Recent advances in flat sheet mixed matrix membrane modified by Mg-based layered double hydroxides(LDHs)for salt and organic compound separations

Magnesium(Mg)is a widely used and attractive metal,known for its unique physical and chemical properties,and it has been employed in the manufacture of many practical materials.Layered Double Hydroxides(LDHs),particularly Mg-based LDHs,rank among the most prevalent two-dimensional materials utilized in separation processes,which include adsorption,extraction,and membrane technology.The high popularity of Mg-based LDHs in separation applications can be attributed to their properties,such as excellent hydrophilicity,high surface area,ion exchangeability,and adjustable interlayer space.Currently,polymer membranes play a pivotal role in semi-industrial and industrial separation processes.Consequently,the development of polymer membranes and the mitigation of their limitations have emerged as compelling topics for researchers.Several methods exist to enhance the separation performance and anti-fouling properties of polymer membranes.Among these,incorporating additives into the membrane polymer matrix stands out as a cost-effective,straightforward,readily available,and efficient approach.The use of Mg-based LDHs,either in combination with other materials or as a standalone additive in the polymer membrane matrix,represents a promising strategy to bolster the separation and anti-fouling efficacy of flat sheet mixed matrix polymer membranes.This review highlights Mg-based LDHs as high-potential additives designed to refine flat sheet mixed matrix polymer membranes for applications in wastewater treatment and brackish water desalination.

The superhydrophobic sponge decorated with Ni-Co double layered oxides with thiol modification for continuous oil/water separation

In this paper, the superhydrophobic polyurethane sponge(SS-PU) was facilely fabricated by etching with Jones reagent to bind the nanoparticles of Ni-Co double layered oxides(LDOs) on the surface, and following modification with n-dodecyl mercaptan(DDT). This method provides a new strategy to fabricate superhydrophobic PU sponge with a water contact angle of 157° for absorbing oil with low cost and in large scale. It exhibits the strong absorption capacity and highly selective characteristic for various kinds of oils which can be recycled by simple squeezing. Besides, the as-prepared sponge can deal with the floating and underwater oils, indicating its application value in handling oil spills and domestic oily wastewater. The good self-cleaning ability shows the potential to clear the pollutants due to the ultralow adhesion to water. Especially, the most important point is that the superhydrophobic sponge can continuously and effectively separate the oil/water mixture against the condition of turbulent disturbance by using our designed device system, which exhibit its good superhydrophobicity, strong stability.Furthermore, the SS-PU still maintained stable absorption performance after 150 cycle tests without losing capacity obviously, showing excellent durability in long-term operation and significant potential as an efficient absorbent in large-scale dispose of oily water.

Recent advance on VOCs oxidation over layered double hydroxides derived mixed metal oxides

Catalytic oxidation is regarded as one of the most promising strategies for volatile organic compounds(VOCs)purification.Mixed metal oxides(MMOs),after topological transformation using layered double hydroxides(LDHs)as precursors,are extensively used as catalysts for VOCs oxidation due to their uniformity advantage.This review summarizes the developments in the LDH-derived VOCs heterogeneous catalytic oxidation over the last 10 years.Particularly,it addresses the VOCs abatement performance over MMO,noble metal/MMO,core-shell structured MMO,and integral MMO film catalysts originating from LDHs.Moreover,it highlights the water vapor effect and oxidation mechanism.This review indicates that LDH-based catalysts are a category of important VOCs oxidation materials.

Zwitterionic monolayer grafted ceramic membrane with an antifouling performance for the efficient oil-water separation

Enormous demands on the separation of oil/water(O/W)emulsions in various industries,such as petrochemical,food and pharmaceutical industries,are looking for high performance and energy-efficient separation methods.Ceramic membranes have been used to deal with O/W emulsions,for its outstanding characteristics of easy-operation,high-flux,and long-term stability.However,membrane fouling is still a challenge in the industrial application of ceramic membranes.Herein,antifouling ceramic membranes were fabricated by grafting zwitterions on the membrane surface via an environment-friendly two-step grafting method,which improves the antifouling property and permeability.Successful grafting of such zwitterion on the ceramic surface was assessed by the combination of FTIR and XPS characterization.More importantly,the hydration can be formed by electrostatic interactions layer on the modified membrane,which was confirmed by TGA characterization.The antifouling performance of prepared zwitterionic ceramic membranes in the separation of O/W emulsions was systematically tested.The results suggested that zwitterion can significantly improve the flux of ceramic ultrafiltration membrane,and can also improve antifouling property dramatically by reducing the irreversible fouling in the separation of O/W emulsions.Therefore,zwitterionic ceramic membranes hold promising potentials as an antifouling,highly efficient and green method in the practical purification of the O/W emulsions.

Groundwater monitoring of an open-pit limestone quarry:Water-rock interaction and mixing estimation within the rock layers by geochemical and statistical analyses

Water-rock interaction and groundwater mixing are important phenomena in understanding hydrogeological systems and the stability of rock slopes especially those consisting largely of moderately watersoluble minerals like calcite. In this study, the hydrogeological and geochemical evolutions of groundwater in a limestone quarry composed of three strata: limestone layer(covering), interbedded layer under the covering layer, and slaty greenstone layer(basement) were investigated. Water-rock interaction in the open-pit limestone quarry was evaluated using PHREEQC, while hierarchical cluster analysis(HCA)and principal component analysis(PCA) were used to classify and identify water sources responsible for possible groundwater mixing within rock layers. In addition, Geochemist's Workbench was applied to estimate the mixing fractions to clarify sensitive zones that may affect rock slope stability. The results showed that the changes in Ca2+and HCO3àconcentrations of several groundwater samples along the interbedded layer could be attributed to mixing groundwater from the limestone layer and that from slaty greenstone layer. Based on the HCA and PCA results, groundwaters were classified into several types depending on their origin:(1) groundwater from the limestone layer(LO),(2) mixed groundwater flowing along the interbedded layer(e.g., groundwater samples L-7, L-11, S-3 and S-4), and(3) groundwater originating from the slaty greenstone layer(SO). The mixing fractions of 41% LO: 59% SO, 64% LO: 36% SO, 43%LO: 57% SOand 25% LO: 75% SOon the normal days corresponded to groundwaters L-7, L-11, S-3 and S-4,respectively, while the mixing fractions of groundwaters L-7 and L-11(61% LO: 39% SOand 93% LO: 7% SO,respectively) on rainy days became the majority of groundwater originating from the limestone layer.These indicate that groundwater along the interbedded layer significantly affected the stability of rock slopes by enlarging multi-breaking zones in the layer through calcite dissolution and inducing high water pressure, tension cracks and potential sliding plane along this layer particularly during intense rainfall episodes.

Dominance-caused differences in transpiration of trees in a Karst broadleaved mixed forest

Estimating stand transpiration of natural forests using traditional methods through up-scaling of sap fl ux density from sample trees based on stand sapwood area only is diffi cult because of the complexity of species,ages,and hierarchical structure of natural forests.To improve stand transpiration estimation,we developed an up-scaling method by considering the tree dominance eff ect based on the assumption that individual tree transpiration is aff ected by crown dominance and species,in addition to factors previously considered such as meteorological conditions,sapwood area,and soil moisture.In this study,the meteorological factors,soil moisture,and sap fl ux density of 15 sample trees of diff erent species and dominance in a natural evergreen and deciduous broadleaved mixed forest were simultaneously monitored from March 2012 to February 2014 in the Karst mountain region in southwestern China.After establishing a single tree transpiration model which considers the eff ects of dominance and species,an up-scaling method was explored to estimate stand transpiration.The results show that the transpiration intensity increased exponentially with increasing tree dominance.The contribution to annual stand transpiration from a few dominant trees(5.4%of trees, 28.2% of basal area) was up to 65.0%. The correspondingcontribution was 16.2% from sub-dominant trees(7.6% of trees, 16.2% of basal area) and 22.8% from middleandlower-layer trees (87.0% of trees, 55.6% of basal area).The variation of individual tree transpiration was mainly(97.9%) explained by tree dominance, but very weakly bytree species. The estimated annual stand transpiration was300.2 mm when using the newly developed method whichconsiders tree dominance, 52.5 mm (14.9%) lower than theestimation (352.7 mm) of traditional method which considersonly the sapwood area eff ect, and 8.5 mm (2.7%) lowerthan the estimation (308.6 mm) which considers the eff ectsof both species composition and sapwood area. The maintree characteristics aff ecting stand transpiration are tree size(sapwood area) and dominance. Consideration of tree dominancewill signifi cantly improve stand transpiration estimationand provide a more solid basis for guiding integratedforest-water management at stand scale.

Study on Flow Unit of Heavy Oil Bottom Water Reservoir with Over-Limited Thickness in Offshore Oilfield

The upper Ming section of L oilfield is a typical offshore heavy oil bottom-water reservoir with thick fluvial layers. All horizontal wells are developed by natural energy. Due to the few drilling holes and influence by the resolution of seismic data, it is difficult to describe reservoirs with thickness over 20 meters. In this paper, seismic resonance amplitude inversion technology is introduced to restore the real response of thick reservoirs and interbeds by drilling and drilling verification, and the geological bodies with different thickness are displayed by frequency division RGB three primary colors. Flow units of heavy oil reservoirs with bottom water are divided according to the three major factors of interlayer, lithologic internal boundary and water-oil thickness ratio which have the greatest influence on horizontal well development, thick sand bodies are divided into 10 different flow units in three levels, each unit is separated from each other, and the reservoir structure, water-cut characteristics and water-flooding characteristics are different. The reliability of the research is improved by using the dynamic data of horizontal wells and newly drilled passing wells, which provides a basis for tapping the potential of heavy oil reservoirs with bottom water.

大庆油田裸眼井测井技术进展与展望

为了提高大庆油田裸眼井测井技术支撑能力和研究成果领先水平,全面回顾了大庆油田测井采集系列及解释技术的创新发展历程,系统总结了特高含水期剩余油解释、火山岩等复杂岩性测井评价、碎屑岩储量参数解释、非常规油气“甜点”分类、缝洞型碳酸盐岩储层测井评价等油田勘探开发测井评价技术。在客观分析大庆油田勘探开发测井解释评价需求和面临瓶颈问题的基础上,结合当前油田测井评价对象规模小、物性差、埋藏深、地层结构复杂、非均质性强的特点。指明了测井解释评价核心技术主攻方向。围绕新阶段测井采集及解释评价技术体系完善与建立,对高分辨率和成像测井采集、后油藏时期和非常规测井解释评价、新一代智能解释技术体系等未来发展进行了展望。

气水两相下降流中泡状流与段塞流转换边界研究

针对塔河油田气水混注驱替“阁楼油”过程中泡状流与段塞流转换边界不清的问题,利用数值模拟方法对气水两相下降流中泡状流与段塞流进行了模拟分析。结果表明:在气相表观流速为0.01~1.00 m/s、液相表观流速为0.03~2.00 m/s、管径为76 mm的模拟条件下,管道中主要为泡状流和段塞流;与模拟结果相比,Barnea、Kokal、薛玉卿模型预测的转换边界偏小,Bhagwat和Yijun模型预测的转换边界偏大;随着气相表观流速增加,泡状流向段塞流转换时所需液量逐渐增大;在低液量条件下,越靠近管道中心,气泡数量越多,空隙率越大;随液量增加,单个小气泡体积减小,气泡在整个管道横截面上分布越均匀。基于漂移模型,考虑气泡群滑脱速度,建立了新的泡状流与段塞流转换边界模型,216组文献数据验证结果显示,新模型准确率为95.37%,准确度较高。建立的泡状流—段塞流转换边界模型,不仅可提高井筒压力、温度模型的计算精度,同时对塔河油田现场注入井井口参数优化、注入设备优选和提高“阁楼油”驱替效率有很好的理论指导意义。

油水气混合的数字化微量润滑装置

微量润滑装置对油水气量的准确控制及其雾化效果,将直接影响切削冷却效果,进而影响零件加工质量。为改善微量润滑装置的辅助切削效果,研制了一种具有油水气混合的数字化微量润滑装置,有效改善了润滑油雾喷射的连续性和均匀性。基于微量润滑雾化技术,设计开发了数字化微量润滑装置,搭建铣削工艺实验平台,测试新型微量润滑装置的辅助切削效果。结果表明,所研制的油水气混合的数字化微量润滑装置能够明显提高油雾质量和辅助切削效果。

风化店地区低阻油层成因分析及识别

针对风化店地区孔店组低阻油层识别困难、测井解释难度大的特点,充分利用测井、录井等资料研究分析低阻油层形成原因。研究认为该区低阻油层受黏土矿物含量、地层水矿化度、薄互层三个方面影响。在系统分析储层四性关系的基础上,分区块、分层位建立了储层参数模型和高精度、适用性强的油、水解释图版标准,准确识别低阻油层,及时应用于现场生产中,取得了明显的效果,为进一步开展老油田低阻油层识别、挖潜上产提供了借鉴和技术保障。

CO_(2)快速吞吐提高页岩油采收率现场试验

页岩油注CO_(2)吞吐提高采收率技术处于探索阶段,目前面临着CO_(2)与页岩储层及流体相互作用机制不明确、数值模拟技术不成熟、缺乏规模注采及低成本回收工艺等技术难题。为探索页岩油注CO_(2)提高采收率主控机理,以苏北盆地溱潼凹陷古近系阜宁组二段页岩油为对象开展了超临界CO_(2)水岩反应实验,分析了高温高压条件下页岩矿物溶蚀作用及其对孔隙度和渗透率的影响,并通过注CO_(2)恒质膨胀实验、最小混相压力测试评价了地层超压条件下注CO_(2)后原油高压物性变化特征,并在此基础上开展考虑多因素数值模拟研究优化了设计注入参数,最终通过矿场试验验证了技术可行性。研究结果表明:(1) CO_(2)水岩反应以碳酸质矿物溶蚀占主导,长英质矿物部分溶解,生成中大孔隙;(2)在地层原油中注入适量的CO_(2),显著萃取了原油中间烃组分,原油黏度从5.151 mPa·s下降到1.250 mPa·s,且CO_(2)首先萃取轻烃组分,随生产时间增加萃取组分逐渐变为重烃;(3)基于人工压裂与天然缝网混合介质组分数模模型,优化设计单井吞吐注气量1.7×10~4 t,注气速度500~600 t/d,焖井时间50 d;(4)低压侧加热的页岩油CO_(2)吞吐地面工艺,可依据CO_(2)注入地面工艺多参数数据模型,实现精准控温,避免注入管线冻堵及井下油管和套管材料低温脆断问题;(5)产出气CO_(2)浓度高于80%时,采用气相回收直注工艺,实现产出气回收成本降至104元/t。结论认为,CO_(2)快速吞吐有效提高了页岩油采收率,形成的机理认识和技术系列可为页岩油注CO_(2)吞吐开发提供参考和借鉴。

基于分子动力学仿真的混合油中水分子扩散行为及其介电常数研究

绝缘油是油浸式变压器内绝缘的重要组成部分,其绝缘性能对电力系统的稳定运行至关重要。实验研究表明植物油与矿物油共混可有效提升其绝缘性能,但改性机理尚不明确。该文利用分子动力学研究了植物油、矿物油不同共混比例下油中水分子的扩散行为及其介电常数。结果表明:随着植物油占比增加,水分子的扩散系数逐渐降低,抑制了油中“水桥”的形成,提升了混合油的绝缘性能。水分子与混合油组分分子之间相互作用能与氢键计算结果表明,植物油中强极性基团的引入增大了混合油与水分子的相互作用能与氢键数目,抑制了水分子的热运动,导致其扩散系数降低;而随着植物油占比增加,混合油的静态介电常数显著增大,且随着含水量的提高显著上升,这是由于水分子及植物油中强极性基团的引入增大了混合油中参与极化的粒子数目,导致体系介电常数显著增高。综上所述,强极性基团是影响混合油绝缘性能的重要因素,共混时需综合考虑其对水分子扩散行为的抑制及对介电常数的增大效应,以达到提升混合油绝缘性能的目的。

薄板式静态混合器混合性能数值模拟

薄板式静态混合器内构件简单、通量高、压降低,可以有效降低稀释水掺混能耗。文中以不均匀系数ψ和管路压降Δp作为评价指标,利用CFD(计算流体动力学),对比分析单直管、单顺流羽状管、单逆流羽状管和双顺流羽状管等4种注水方式的混合效果和压降。研究发现,在注水管安装在L/D=5.3处,单管注入时,注水两侧形成的径向二次流强度Se变化缓慢,稳定的涡旋流在混合器内产生混合“死区”,降低了静态混合器的油水混合速度;当ψ降至0.05时,混合距离超过18D。此混合死区解释了单管注入时分散相注入点附近易出现局部高浓度区。双顺流羽状管注入时,对撞水相产生较高径向二次流强度Se,且迅速降低。快速变化的流场显著减少混合距离,与单管注入相比,ψ降至0.05时混合距离减少76.9%,Δp增加1.5%。

缆控智能分层注水一体化工艺的创新应用

缆控智能分层注水一体化工艺以井下智能测调配水器为核心,集成了流量计、控制电路、电机减速器、可调水嘴和封隔器验封等关键技术。通过实时监测和自动测调控制算法,系统能够精确控制各分层配水器水嘴开度,实现对油田分层注水的数字化和网络化管理。此工艺的关键技术涵盖了注水管柱的设计与功能、地面控制器的组成与功能、井下控制装置如智能测调配水器、高精度流量计和一体化可调水嘴的研发与应用,以及供电和通信电缆的密封与保护技术。实践证明,缆控智能分层注水一体化工艺在提高注水效率、降低人工干预、提升注水合格率等方面表现突出,已在多个油田项目中取得显著成效,大幅度降低了生产成本,提高了油田开发效益。

嗜盐原油降解混合菌处理采出水特性研究

针对高矿化度高硫化物的油田采出水的生物处理,从含油污泥、采出水等样品中经初筛、复筛获得嗜盐原油降解菌14株,选取降解率最高的4株进行复配,构建出嗜盐原油降解混合菌TG-1。16 SrDNA序列分析表明4株菌分别为不动杆菌(Acinetobacter);副蕈状芽胞杆菌(Bacillus paramycoides);芽孢杆菌(Bacillus sp.);肠杆菌(Enterobacter sp.)。考察了TG-1处理采出水性能,发现最适矿化度范围在30 g/L以下,最高耐受硫化物质量浓度可达150 mg/L,原油质量浓度不高于500 mg/L去除效果最好。将TG-1应用于生物接触氧化装置中,在pH值7~8、温度30℃左右、溶解氧4~5 mg/L、水力停留时间为4~12 h以及进水原油质量浓度为10~100 mg/L的条件下,出水原油质量浓度小于15 mg/L,满足克拉玛依油田注水水质标准A2。

基于J函数建模的M油藏水淹层测井评价

滨里海盆地M油藏属于稠油油藏,目的层埋深较浅,储层较为疏松。油田开发主要以热采为主,水窜容易造成油藏水淹,且新井初期含水率较高,为此开展水淹层测井评价对于制定科学合理开发调整方案,提高油田开发效率具有重要的意义。通过J函数建模求取原始含油饱和度来评价水淹层,基于M油藏取芯井的岩心资料,结合粒度分析、铸体薄片、扫描电镜、物性分析及压汞实验等方法,通过毛管压力曲线对目的层J函数进行建模,计算原始含油饱和度,对比原始含油饱和度与目前含油饱和度评价水淹层。结合生产测试结论,证明J函数方法在水淹层评价方面效果较好,这种方法对于构造油藏水淹层评价具有重要的参考意义。

多层砂岩油藏分层注水井分注井段优化方法

针对现有分层注水井分注层段确定方法实用性较差的技术问题,开展了分注层段优化方法研究。应用生产动态大数据分析方法,确定出与分注段划分密切相关的10项地质参数;利用归一化、变权及矩阵等数学变换方法,建立了分注层段计算数学模型;结合油藏数值模拟技术和矿场动态监测拟合技术,形成了以10项地质参数为基础,以提高油层动用程度为目标的合理分注政策界限优化方法。实例计算表明,该方法所需参数容易获得,计算过程简单,克服了现有方法仅考虑静态地质参数适用性差,或需要建立复杂地质模型开展数值模拟的繁琐计算过程等,实现了利用注入端、采出端及井网间三类地质参数辅以简单数学计算即可确定分注方案的新方法。以井组gXⅡ为例,应用该方法优化并现场实施,油层动用程度提高了15.7个百分点、产油量增加了23.4 t/d、综合含水率下降了1.16个百分点,验证了分注井段优化新方法的实用价值。

富水粉细砂层盾构同步注浆复合浆液配比试验

为提高富水粉细砂地层盾构同步注浆的效率和质量,精准控制管片上浮位移,进行配比试验以期得到对富水地层具有良好适应性的浆液。基于常规惰性浆液通过单因素试验,确定出高分子材料羟乙基纤维素(HEC)和聚羧酸(PC)两种外加剂的掺量范围,然后采用正交试验,对水胶比、水玻璃、羟乙基纤维素和聚羧酸4因素3水平的试验结果进行极差分析,得到流动性好、凝胶时间可控、结石率高的复合浆液配合比。结果表明,针对富水粉细砂地层的复合浆液最佳配比为:水胶比0.8(A2),水玻璃掺量30%(B2),PC掺量0.1%(C1),HEC掺量0.2%(D2),这一配比在保证流动性(稠度10~12 cm)、凝胶时间(90~150 s)、结石率(97.53%)和抗压强度(2.63 MPa)的同时,优化了浆液的抗水分散性和经济性。采用推荐浆液配比进行同步注浆,管片的上浮位移可以控制在20 mm以内,满足规范要求。

高倾角厚油层注水开发影响因素数值模拟——以H断块P油藏为例

油水重力分异作用对高倾角厚油层注水开发效果影响较大,以H断块P油藏为研究对象,结合实际油藏地质参数,建立高倾角厚油层机理模型,并应用数值模拟方法系统研究了注采位置、地层倾角、油层厚度、储层韵律、注采比、采油速度、地层压力保持水平等7个主要因素对注水开发效果的影响。结果表明,构造低部位注水高部位采油和较大的地层倾角有利于发挥油水重力分异作用从而提高采收率;油层厚度增大采收率降低;反韵律储层因底部较低的渗透率抑制了注入水的重力低伏,采收率较其他韵律储层更高;最佳注采比为1.0,最佳采油速度为3.0%,地层压力保持在原始地层压力的70%~80%时,可以获得更好的开发效果。研究成果可为此类油藏制定注水开发策略提供参考。