/L),油水(平衡)界面张力显现低谷区,其中NNA-9和NNA-12显现较宽的超低界面张力区(10-3mN/m).当矿化度分别为60、80、100 g/L,钙镁离子浓度由0增至1.2g/L时,NNA-9和NNA-12在中间钙镁浓度区也显现界面张力低谷区;NNA-9的低谷区随矿化度加大而变深,在矿化度20g/L、钙镁浓度约为0.3～0.8g/L区间有超低值;NNA-12的界面张力则在矿化度80 g/L时最低,超低值出现在钙镁浓度0.4～0.9g/L区间.NNA-9在矿化度40 g/L模拟水中的1 g/L溶液,在110℃老化192小时后,有效物含量为42%,界面张力为8.94×10-3mN/m.     

烯烃加成法合成脂肪醇聚氧乙烯醚磺酸盐

以脂肪醇聚氧乙烯醚、氯丙烯为原料,经烯烃加成法进行烯丙基化反应及磺化反应合成脂肪醇聚氧乙烯醚磺酸盐。烯丙基化步骤中,以聚乙二醇作相转移催化剂,得到中间体烯丙基醚产率为94.4%;在磺化步骤中,以亚硫酸氢盐-亚硫酸盐作磺化剂,联合硝酸盐+产物作催化剂,得到磺酸盐产品产率为85.0%。其优化工艺为:烯丙基化步骤反应温度120℃,n(氯丙烯)∶n(聚氧乙烯醚)=2.0,反应时间6h;磺化步骤反应温度应选择在95～97℃(沸腾),n(磺化剂)∶n(烯丙基醚)=1.8,反应时间8h。     

脂肪醇醚磺酸盐在三次采油中的应用

三次采油技术主要有热驱油法,二氧化碳注入法、碱水驱油法、表面活性剂/聚合物驱油法等。本文着重介绍脂肪醇醚磺酸盐的合成方法及其在三次采油中的应用。     

脂肪醇醚磺酸盐和壬基酚醚表面活性剂的吸附性能研究

为研究驱油体系中阴离子-非离子表面活性剂在砂岩表面的吸附滞留问题,分别利用两相滴定法和硫氰酸钴盐比色法研究了非离子表面活性剂TX-10和非离子改性的阴非离子磺酸盐表面活性剂C16EOS在砂岩上的静态吸附性能,并讨论了温度、盐对吸附性能的影响。结果表明同样温度下C16EOS的吸附量高于TX-10,温度上升,吸附量下降;1% CaCl2电解质的加入,使C16EOS和TX-10的吸附量分别增加1.20mg/g和1.06mg/g;等质量浓度混合的表面活性剂体系中C16EOS和TX-10的吸附量均比单一表面活性剂低,65℃时,单一表面活性剂C16EOS和TX-10的吸附量分别为7.87mg/g和7.59mg/g,而混合体系中吸附量则为6.76mg/g和6.48mg/g,说明加入非离子表面活性剂会大幅降低醇醚磺酸盐在砂岩表面的吸附。     

磺酸盐与磺酸盐表面活性剂协同作用研究

为获得具有性能优良的表面活性剂,研究了磺酸盐与磺酸盐表面活性剂在降低油水界面张力方面的协同作用。选取了十二烷基苯磺酸钠(C12ΦS)与4-(7'-十四烷基)苯磺酸钠(7C14ΦS)、4-(8'-十八烷基)苯磺酸钠(8C18ΦS),绘制了磺酸盐及复配体系的烷烃扫描曲线,考察了表面活性剂的亲水亲油性能、复配比例对协同作用的影响及磺酸盐及复配体系降低原油界面张力的能力。证实了磺酸盐与磺酸盐复配协同作用源自亲水亲油性能的改善,亲油性磺酸盐8C18ΦS与亲水性磺酸盐C12ΦS、7C14ΦS复配,可以获得具有适中亲水亲油性能的复配体系,实现协同降低界面张力作用,通过适当的磺酸盐表面活性剂复配可使长庆油田原油与1%Na Cl水溶液的界面张力降低至超低值。     

脂肪醇聚氧乙烯醚(5)磺酸盐的合成与耐温耐盐性能

以脂肪醇聚氧乙烯醚(5)(AEO-5)为原料,先与金属钠反应生成醇钠,再与氯乙基磺酸钠反应生成脂肪醇聚氧乙烯醚(5)磺酸钠(AESO),考察了反应温度、反应时间以及氯乙基磺酸钠与醇钠摩尔比对合成AESO反应的影响,并对提纯产物进行红外光谱表征,同时考察了其表面及耐温耐盐性能。结果表明,在64℃、氯乙基磺酸钠与醇钠摩尔比为1.2的条件下反应5h,AESO收率最高;AESO的表面及耐温耐盐性能均优于醇醚硫酸盐(AES),可适用于高温高矿化度油藏的三次采油。     

磺酸盐与非离子表面活性剂协同作用的研究

为研究磺酸盐与非离子表面活性剂在降低油水界面张力方面的协同作用,选取了3种支链烷基苯磺酸盐与3种聚氧乙烯醚非离子表面活性剂,测量了表面活性剂及其复配体系与系列正构烷烃间的界面张力,考察了表面活性剂的亲水亲油性能、复配体积比及NaCl浓度对协同作用的影响。结果表明,磺酸盐与非离子表面活性剂复配体系的亲水亲油性能具有加和性,亲油性的磺酸盐8C18ΦS与亲水性的非离子表面活性剂复配可以获得亲水亲油性适中的复配体系,使界面张力降低,实现协同作用;而亲水性的磺酸盐3C10ΦS、7C14ΦS与亲水性的非离子表面活性剂的复配体系仍然是亲水性的,界面活性低。此外,复配体积比、NaCl加量也可有效影响复配体系的协同作用。其中,在复配比2∶1、NaCl加量1%时,8C18ΦS与LAP-9复配体系的界面张力最低值为4.0×10-4mN/m,而3C10ΦS、7C14ΦS与LAP-9复配体系的界面张力较高,分别位于0.4 1.0 mN/m与0.035 0.13mN/m之间。图7参16     

Synthesis and Interfacial Behavior of Decyl Methylnaphthalene Sulfonate

Abstract

High purity decyl methylnaphthalene sulfonate (DMNS) surfactant was synthesized. The purity of product was determined by HPLC, and the structure was confirmed by IR, UV, and ESI-MS. The surface and oil-water interfacial activities of DMNS surfactant were studied. The effects of concentrations of the surfactant, alkali, and inorganic salt on the dynamic interfacial behavior of crude oil/Shengli Oil Field/surfactant oil flooding systems were studied, and comparitive studies of systems with strong and buffered alkali were also carried out. Results showed that DMNS surfactant possessed great capability and efficiency for lowering solution surface tension and oil-water interfacial tension. The critical micelle concentration (cmc) was 0.02% and the surface tension at this concentration was 31.61 mN.m^?1. At proper concentrations of the surfactant, alkali, and inorganic salt, the dynamic interfacial tension between the crude oil of the Shengli Oil Field and the surfactant oil flooding system reached a minimum value of 10^?5–10^?6 mN.m^?1 in a very short time (3–20 min) and maintained an ultra-low value (< 10^?2 mN.m^?1) for a long period of time (15–87 min). The crude oil/surfactant systems presented satisfactory interfacial behavior. DMNS has great potential to be used in enhanced oil recovery (EOR) with low cost and high efficiency.     

Surfactant induced reservoir wettability alteration: Recent theoretical and experimental advances in enhanced oil recovery

Reservoir wettability plays an important role in various oil recovery processes.The origin and evolution of reservoir wettability were critically reviewed to better understand the complexity of wettability due to interactions in crude oil-brine-rock system,with introduction of different wetting states and their influence on fluid distribution in pore spaces.The effect of wettability on oil recovery of waterflooding was then summarized from past and recent research to emphasize the importance of wettability in oil displacement by brine.The mechanism of wettability alteration by different surfactants in both carbonate and sandstone reservoirs was analyzed,concerning their distinct surface chemistry,and different interaction patterns of surfactants with components on rock surface.Other concerns such as the combined effect of wettability alteration and interfacial tension (IFT) reduction on the imbibition process was also taken into account.Generally,surfactant induced wettability alteration for enhanced oil recovery is still in the stage of laboratory investigation.The successful application of this technique relies on a comprehensive survey of target reservoir conditions,and could be expected especially in low permeability fractured reservoirs and forced imbibition process.     

表面活性剂驱乳化作用对提高采收率的影响

表面活性剂驱是高温高盐油藏提高原油采收率的重要技术措施,但其乳化作用对提高采收率的影响并未受到足够重视。为了分析濮城油田高温高盐油藏表面活性剂驱乳化作用对提高采收率的影响,通过对表面活性剂降低油水界面张力的性能评价,优选出2种表面活性剂YD-G1和SHY-1,用高矿化度的濮城油田现场注入水配制质量分数为0.3%的溶液,将其放入120℃恒温箱30 d后,油水界面张力仍能达到10-3mN/m的超低数量级,表明2种表面活性剂均具有良好的耐温抗盐性能。将2种表面活性剂与濮城油田脱水脱气原油配制成乳状液,在同等质量分数下YD-G1乳状液的析水率低于SHY-1,且液滴的平均粒径也更小,表明YD-G1溶液比SHY-1溶液的乳化能力强。驱油实验结果表明,YD-G1溶液比SHY-1溶液的驱油效果更佳,表明乳化作用是提高采收率的关键因素之一。通过室内实验优化设计,确定YD-G1溶液的最佳注入量为0.5倍孔隙体积,最佳注入质量分数为0.3%。     

The Synthesis and Performance of Sodium Methyl Ester Sulfonate for Enhanced Oil Recovery

Abstract

Due to the high cost of surfactant production caused by petrochemical feedstocks, much attention has been given to nonedible vegetable oils as an alternative source of feedstock. A new nonedible oil-derived surfactant based on the Jatropha plant is synthesized. A single-step route was used for synthesizing sodium methyl ester sulfonate (SMES) for enhanced oil recovery application. The performance of the resultant surfactant was studied by measuring the interfacial tension between the surfactant solution and crude oil and its thermal stability at reservoir temperature. The SMES showed a good surface activity, reducing the interfacial tension between the surfactant solution and crude oil from 18.4 to 3.92 mN/m. The thermal analysis of SMES indicates that 26.1% weight loss was observed from 70°C to 500°C. The advantage of the new SMES is the low cost of production, which makes it a promising surfactant for enhanced oil recovery application and other uses.     

塔中402CIII高温高盐油藏表面活性剂

针对塔中402CIII均质段油藏高温高盐高硬度的特点,优选出驱油用表面活性剂BS-12（甜菜碱）,优化了使用浓度,考察了乳化、吸附及驱油性能。实验结果表明,在油藏条件下（温度110℃、矿化度11.52×10⁴ mg/L、钙镁离子浓度7654 mg/L）,BS-12溶液与地层水有良好的配伍性,质量分数0.03%~0.05%的BS-12溶液与塔中原油间的界面张力为1.5×10^-2~5.2×10^-2 mN/m。110℃老化30 d后的界面张力仍保持在10^-2 mN/m数量级,热稳定性好。0.03%、0.05% BS-12溶液与原油形成的乳状液在放置12 h后趋于稳定,析水率分别为69%和50%,乳状液液滴分布稀疏,直径为0.3~1.0 μm。在水砂比为20:1时,0.05% BS-12在油砂表面的静态吸附量为6.592 mg/g。动态吸附量为4.938 mg/g,动态吸附滞留量为1.411 mg/g。岩心驱替实验表明,注入0.2%、0.3 PV表面活性剂后,采收率增幅可达4.14%。     

S7断块驱油用阴/非离子表面活性剂性能评价

针对S7断块低渗透油藏特征,开发出驱油用阴/非离子表面活性剂SHSA-JS,并对其进行性能研究。结果表明,在温度为83℃,SHSA-JS溶液浓度窗口为0.05%~0.6%,注入水矿化度为1 000~25 000 mg/L、二价离子(Ca2+,Mg2+)含量为2 410 mg/L的条件下,SHSA-JS可使油水界面张力达到10-2mN/m数量级;储层净砂和石英砂对0.3%SHSA-JS溶液的静态吸附量分别为4.50 mg/g和0.32 mg/g;静态洗油效率在41.8%以上,0.3%SHSA-JS溶液注0.4 PV孔隙体积后可在水驱基础上平均提高采收率7.71%。该表面活性剂可满足S7断块低渗透油藏对驱油用表面活性剂的要求。