不同分解温度下记忆效应对CO2/CH4混合气体水合物合成的影响

在非常规天然气以及天然气水合物二氧化碳(CO₂)置换开采过程中，明确CO₂/CH₄混合气体水合物(以下简称“CO₂/CH₄水合物”)的合成和分解机理，对水合物法分离混合气体、CO₂封存与CH₄高效开采有重要意义。以多孔介质+去离子水体系中的CO₂/CH₄水合物为研究对象，进行了二次合成和分解实验，研究了分解时间为0.5 h、分解温度为5～25℃条件下的记忆效应对CH₄/CO₂水合物合成的影响，主要从二次合成诱导期、气体消耗量和消耗速率，以及各组分气体消耗情况3个方面进行了分析。结果表明，分解温度越低，二次合成诱导期越短；记忆效应降低了二次合成速率；当分解温度为10℃时二次合成速率最快，气体消耗速率峰值为8.10 mmol/min；在相同的合成温度和压力下，升温分解后的记忆效应使二次合成时CO₂水合物合成量提高至初次合成量的1....     

鄂尔多斯盆地页岩油水平井CO2区域增能体积压裂技术

针对鄂尔多斯盆地页岩油储层压力低、缝网复杂程度低和黄土塬水资源缺乏等问题，以该盆地庆城油田页岩油为研究对象，进行了滑溜水和CO₂压裂物理模拟试验，利用高能CT监测了CO₂压裂裂缝扩展规律，分析了CO₂压裂形成复杂裂缝的可行性；利用油藏数值模拟方法，优化了CO₂注入关键参数，形成了适合庆城油田页岩油的CO₂区域增能体积压裂技术。研究表明：前置CO₂压裂可提高长7段页岩油储层裂缝复杂程度，裂缝沿层理弱面扩展并纵向穿层形成缝网；增能理念应由单井段间交替增能向平台整体注入实现井间、段间协同一体增能转变，单井采用全井段注入增能模式，可实现缝控区域全覆盖。庆城油田某平台进行了页岩油CO₂区域增能体积压裂试验，与采用常规体积压裂技术的邻井相比，3口试验水平井平均压力保持程度提高1.5倍，单井平均初期产油量提高28.6%。研究和现场试验结果表明，CO₂区域增能体积压裂能提高裂缝复杂程度，增加区域地层能量，提高单井产能，可为鄂尔多...     

南川常压海相页岩气注CO2吞吐提高采收率工程实践

当前研究实验和模拟论证了注CO₂吞吐提高页岩气采收率的理论可行性,然而其实际工程效果尚未得到现场试验的验证。为此,基于四川盆地南川常压海相页岩气藏地质赋存及生产特征,开展了页岩等温吸附和CO₂—CH₄竞争吸附机理研究,实施了国内首次常压海相页岩气衰减井CO₂吞吐现场试验,并提出了构建成套技术体系的攻关方向。研究结果表明：(1)气井生产到后期进入低压低产阶段,表现出地层能量不足的特征,是提高气井采出程度的重要阶段;(2)常压页岩的CH₄和CO₂吸附能力明显高于低压或高压页岩,采用CO₂提采更具可行性和必要性;(3)相同条件下的常压、高压和低压3组页岩样品均表现出对CO₂的吸附量大于对CH₄的吸附量,且对气体的吸附能力依次为南川(常压海相)页岩>长宁(高压海相)页岩>延长(低压陆相)页岩;(4)试验井注CO₂吞吐增产效果明显,页岩气单井预测最终可采储量(EUR)...     

页岩油CO2非混相吞吐与埋存实验及影响因素

将CO₂注入页岩,不但能提高页岩油采收率,还能达到埋存CO₂的目的,但CO₂吞吐和埋存的影响因素较多且相互作用。为搞清楚页岩油CO₂非混相吞吐与埋存特征,通过开展页岩岩心CO₂吞吐、吸附实验,定量评价了CO₂注入压力、CO₂相态类型、储层温度、闷井时间、裂缝、吞吐次数对CO₂吞吐效果以及颗粒直径、CO₂注入压力、储层温度对CO₂埋存效果的影响程度。研究表明：增大注入压力不但有利于CO₂吞吐,还能增大吸附量;增加注入压力会诱导天然微裂缝的扩展、延伸,有利于扩大CO₂波及面积,减小原油渗流阻力;当储层温度小于50℃时,温度升高有利于提高吞吐采收率,但会降低CO₂吸附量;当温度大于等于50℃时,温度升高不利于CO₂吞吐和埋存;在超临界条件(7.4 MPa、31℃)下CO₂     

页岩油井缝网改造后CO2吞吐与埋存特征及其主控因素

为了明确裂缝性页岩储层注CO₂吞吐后的埋存效果，探究注CO₂吞吐实现CO₂有效埋存的可行性，通过建立含复杂缝网的页岩油井CO₂吞吐与埋存数值模型，对比不同生产与裂缝参数下的吞吐与埋存特征，并引入灰色关联分析方法确定了影响CO₂吞吐与埋存效果的主控因素。结果表明：CO₂吞吐不仅可以提高页岩油的采收率，而且可以实现部分CO₂的有效埋存，埋存系数可达0.40；注CO₂吞吐开发页岩油藏时，吞吐和埋存效果随着吞吐轮次、注入速度、闷井时间和周期注入量等生产参数的增大而增强，其中吞吐轮次对吞吐效果影响最大，可使累计产油量增加22.12%，注入速度对埋存效果影响最大，可使埋存系数达到0.40;CO₂吞吐时间越晚，累计产油量越少，但埋存系数越大，累计产油量每年减少3.47%，埋存系数每年增加39.48%；页岩储层裂缝条数、长度的增加有利于提高采收率、实现更多的CO₂埋藏，累计产油量最大可...     

全球海上CO2封存现状及中国近海机遇与挑战

海上CO₂封存是碳封存的路径之一。全球已广泛开展的CO₂海洋封存研究与商业示范案例对中国近海盆地CO₂封存研究具有借鉴意义。本文从全球CO₂海洋封存发展现状出发,结合典型CO₂海洋封存示范工程,根据项目背景、政策/资金/技术支持、国际合作以及地质工程特性等相关项目概况,对比分析中国实施CO₂海洋封存项目潜在的机遇与挑战,最后对CO₂海洋封存技术在中国近海的发展进行了展望。未来中国近海盆地CO₂海洋封存研究应从全海域级、盆地级、区带级以及场地级,由面到点、逐级递进、不断聚焦,构建适合中国近海盆地特点评价优选体系标准和相应的客观量化评价方法体系。     

南海富CO2天然气分类利用技术

南海丰富的天然气资源普遍具有CO₂含量高(20%～80%)的特点,现有工艺只适宜于加工CO₂含量相对较低的天然气资源,且过程中均有大量CO₂排放,碳资源利用率较低,在一定程度上限制了南海大气田的大规模开发利用。本文介绍了南海富CO₂天然气脱碳后商用及尿素和甲醇等化工利用两方面的现状,基于南海天然气的组成特点,提出了按CO₂含量小于20%、20%～30%、大于30%的3种区间,分别采用脱碳+海洋封存、CO₂捕集+化工利用、CH₄-CO₂干重整+费托合成方案的分类利用新思路,并介绍了CH₄-CO₂干重整、CO₂捕集、 CO₂海洋封存、 CO₂矿化、CO₂化工利用等南海富CO₂天然气分类利用核心技术以及中国海油在这5类核心技术方面的研究进展。本文研究有助于推动富CO<...     

CO2地质封存系统泄漏风险评价

CO₂地质封存是缓解温室效应的重要手段，而封存系统的泄漏风险评价是安全封存的基础。首先，综合分析影响CO₂地质封存系统泄漏的因素，认为诱发泄漏风险的原因主要是CO₂低温冷流体产生对井筒和盖层的交变应力和CO₂-水-岩腐蚀反应综合作用下导致井筒和盖层的完整性失效。考虑多因素综合作用对CO₂地质封存系统泄漏的影响，并基于模糊综合评价理论(FCE)，建立了CO₂泄漏风险因素间的层次关系模型，进行了CO₂地质封存系统泄漏风险评价，其过程包括应用非线性正态隶属函数建立CO₂泄漏风险因素对评语的隶属度矩阵，并应用层次分析方法构建泄漏风险影响因素间的比较矩阵，以获得泄漏风险因素的权重子集，并对给定实例CO₂地质封存系统泄漏风险进行评价，进而得出所评价的CO₂地质封存井筒当前处于泄漏低风险，盖层处于泄漏中风险，封存系统处于泄漏中风险。通过采集CO₂地质封存过程中泄...     

页岩储层超临界CO2压裂液滤失规律实验研究

压裂施工过程中,压裂液的滤失量是影响压裂裂缝几何形态和压裂效果的主要因素,但目前中国还没有对页岩储层超临界CO₂压裂液滤失规律实验方面的报道。因此,结合中国典型页岩气储层特征,研究了非线性滤失条件下,不同初始相态的CO₂压裂液在地层岩心中的滤失规律,在此基础上分析了CO₂压裂液滤失规律的主要影响因素,以及不同实验条件下CO₂压裂液的滤失机理。实验结果表明,CO₂压裂液的滤失规律受注入压力、压差、裂缝开启度及压裂液黏度等因素的影响,随着注入压力、压差、裂缝开启度的增大,CO₂压裂液滤失速率增大;不同滤失实验条件下,影响CO₂压裂液滤失规律的主导因素不同,当CO₂压裂液处于超临界状态(7.38 MPa,31.1℃)时,由于黏度较大,超临界CO₂压裂液的滤失系数相对较小。      

CH4- CO2体系固体CO2形成条件的预测模型

采用膨胀机制冷工艺回收天然气中的乙烷时,膨胀机出口与脱甲烷塔顶部的温度较低,容易发生CO₂冻堵,影响装置的正常运行。准确预测固体CO₂的形成条件,有助于及时采取相应的措施调整凝液回收装置的操作工况,避免CO₂冻堵。为此,分析了CO₂固体的形成条件,根据相平衡原理,采用标准形式的Peng Robinson状态方程建立了液固平衡模型（LSE）和气固平衡模型（VSE）,据此分别对CH₄-CO₂2气相体系和CH₄-CO₂2液相体系中的固体CO₂形成温度进行了计算,并与用HYSYS软件预测的固体CO₂形成温度进行了比较。结果表明：该计算模型的准确度较高,与实验数据的误差在2 ℃以内;而HYSYS软件预测的CH₄-CO₂气相体系的固体CO₂形成温度较实验数据偏高1～5 ℃,预测的CH₄-CO₂液相体系的固体CO₂形成温度较实验数据偏低1～6 ℃。     

Exploitation of fractured shale oil resources by cyclic CO2 injection

With shale oil reservoir pressure depletion and recovery of hydrocarbons from formations, the fracture apertures and conductivity are subject to reduction due to the interaction between stress effects and proppants. Suppose most of the proppants were concentrated in dominant fractures rather than sparsely allocated in the fracture network, the fracture conductivity would be less influenced by the induced stress effect. However, the merit of uniformly distributed proppants in the fracture network is that it increases the contact area for the injection gas with the shale matrix. In this paper, we address the question whether we should exploit or confine the fracture complexity for CO₂-EOR in shale oil reservoirs. Two proppant transport scenarios were simulated in this paper: Case 1—the proppant is uniformly distributed in the complex fracture system, propagating a partially propped or un-propped fracture network; Case 2—the proppant primarily settles in simple planar fractures. A series of sensitivity studies of the fracture conductivity were performed to investigate the conductivity requirements in order to more efficiently produce from the shale reservoirs. Our simulation results in this paper show the potential of CO₂ huff-n-puff to improve oil recovery in shale oil reservoirs. Simulation results indicate that the ultra-low permeability shales require an interconnected fracture network to maximize shale oil recovery in a reasonable time period. The well productivity of a fracture network with a conductivity of 4 mD ft achieves a better performance than that of planar fractures with an infinite conductivity. However, when the conductivity of fracture networks is inadequate, the planar fracture treatment design maybe a favorable choice. The available literature provides limited information on the relationship between fracture treatment design and the applicability of CO₂ huff-n-puff in very low permeability shale formations. Very limited field test or laboratory data are available on the investigation of conductivity requirements for cyclic CO₂ injection in shale oil reservoirs. In the context of CO₂ huff-n-puff EOR, the effect of fracture complexity on well productivity was examined by simulation approaches.     

延长油田致密砂岩油藏CO2驱油机理研究

CO_2驱是提高低渗透油田产量、缓解温室效应的有效途径。针对鄂尔多斯盆地油藏压力系数低、原油轻质组分含量高的特点,通过PVT和最小混相压力等测试分析方法,揭示了低压、低孔、低渗油藏CO_2驱提高采收率主要机理。开展了CO_2注入储层与无机、有机物作用后的沉淀研究,表明CO_2在无机盐溶液中不会形成沉淀堵塞孔隙,CO_2与有机质作用后沉积点高于油藏压力,且注入压力越高,CO_2在地层原油中的溶解能力越强,目标区块CO_2注入后不易形成沥青质沉淀。物模驱替实验结果表明,均质岩心的采出程度明显高于非均质岩心,且随着岩心非均质性的增加,水驱采出程度、气驱采出程度及最终采出程度均明显下降。     

A numerical simulation study of CO 2 injection for enhancing hydrocarbon recovery and sequestration in liquid-rich shales

Less than 10% of oil is usually recovered from liquid-rich shales and this leaves much room for improvement, while water injection into shale formation is virtually impossible because of the extremely low permeability of the formation matrix. Injecting carbon dioxide (CO₂) into oil shale formations can potentially improve oil recovery. Furthermore, the large surface area in organicrich shale could permanently store CO₂ without jeopardizing the formation integrity. This work is a mechanism study of evaluating the effectiveness of CO₂-enhanced oil shale recovery and shale formation CO₂ sequestration capacity using numerical simulation. Petrophysical and fluid properties similar to the Bakken Formation are used to set up the base model for simulation. Result shows that the CO₂ injection could increase the oil recovery factor from 7.4% to 53%. In addition, petrophysical characteristics such as in situ stress changes and presence of a natural fracture network in the shale formation are proven to have impacts on subsurface CO₂ flow. A response surface modeling approach was applied to investigate the interaction between parameters and generate a proxy model for optimizing oil recovery and CO₂ injectivity.     

CO2准干法压裂技术研究及应用

致密砂岩气藏普遍具有储层物性差、孔喉细、黏土矿物含量高的特征,水力压裂易导致储层产生水敏、水锁等液相伤害,影响增产效果。针对此问题,研究了CO₂准干法压裂技术,重点开展了准干法压裂工作液组成、携砂性能、耐温耐剪切性能等方面的研究,形成了一种液态CO₂中含有少量水基压裂液的均匀混合相体系,具有液相伤害小、造缝携砂性能好、现场操作性强等特点,可满足大砂量、高砂比压裂施工要求。该技术在冀东油田南堡5号构造深层致密砂岩气藏进行先导试验,压后单井日增油2.5倍,日增气8.6倍,增产效果理想。      

CO2 sequestration through enhanced oil recovery in a mature oil field

Recent advances in enhanced oil recovery (EOR) technology create new opportunities for CO₂ sequestration. This paper proposes a technical–economic model for underground storage of CO₂ emitted by a fertilizer industry in the Northeast of Brazil, in a hypothetical mature oil reservoir through EOR operation. Simulations based on mass, energy and entropy balances, as well as economic analysis, were assessed for the process of CO₂ sequestration combined with EOR. This model takes into account the energy requirements for the whole CO₂ sequestration process, as well as the emissions inherent to the process. Additionally, a breakdown cost methodology is proposed to estimate the main financial determinants of the integrated EOR with CO₂ sequestration (costs of CO₂ purchase, compression, transportation and storage). Project evaluation is derived from a cash flow model, regarding reservoir production profile, price and costs, capital expenditures (CAPEX), operating expenditures (OPEX), carbon credits, depreciation time, fiscal assumptions etc. A sensitivity analysis study is carried out to identify the most critical variables. Project feasibility, as expected, is found to be very sensitive to oil price, oil production, and CAPEX. Moreover, there is the contribution from the mitigation of the greenhouse gas (GHG) by storing a significant amount of CO₂ in the reservoir where it can remain for thousands of years.     

Modeling CO2 miscible flooding for enhanced oil recovery

The injection of fuel-generated CO2 into oil reservoirs will lead to two benefits in both enhanced oil recovery (EOR) and the reduction in atmospheric emission of CO2. To get an insight into CO2 miscible flooding performance in oil reservoirs, a multi-compositional non-isothermal CO2 miscible flooding mathematical model is developed. The convection and diffusion of CO2-hydrocarbon mixtures in multiphase fluids in reservoirs, mass transfer between CO2 and crude, and formation damages caused by asphaltene precipitation are fully considered in the model. The governing equations are discretized in space using the integral finite difference method. The Newton-Raphson iterative technique was used to solve the nonlinear equation systems of mass and energy conservation. A numerical simulator, in which regular grids and irregular grids are optional, was developed for predicting CO2 miscible flooding processes. Two examples of one-dimensional (1D) regular and three-dimensional (3D) rectangle and polygonal grids are designed to demonstrate the functions of the simulator. Experimental data validate the developed simulator by comparison with 1D simulation results. The applications of the simulator indicate that it is feasible for predicting CO2 flooding in oil reservoirs for EOR.     

CO2与吉木萨尔储层岩石相互作用实验研究

CO₂前置蓄能压裂焖井期间,CO₂持续与储层岩石发生作用。为探索CO₂对吉木萨尔页岩作用效果及变化规律,明确提高采收率机理,分别对浸泡前后的吉木萨尔页岩进行渗透率测试实验、X射线衍射实验和扫描电镜实验,在分析渗透率宏观变化规律的基础上,对矿物组成、微观表面形态和孔喉结构变化规律进行解释。实验结果表明:使用CO₂水溶液对吉木萨尔页岩长期浸泡后,其渗透率增大,浸泡7天增大约65%,浸泡14天增大约1.4倍;CO₂水溶液对碳酸盐岩矿物有明显的溶蚀作用,在地层条件下使用CO₂水溶液对岩样碎块浸泡5天后,碳酸盐岩溶蚀率可达到45.2%;从微观表面溶蚀情况来看,经CO₂水溶液浸泡后,原有孔隙被溶蚀扩大或出现新的孔隙,从而提高了渗透率。现场试验结果表明,通过增加裂缝复杂度、增加焖井时间和使用“CO₂₊水基压裂液”复合压裂的方法对增强碳酸盐岩矿物溶蚀及提高地层渗透率有显著影响。      

氨基碳点/聚酰亚胺混合基质膜的制备及CO2分离性能研究

将水热合成法制备的氨基碳点与聚酰亚胺复合得到混合基质膜。通过SEM、FT-IR、XRD和DSC考查了氨基碳点掺杂质量分数对混合基质膜形貌和结构的影响。氨基碳点表面的氨基可以提供碱性环境,同时增加了膜内的自由体积,促进CO₂传递。当氨基碳点掺杂质量分数为0.3%时,混合基质膜的CO₂分离性能最佳,其CO₂、CH₄、N₂渗透通量分别为85.87 barrer、1.69 barrer、2.62 barrer,CO₂/CH₄、CO₂/N₂选择性分别为50.81和32.77。      

Optimal activated carbon for separation of CO2 from (H2 + CO2) gas mixture

Seven types of activated carbon were used to investigate the effect of their structure on separation of CO₂ from (H₂ + CO₂) gas mixture by the adsorption method at ambient temperature and higher pressures. The results showed that the limiting factors for separation of CO₂ from 53.6 mol% H₂ + 46.4 mol% CO₂ mixture and from 85.1 mol% H₂ + 14.9 mol% CO₂ mixture were different at 20 C and about 2 MPa. The best separation result could be achieved when the pore diameter of the activated carbon ranged from 0.77 to 1.20 nm, and the median particle size was about 2.07 lm for 53.6 mol% H₂ ? 46.4 mol% CO₂ mixture and 1.41 lm for 85.1 mol% H₂ + 14.9 mol% CO₂ mixture. The effect of specific area and pore diameter of activated carbon on separation CO₂ from 53.6 mol% H₂ ? 46.4 mol% CO₂ mixture was more significant than that from 85.1 mol% H₂ ? 14.9 mol% CO₂ mixture. CO₂ in the gas phase can be decreased from 46.4 mol% to 2.3 mol%–4.3 mol% with a two-stage separation process.     

含杂质CO2管道输送水合物形成规律研究

在延长油田产生的CO₂气体输送过程中,管线会发生水合物冰堵,影响气体输送流量,为了探究CO₂水合物在管道输送过程中的形成规律,利用PVTSIM软件生成了CO₂水合物的相平衡曲线,并通过OLGA软件对水平管和弯管输送的水合物形成规律进行了模拟分析。结果表明:在低温高压条件下,水平管和弯管输送过程中均会有水合物形成,其生成过程是一种类似于盐类的结晶过程,通常包括成核和生长两个阶段,然后依靠流体颗粒之间的黏附力致使水合物聚集,与直管段相比,弯管段更容易产生水合物;水合物生成速率均由小到大,然后快速进入稳定阶段,最后趋于0。现场管线的水合物也多发生在弯管处,从而进一步验证了CO₂水合物的形成规律。因此,在管道输送过程中应避免高压出口和低温入口条件,保证管道安全运营。 