CO2混相压裂液对低渗透储层岩心的微观作用机理

为明确CO₂混相压裂液与储层岩心的作用机理,以柳赞断块储层岩心为实例,利用岩心驱替、SEM、XRD和CT 等实验方法开展 CO₂混相压裂液体系中不返排酸、CO₂+增溶剂(或缩膨剂或降黏剂)在地层压力和地层温度下与岩心相互作用前后岩心孔隙结构、岩心矿物成分及渗透率的变化规律实验。研究表明：不返排酸和CO₂与不同水溶性添加剂混合形成碳酸溶液均具有溶蚀长石和黏土矿物的作用,且优先溶蚀长石,溶蚀后可生成高岭石和石英等矿物,其中不返排酸的溶蚀作用最强,其次是CO₂与增溶剂混合液、CO₂与降黏剂混合液;CO₂混相压裂液注入前后液测渗透率与气测渗透率呈相同的增大趋势,且液测渗透率增大幅度随气测渗透率的变化关系表现为很强的乘幂关系。该研究成果对CO₂混相压裂提高采收率技术提供一定的技术支持。     

饱和CO2地层水驱过程中的水-岩相互作用实验

为了研究CO₂注入后储层岩性和物性的变化情况,利用室内岩心驱替装置,模拟了地层条件下(100℃,24MPa)饱和CO₂地层水驱过程中的水-岩相互作用,并对CO₂注入后,组成储层岩石的矿物溶蚀、溶解和沉淀情况以及渗透率变化的原因进行了研究。通过对实验前后反应液离子成分变化、岩心扫描电镜和全岩X-射线衍射(XRD)资料的分析表明：实验后砂岩岩心中的碳酸盐矿物出现明显的溶解现象,且方解石溶解程度最高,片钠铝石次之,铁白云石最低;反应液中K⁺质量浓度的变化主要是由碎屑钾长石颗粒溶蚀造成的;实验后有少量的高岭石和中间产物生成,其中间产物的成分主要为C、O、Na、Cl、Al和Si,并有向碳酸盐矿物转变的趋势;新生成的高岭石、中间产物和由碳酸盐胶结物溶解释放出的黏土颗粒一起运移至孔喉,从而堵塞孔隙,降低了岩心渗透率。通过以上实验再现了CO₂注入后,短时期内储层岩石中长石和碳酸盐类矿物的溶蚀和溶解过程以及新矿物沉淀情况,并且揭示了储层渗透率变化的原因,从而为CO₂的地下捕获机制提供了地球化学依据。     

碱、表面活性剂和聚合物对储层溶蚀作用及其机理研究

本文开展了碱液、"碱/表面活性剂"AS二元复合体系、"碱/表面活性剂/聚合物"ASP三元复合体系对储层岩石矿物的静态溶蚀实验,考察了实验过程中液相内目标离子(Ca²⁺、Mg²⁺、Si⁴⁺、OH^-、CO₃^2-、HCO₃^-和Cl^-等)浓度变化规律和岩样表面主要元素（Al和Si等）含量变化。结果表明,碱对岩样的溶蚀作用主要针对黏土矿物,对长石骨架作用较小。三元复合体系处理岩样后的液相内硅铝离子浓度增加,钙、镁离子浓度降低,岩样表面硅、铝元素含量降低。随碱浓度增加、液固比增加或处理时间延长,溶蚀作用增强,表面活性剂和聚合物可以减轻碱对岩样的溶蚀作用。处理初期溶蚀作用较强,处理60d后,液相中硅酸分子发生聚合作用,并在碱性条件下脱水生成硅垢,聚合物又促进硅胶体聚集和成垢。图14表4参17     

液固相变吸收剂的CO2吸收性能及相分离行为机理研究

以N-甲基二乙醇胺(MDEA)+哌嗪(PZ)水溶液作为复合吸收剂的化学吸收法是捕集二氧化碳(CO₂)的重要手段之一，但该复合吸收剂再生能耗较高，限制了其在碳捕集领域的应用。为克服该缺点，在该复合吸收剂中加入某种溶剂形成相变吸收剂，可减少吸收剂进入解吸单元的总量，从而降低再生能耗。设计了一种组成为MDEA+PZ+N-甲基吡咯烷酮(NMP)+水(H₂O)的液固相变吸收剂，并考察了其吸收CO₂的性能，测定了NMP、PZ质量分数对液固相变吸收剂CO₂溶解度的影响，分析了相分离行为机理。结果表明，该吸收剂的CO₂溶解度随着NMP质量分数的增加而降低，随着PZ质量分数的增加而增加；当吸收剂中NMP、PZ的质量分数分别达到50%、3%及以上时，吸收CO₂后生成PZ-氨基甲酸酯达到饱和析出形成固相，固相先随CO₂溶解度增加而增加，后随着CO₂溶解度继续增加，生成更易溶于水的PZ-二氨基甲酸酯，导致固相减少。     

中国东北地区幔源-岩浆CO2赋存的地质记录

在松辽盆地南部及海拉尔盆地CO₂气藏和片钠铝石研究的基础上,根据中国东北地区CO₂气藏中CO₂的碳同位素、氦同位素,各盆地片钠铝石的碳、氧同位素的数据,以及CO₂气藏（苗）与断裂和火山岩的关系,对中国东北地区CO₂的成因及其与片钠铝石的关系进行了研究。分析认为中国东北地区的CO₂绝大多数为幔源-岩浆成因,且形成片钠铝石的CO₂与幔源-岩浆CO₂同源;片钠铝石是CO₂的“示踪矿物”,记录了地质历史时期CO₂的聚集;地层水和原油中溶有大量的无机成因CO₂,经CO₂改造的地层水具有高矿化度及Na⁺ 、K⁺ 、HCO₃^-、CO₃^2-浓度高的特点。依据片钠铝石与CO₂的关系,地层水中离子浓度的变化,以及原油中溶解大量CO₂的事实,总结了中国东北地区幔源-岩浆CO₂赋存的地质记录。     

CO2快速吞吐提高页岩油采收率现场试验

页岩油注CO₂吞吐提高采收率技术处于探索阶段,目前面临着CO₂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CO₂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CO₂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CO₂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CO₂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) CO₂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CO₂,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CO₂首先萃取轻烃组分,随生产时间增加萃取组分逐渐变为...     

苏北盆地黄桥地区富CO2流体对油气储-盖系统的改造作用

查明富CO₂流体对储-盖系统的改造作用,对于研究CO₂活动与油气成藏效应、CO₂储存和CO₂驱油提高采收率有着重要意义。选取下扬子苏北盆地黄桥地区和句容地区的二叠系龙潭组储层和大隆组盖层组合,分别作为有无CO₂流体活动的对比研究对象。通过薄片观察统计、矿物成分和碳同位素分析,查明了两个地区储层的异同点。黄桥地区储层的自生矿物以石英次生加大边和高岭石充填为主,发育少量片钠铝石,句容地区不发育片钠铝石,且次生石英含量不高;黄桥地区储层孔隙度明显高于句容地区,薄片下观察到大量长石溶蚀孔隙,偶见长石溶蚀孔内生长片钠铝石雏晶,是CO₂与长石发生水岩相互作用的直接证据;黄桥地区和句容地区盖层均为黑色块状泥岩,黄桥地区盖层发育微裂隙,但裂隙均已再充填方解石脉,碳同位素数据表明方解石脉为富CO₂流体活动结果,在句容地区泥岩盖层中未见大量裂隙和矿物脉。综合研究分析表明,富CO₂流体充注引起储层砂岩中长石大量溶蚀,增加了孔隙空间,片钠铝石、次生石英和高岭石自生矿物组合序列沉淀,同时富CO₂流体的连续活动导致泥岩盖层发生方解石沉淀,充填盖层裂缝,有利于提高盖层的封盖能力。     

硅烷修饰SBA-15与固载聚醚离子液体化催化剂的制备与性能

将3种聚醚离子液体,即Cl[PECH-MIM]-OH、Cl [PECH-MIM]-COOH和Cl [PECH-MIM]-NH₂,分别与助催化剂ZnBr₂反应制得复合型聚醚离子液体,再用硅烷(CPTES)修饰分子筛SBA-15,并将其固载复合聚醚离子液体,制得固载化催化剂SCP-OH/[ZnBr₂]、SCP-COOH/[ZnBr₂] 和 SCP-NH2/[ZnBr₂]。利用红外光谱仪、热重分析仪、电镜扫描仪对SBA-15及3种固载化催化剂进行化学结构、热性能和表观形貌的表征,并研究其催化环氧丙烷(PO)与CO₂合成碳酸丙烯酯(PC)反应的性能。结果表明,复合型聚醚离子液体成功固载于硅烷分子筛上,实现了离子液体的相态转变及其高效的非均相转化CO₂。对于3种固载化离子液体催化环氧丙烷与CO₂的羰基化反应SCP-COOH/[ZnBr₂ 的催化性能最佳,在CO₂压力3.0 MPa、反应温度130  ℃、液时空速为0.5 h^-1的反应条件下,PO转化率为83.8%、产物PC选择性为94.1%,并且连续使用80 h后仍保持良好的催化性能。     

川西坳陷中段上三叠统须家河组水岩相互作用机制

水岩相互作用是成岩矿物演化和地层水离子变化之间的桥梁,两者通过水岩反应达到水岩体系的平衡,呈现出此消彼长的关系,并留下了水岩相互作用的证据。本文通过川西坳陷中段须家河组储层成岩矿物的微观特征以及地层水离子地球化学特征等的综合分析,对其水岩相互作用机制及概念模式进行了探讨,认为研究区须家河组二段（简称须二段）和须家河组四段（简称须四段）不同的水岩体系、围岩基质及地层水背景是造成两者水岩作用机制存在差异的根本原因。由于较大的K⁺/H⁺活度比,须二段长石得到有效保存;须四段长石缺失的最重要原因是其本身的物源较为贫长石,同时,低K⁺/H⁺活度比导致长石溶蚀进一步降低了其中的长石含量。长石的溶解、自生矿物的沉淀和黏土矿物的转化主要受长石溶蚀-离子（K⁺）迁移性-伊利石化三元体系中最慢反应进程控制。碳酸盐胶结物的碳氧同位素分析表明须四段的水岩体系更为开放,酸性流体数量大于须二段,须二段缺少有机CO₂记录,推测与酸性流体数量较少、烃源岩为海相灰质泥页岩及构造抬升剥蚀有关,CO₂运移分馏的影响较小。在此基础上,分别建立了铝硅酸盐和碳酸盐水岩作用概念模式,认为泥页岩并不是水岩体系中的封闭性因素,相反是水岩体系的第一开放对象,泥页岩（煤层）同时是物质提供者和接受者,是整个水岩体系不可或缺的部分。     

缝洞型油藏不同注入气最小混相压力计算方法

近年来,塔河油田缝洞型油藏注氮气驱替增油效果显著,但气体驱替发生混相的机理尚不明确,且无针对缝洞型油藏不同油品性质、不同注入气体的最小混相压力计算公式。为解决上述问题,基于长细管原理,设计了缝洞型油藏最小混相压力实验,并测试了4种油样在N₂、N₂+ CO₂复合气（N₂与CO₂含量的比分别为80∶20、50∶50、30∶70）及CO₂等5种注入气中的最小混相压力。基于Alston关联式,引入CO₂占注入复合气比例R,通过多元回归方法,建立了适合塔河油田不同油品性质、不同注入气体条件下的最小混相压力计算方法。实例应用表明,W-1井油藏压力为62MPa,注气方案采用N₂与CO₂含量比为40:60,现场实施后,取得较好效果,换油率达到0.5t/m³。该方法为注入气的筛选提供了重要的依据。     

塔河油田某注采井生产油管腐蚀失效分析

塔河油田某注采井在修井起出管柱过程中发现油管柱出现了腐蚀穿孔和断脱。为了找到腐蚀失效原因,并采取针对性的防护措施保证井筒安全,通过对油管管材的理化性能测试、冲击性能测试、拉伸性能测试,结合扫描电子显微镜(SEM)、X射线衍射分析(XRD)等腐蚀特征及腐蚀产物表征分析方法,对井下管柱进行了腐蚀失效分析。结果表明,油管腐蚀是由H_2S-CO_2-Cl~--H_2O体系引起的电化学腐蚀,以CO_2腐蚀为主,同时存在H_2S腐蚀,Cl~-对腐蚀穿孔有一定的促进作用。建议添加缓蚀剂或对油管添加表面涂层、镀层、油管衬里,提高油管服役寿命。     

Burning Rate Equations as a Function of Pressure and Temperature for 1HT/CuO/Additive Mixtures

The burning rate of energetic materials depends on pressure and initial temperature. The relation between the burning rate and pressure has been well studied. However, the effect of the initial temperature on the burning rate has not been investigated quantitatively. In this study, the burning rates of 1H-tetrazole, copper (II) oxide, and additive mixtures were examined under conditions ranging from 5 to 9 MPa and 243 to 343 K, and equations for the burning rate as a function of pressure and temperature were obtained. In general, the burning rates predicted by the correlation equations were in good agreement with the observed values. The temperature sensitivities were also predicted and compared with the observed values and good agreement was found between the predicted and observed values.     

Catalyst Effects of Nanometer CuCr2O4 on the Thermal Decomposition of TEGDN Propellant

The catalyst effects of nanometer CuCr₂O₄ on the thermal decomposition of triethyleneglycol dinitrate (TEGDN) propellant were investigated using thermogravimetric analysis, differential scanning calorimetry, mass spectrometry, and Fourier transform infrared spectroscopy. The Ozawa equation and step integral equation were used to calculate the activation energy. The results showed that the thermal decomposition reaction of TEGDN propellant can be seen as two reactions. Nanometer CuCr₂O₄ added in TEGDN propellant reduced the activation energy of the second reaction step; therefore, the second reaction step was sped up. Mass spectrometry, Fourier transform infrared spectrometry and the combustion residue analysis results also supported this conclusion.     

Low temperature functional analysis of bitumen modified with composite of nano-SiO2 and styrene butadiene styrene polymer

Most parts of Iran have completely different climates in different seasons of year. In other words, in summer it is very warm and in winter it becomes very cold. Achieving modified bitumen that could function adequately in both high and low temperature has always been under attention of researchers. One of bitumen modifiers is styrene butadiene styrene polymer. Because bitumen modified by styrene butadiene styrene does not show expected field function in both high and low temperatures, largely due to phase separation of bitumen and polymer, in the present study it has been tried to analyze the low-temperature function of bitumen modified by combining nano-SiO₂ and styrene butadiene styrene polymer. The study reveals that adding nano-SiO₂ by 3% and 4% of bitumen weight to the double combination of bitumen and styrene butadiene styrene polymer has improved its function in low temperature. This study has innovation as it deals with the analysis of low temperature function of nano-SiO₂ and SBS in modification of bitumen for the first time in the world.     

High-temperature functional analysis of bitumen modified with composite of nano-SiO2 and styrene butadiene styrene polymer

In recent decades, researchers have always considered the production of modified bitumen that could perform suitably in both high and low temperatures. One bitumen modifier is styrene butadiene styrene (SBS) polymer. Because bitumen modified with styrene butadiene styrene polymer does not show expected field performance in high and low temperatures largely due to phase separation of bitumen and polymer, the present research study is an attempt to use the composite of nano-SiO₂ and styrene butadiene styrene polymer in modification of bitumen and analyze its high-temperature performance. The study revealed that adding nano-SiO₂ to bitumen modified with SBS polymer resulted to an improvement of complex modulus, phase angle, resistance potential against rutting, storage modulus, loss modulus, and high-temperature functional performance in general. Additionally, the study uncovered that adding nano-SiO₂ with 3% and 4% of bitumen weight, compared with other composites, considerably improved the high-temperature functional performance of bitumen modified with styrene butadiene styrene polymer. As 4.5%SBS+4%nano-SiO₂ could not estimate less than 3 Pa.sec rotational viscosity in 135°C, 4.5%SBS+3%nano-SiO₂ is offered as the optimal composite. The study is the first one in its own type in the world and is, therefore, innovative.     

Double Action of Cr3+ Gel on Modifying Profile and Removing CaCO3 in ASP Flooding

Abstract

To decrease fluid emulsification and system scale caused by NaOH/surfactant/polymer flooding, a pilot test of Na₂CO₃/surfactant/polymer flooding was developed in Daqing Oilfield. The results show that the two problems mentioned above were controlled, but scale in the injecting system is becoming a new technical problem and the scale aggravates reservoir heterogeneity. By analyzing the scaling mechanism and the properties of the profile control agent, the study presents technique of Cr³⁺ polymer gel for improving the fluid sucking profile of an injection well in Na₂CO₃/surfactant/polymer flooding. The optional formula, property evaluation, and compatibility condition between Na₂CO₃/surfactant/polymer flooding and polymer gel were studied, and a pilot test was used to judge the availability of Cr³⁺ polymer gel in 2-1-P56 well of Daqing Oilfield. The study shows that polymer gel functions include scavenging and blanking off high permeability zone. The scale of the instrument of injection, pipes, and well wall is thoroughly explained. The fluid entry in the high-permeability layer decreased from 100 to 64.9%, and fluid entry in the low-permeability layer increased from 0 to 35.1%. The profile control of the injection well was effectively improved.     

Rapid prediction of hydrate condition for promoting CO2 recovery in the oil and gas industry

Gas hydrates may form in the petroleum and gas industry and can lead to significant problems such as plugging the pipelines and increasing velocity movement of the hydrate plugs in the pipelines. In this contribution, a simple strategy based on principal component analysis and partial least square methods has been utilized in order to estimate hydrate formation condition of carbon dioxide and tetra butyl ammonium chloride. In this regard, the developed tool has been evaluated by some reported data points in order to obtain its accuracy. This tool was simple to apply and can be of great help for gas transmission engineers to have an accurate estimation of hydrate conditions.     

An Efficient Methodology for Performance Optimization and Uncertainty Analysis in a CO2 EOR Process

Abstract

A pragmatic technique is proposed and successfully applied to determine the optimal production–injection scheme in a CO₂ flooding reservoir under uncertainty. Well rates of injectors and bottomhole pressures of producers are chosen as the controlling variables. Geological uncertainty is accounted for using the multiple reservoir models. An objective function associated with net present value (NPV) is defined, and a modified genetic algorithm is employed to determine the optimal production–injection scheme. It is shown from a field case study that the optimized scheme can not only increase the expected oil recovery and NPV by 7.8 and 6.6%, respectively, but can also achieve a considerably small range of possible NPVs.     

LNG冷能用于朗肯循环和CO2液化新工艺

针对CO_2排放过量的问题,提出了两种利用液化天然气冷能进行朗肯循环发电和液化CO_2的新工艺流程。流程1在常规朗肯循环的基础上增加了再热循环和回热循环;流程2在保证预冷和液化CO_2所需冷能不变的情况下,在流程1的基础上集成了氮气液化系统,目的是降低蒸发器内冷热物流的品位差,提高蒸发器的火用效率。分析了烟气温度、循环工质压力和流量对流程比功和火用效率的影响。模拟计算得到,流程1、流程2的火用效率分别可达到49.70%和49.80%,对应比功分别为237.70 kJ/kg LNG和235.20 kJ/kg LNG,CO_2的液化率为0.60 kg/kg LNG。结合具体实例进行计算,证明新流程具有良好的经济效益和环境效益。     

H6P2W18O62/MCM-48催化剂的制备、表征及催化绿色合成己二酸

以MCM-48为载体,通过浸渍法制备了H6P2W18O62/MCM-48催化剂,并采用FT-IR、XRD、SEM、EDS对催化剂进行表征。以微波促进30%(质量分数)H2O2氧化环己酮合成己二酸反应为探针,考察了H6P2W18O62/MCM-48的催化性能,并通过正交实验确定了优化的工艺条件。结果表明,采用H6P2W18O62负载量40%的H6P2W18O62/MCM-48催化剂,在优化的合成己二酸的工艺条件下,即催化剂质量分数(以环己酮质量计)5.1%、n(C6H10O)∶n(H2O2)∶n(H2C2O4.2H2O)=100∶450∶1.88、反应温度95℃、微波功率300 W、反应时间3.5h,己二酸收率可达81.3%;催化剂重复使用5次,己二酸收率仍可达到64.6%。