Complexation of Surfactant/β‐Cyclodextrin to Inhibit Surfactant Adsorption onto Sand,Kaolin, and Shale for Applications in Enhanced Oil Recovery Processes. Part II: Dynamic Adsorption Analysis

Surfactant adsorption onto solid surfaces is problematic in some industrial processes, such as in surfactant flooding for enhanced oil recovery. In this work, it was hypothesized that the use of a surfactant delivery system could prevent surfactant adsorption onto solid surfaces. Therefore, the encapsulation of sodium dodecyl sulfate (SDS) into the hydrophobic core of β‐cyclodextrin (β‐CD) to generate a surfactant delivery system (SDS/β‐CD) was evaluated in this work. This complexation was characterized using optical and scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FT‐IR). Dynamic adsorption evaluation was applied to determine the effectiveness of the complexation in inhibiting surfactant adsorption onto a variety of solid adsorbents including sand, and mixtures of sand–kaolin and sand–shale. Surfactant adsorption was also evaluated applying the quartz crystal microbalance technology (QCM‐D). The formation and morphology of the complexation was confirmed by optical microscopy, SEM, and FT‐IR. Dynamic adsorption tests demonstrated the effectiveness of the surfactant delivery approach in preventing the adsorption of surfactant (up to 74 % adsorption reduction). The QCM‐D technology confirmed these observations. Several mechanisms were proposed to explain the inhibition of surfactant adsorption including steric hindrance, self‐association of inclusion complexes, hydrophilicity increase, and disruption of hemimicelles formation.     

Complexation of Surfactant/β‐Cyclodextrin to Inhibit Surfactant Adsorption onto Sand,Kaolin, and Shale for Applications in Enhanced Oil Recovery Processes. Part I: Static Adsorption Analysis

Surfactant adsorption onto solid surfaces is a major issue during surfactant flooding in enhanced oil recovery applications; it decreases the effectiveness of the chemical injection making the process uneconomical. Therefore, it was hypothesized that the adsorption of surfactant onto solid surfaces could be inhibited using a surfactant delivery system based on the complexation between the hydrophobic tail of anionic surfactants and β‐cyclodextrin (β‐CD). Proton nuclear magnetic resonance spectroscopy was used to confirm the complexation of sodium dodecyl sulfate (SDS)/β‐CD. Surface tension analysis was used to establish the stoichiometry of the complexation and the binding constant (K_a). Static adsorption testing was applied to determine the adsorption of surfactant onto different solids (sandstone, shale, and kaolinite). The release of the surfactant from the β‐CD cavity was qualitatively evaluated through bottle testing. The formation of the inclusion complex SDS/β‐CD with a 1:1 stoichiometry was confirmed. The K_a of the complexations increases as salinity and hardness concentration increases. The encapsulation of the surfactant into the β‐CD cavity decreases the adsorption of surfactant onto solid surfaces up to 79 %. Qualitative observations indicate that in the presence of solid adsorbents partially saturated with crude oil, the β‐CD cavity releases surfactant molecules, which migrate towards the oil–water interface.     

Complexation of Surfactant/β‐Cyclodextrin to Inhibit Surfactant Adsorption onto Sand,Kaolin, and Shale for Applications in Enhanced Oil Recovery Processes. Part III: Oil Displacement Evaluation

This proof of concept research evaluates the performance of a surfactant/β‐cyclodextrin (β‐CD) inclusion complex during chemical flooding for enhanced oil recovery. It was hypothesized that the encapsulated surfactant propagates well through the porous media. Sodium dodecyl sulfate (SDS) was used to study the surfactant/β‐CD complexations. Phase behavior analysis was carried out to prepare the most favorable chemical slug formulation. A series of core flooding tests were conducted to determine the efficiency of the SDS/β‐CD inclusion complex in displacing residual oil. Surfactant flooding was conducted as tertiary oil recovery mode (after mature water flooding) by injecting 0.3 pore volume (PV) of the optimum surfactant slug that was chased by 0.3 PV of a polymer slug; followed by continuous water flooding until oil production stopped. The experimental results indicate that the encapsulated surfactant propagates well through the sandpack system and consistently produces higher incremental oil recoveries that range from 40 to 82 % over the incremental oil recovery achieved by conventional surfactant flooding.     

Adsorption of Noble Metals Using Silica Gel Modified with Surfactant Molecular Assembly Containing an Extractant

Silica gel modified with a surfactant, Triton X-100 molecular assembly containing an extractant, 1-(2-pyridylazo)-2-naphthol, was prepared as an adsorbent to adsorb palladium, platinum, and gold. In this study, methods of metal recovery and mutual separation from the metal coexisting solution were studied by using the modified silica gel (PT100S). The effects of pH, chloride-ion, and metal-ion concentrations on the metal adsorption rate were evaluated through batch experiment. Pd(II) and Au(III) were adsorbed on PT100S, while Pt(IV) was not adsorbed. Furthermore, it was found that Pd(II) reacted with an adsorption site on PT100S, and that Au(III) reacted with a different adsorption site from Pd(II). These results enabled to separate the metals using a column packed with PT100S.     

壳聚糖凝胶吸附蛋白质机理研究

以壳聚糖为原料,经固化、交联、还原的工艺路线,制备了一种层析凝胶,对该凝胶吸附机理进行了研究。动力学研究表明,在初始ρ(牛血清蛋白)=1mg/mL和pH=6 0时,凝胶对牛血清蛋白的吸附在30min内可达平衡,按Lagergren方程计算出一级速率常数为15 63h-1,吸附平衡的实验数据符合Langmuir和Freundlich关系式,红外光谱测定表明,凝胶中与蛋白质或酶离子的相互作用主要是以氢键形式存在的静电引力。     

三元复合驱油体系静态吸附规律研究

为了三元复合驱油体系静态吸附规律研究,通过物理模拟实验,分别使用单一组分的聚合物和单一组分的碱,碱和聚合物、表活剂和聚合物二元复合体系以及三元复合体系进行对比实验。研究结果表明:随着聚合物相对分子质量增大,其吸附能力增强,对表活剂的吸附影响也随之加大,表面活性剂的吸附量呈现先迅速增加,达到峰值后缓慢下降并趋于稳定的规律。碱和聚合物二元复合体系主要表现为聚合物的吸附和与大量碱发生水解反应。而在三元复合体系中,表活剂对聚合物的吸附量影响较小,聚合物与大量碱发生水解作用仍然起主导作用。     

维纶生产中凝胶粒子过滤的研究

纺丝原液中的凝胶粒子不仅影响喷丝头换头率,而且严重影响成品纤维的质量指标。而目前的熔体过滤器只是对所有的杂质进行过滤,并没有考虑针对凝胶粒子自身的特点进行过滤方法的改进与设计。通过分析凝胶粒子的性质、分类、形成机理、主要停留位置以及压差与停留时间对凝胶粒子过滤的影响,提出了凝胶粒子过滤的合理化建议。     

马尔文激光粒度仪在载体硅胶生产中的应用

概述了马尔文激光粒度仪湿法测定载体硅胶样品粒径分布的方法。对分散剂、泵速及超声波的选择条件进行了优化,并对重复性进行了测试。结果表明,在马尔文激光粒度仪湿法测定条件下,实验选择二次蒸馏水作为分散剂,2500r／min为最佳泵速,15W／cm^2的超声波强度和10s的超声波开启时间作为最佳超声波条件。该方法容易建立,精密度高,非常适合在生产过程中对载体硅胶粒径分布的测定。     

壳聚糖凝胶球的制备及对银离子的吸附

以壳聚糖(CTS)为基材、硝酸银为印迹物,提出了一种新的CTS水凝胶球的制备方法.采用Ag+吸附容量作为评价指标,对凝胶球的制备条件进行了优化,并进行了吸附试验.结果显示,当CTS用量为质量分数2.5%、交联剂用量为体积分数3.0%、凝固浴三乙醇胺的质量分数为10.0%、制备温度为25℃,热处理温度为60℃,洗脱剂硫代...     

有机膨润土/淀粉/丙烯酸复合凝胶的制备及吸附性能研究

以有机插层膨润土、淀粉和丙烯酸为原料,N,N'-亚甲基双丙烯酰胺为交联剂制备了一种新型网络凝胶吸附剂.通过红外光谱(FT-IR)、X射线衍射(XRD)和扫描电镜(SEM)对凝胶结构进行了表征.研究了吸附剂对亚甲基蓝的吸附行为,考察了pH值、吸附时间和初始浓度等因素对吸附剂吸附性能的影响,并用不同等温方程对吸附数据进行了拟合.结果表明Skip等温模型的拟合效果更好,吸附剂在26℃,pH =6时对亚甲基蓝的最大量论吸附量为341 mg/g.再生实验表明凝胶吸附剂可多次回收利用.     

碱、聚合物对表面活性剂吸附影响分析

油藏对表面活性剂的吸附作用,是砂岩表面化学物质与表面活性剂间相互作用的结果。ASP复配体系溶液中,碱对表活剂的吸附影响较大,在表活剂溶液中加入碱后,砂岩对表活剂的吸附量下降,且吸附量下降幅度与碱浓度成正比。实验结果表明,碱可以使粘土矿物对阴离子表面活性剂吸附量降低70%~80%,而油藏砂岩对表活剂吸附量可降低10%~40%。聚合物对表活剂的吸附影响较小,数值模拟结果表明吸附量降低15%~30%。这是由于聚合物在表活剂溶液中水解后,部分分子团带有负电荷,这就抑制了砂岩对表活剂的吸附作用;另外,加入聚合物后,复配体系溶液变稠,使得溶液扩散速率降低,减小波及体积,进而削弱表活剂吸附效果。     

Adsorption Behavior of Iminodiacetic Acid Type of Chelating Gel Prepared from Waste Paper

Abstract

Adsorption gel was prepared from waste recycled paper by immobilizing iminodiacetic acid (IDA) functional group by chemical modification. The gel exhibited good adsorption behavior for a number of metal ions viz. Cu(II), Pb(II), Fe(III), Ni(II), Cd(II), and Co(II) at acidic pH. The order of selectivity was found to be as follows: Cu(II)>Pb(II)>Fe(III)>Ni(II)～Cd(II)～Co(II). From the adsorption isotherms, the maximum adsorption capacity of the gel for both Cu(II) and Pb(II) was found to be 0.47 mol/kg whereas that for Cd(II) was 0.24 mol/kg. A continuous flow experiment for Cd(II) showed that the gel can be useful for pre‐concentration and complete removal of Cd(II) from aqueous solution.     

磷肥副产硅胶的粒径分析条件选择

利用激光粒度分析仪(湿法)对磷肥副产硅胶进行粒径测定研究,主要考察了几种不同类型表面活性剂及其添加量、遮光率(样品浓度)、循环速率(搅拌速率)和超声时间(分散时间)等因素的影响,采用响应曲面法,建立遮光率的回归模型,优化得到最适宜分散效果的条件。结果表明,磷肥副产硅胶粒径分析的测定条件为:分散剂为三聚磷酸钠,添加量为4滴,遮光率为30%,循环速率为1 200 r/min,超声时间为3 min。该方法简捷、快速、准确度高且重现性好。     

Solidification by Convective Drying of Particle Layer Wetted with Dilute Agar Gel

Abstract:

Solidified porous slab is formed through convective drying of glass particle layer wetted with aqueous dilute agar gel. Measured critical mean moisture content increases with increasing initial moisture or agar content. The agar gel moves in viscous flow caused by capillary pressure during drying. A new drying model based on the receding evaporation plane model is proposed. Drying period is divided into surface and internal evaporation periods. Wet slab consists of dried and wet zones during the internal evaporation period, while the wet slab consists of wet zone only during the surface evaporation period. In the new model, the evaporation rate from the wet zone in the internal drying period is estimated with the linear driving force (LDF) approximation in the field of adsorption engineering. Critical moisture content, that is, mean moisture content between the surface and internal periods, is estimated with a mass balance on the surface. Simulated results by the new drying model with reasonable fitting parameters agree very well with measured drying data.     

Solidification by Convective Drying of Particle Layer Wetted with Dilute Agar Gel

Solidified porous slab is formed through convective drying of glass particle layer wetted with aqueous dilute agar gel. Measured critical mean moisture content increases with increasing initial moisture or agar content. The agar gel moves in viscous flow caused by capillary pressure during drying. A new drying model based on the receding evaporation plane model is proposed. Drying period is divided into surface and internal evaporation periods. Wet slab consists of dried and wet zones during the internal evaporation period, while the wet slab consists of wet zone only during the surface evaporation period. In the new model, the evaporation rate from the wet zone in the internal drying period is estimated with the linear driving force (LDF) approximation in the field of adsorption engineering. Critical moisture content, that is, mean moisture content between the surface and internal periods, is estimated with a mass balance on the surface. Simulated results by the new drying model with reasonable fitting parameters agree very well with measured drying data.     

聚合物静态吸附研究

针对聚合物在流经油藏多孔介质时所发生的吸附滞留情况及其对驱油效果的影响,通过淀粉-碘化镉比色法对大庆油田杏十三区块聚合物进行静态吸附研究。根据聚合物浓度、温度、水解度以及相对分子量的变化分析对静态吸附量的影响,并得出两种不同类型吸附剂单位质量下对聚合物吸附的变化规律。研究表明,随着聚合物浓度的增加,单位质量的吸附量逐渐增大,而后趋于平缓,且与石英砂相比,聚合物在天然岩芯上的吸附量略大;通过加入氢氧化钠改变聚合物的水解度,聚合物的吸附量随水解度的增大先降低,而后略有回升,同时,随着相对分子量的增加,吸附量缓慢降低;且在一定范围内随着水浴温度的增加而逐渐下降。     

反相悬浮聚合法制备阳离子性CPDAC凝胶微球及其对水污染化合物的吸附性能

以环已烷为分散介质、Span-60为分散剂,采用反相悬浮聚合法,通过阳离子单体丙烯酰氧乙基三甲基氯化铵(DAC)的交联聚合(CP),制备了粒径200~300 mm的凝胶微球CPDAC,考察了主要条件对微球成球性能及粒径的影响,对微球进行了表征,研究了CPDAC对4种阴离子物质的吸附特性. 结果表明,制备CPDAC需严格控制成球条件. 分散相水相采用滴加方式,适宜的分散剂为Span-60,随其用量增加微球粒径变小;油水相体积比小于2:1不能成球,随体积比增大,微球粒径减小;搅拌速率小于250 r/min不能成球,微球粒径随搅拌速率加快而变小. CPDAC凭借强离子交换作用及静电相互作用对CrO42-, MoO42-和酸性染料活性艳红、活性黄4种阴离子物质都有很强的吸附作用,吸附容量分别为213, 275, 1850和1690 mg/g,吸附容量随温度升高而降低.     

竹炭粒径对竹活性炭的吸附性能与孔结构的影响

研究了竹炭粒径对KOH活化法制备的竹活性炭吸附性能和孔结构的影响。结果表明,竹炭粒径0.18~0.27 mm和0.55~0.88 mm时活化得率较高。竹活性炭碘吸附值和亚甲基蓝吸附值都随竹炭粒径的减小而先减小后增大,与活性炭的比表面积BET和总孔容积变化趋势相一致;苯酚吸附值随竹炭粒径的减小而先增大后减小。竹炭粒径对竹活性炭碘吸附值和苯酚吸附值的影响较小,0.11~0.15 mm粒径竹炭制备的活性炭的亚甲基蓝吸附值最大。0.18~0.27 mm和0.55~0.88 mm粒径竹炭制备的活性炭的平均孔径较小,说明0.18~0.88 mm粒径竹炭制备的活性炭的微孔率相对较高,有利于在低分子质量气体吸附方面的应用。因此,竹炭制备高性能活性炭的较佳粒径为0.18~0.88 mm。     

表面活性剂在石油污染治理中的应用

综述了当前表面活性剂在石油污染土壤治理中应用成果及研究现状，并讨论了今后的应用前景。     

硅酸钙粒径分析及吸附去除水中六价铬的研究

采用激光粒度分析仪对粉煤灰提取后的工业废物硅酸钙样品进行分析,结果表明硅酸钙样品的平均粒径在35.36 μm,分选性极好,样品频率曲线形态近似正态分布,峰态呈中等峰态.采用扫描电镜和X-射线能谱对硅酸钙样品表面进行分析,结果表明硅酸钙粒径大小不一、表面疏松多孔,由Ca、Si、O、C元素组成.设计正交实验研究了pH、反应温度、硅酸钙投加量以及六价铬溶液初始浓度对于反应去除率的影响,结果表明影响顺序为硅酸钙投加量＞溶液浓度＞反应温度＞ pH,反应在pH =6,反应温度30℃,硅酸钙投加量为30g/L,溶液浓度为1 mg/L的条件下取得最大去除率,六价铬去除率为16.51％.等温吸附实验结果表明Langmuir和Freundlich等温吸附模型均有较好模拟,硅酸钙对Cr6+的最大吸附容量为0.351 mg/g.