砂岩CO2封存中的多相反应流

柴汝宽 ,  马倩倩 ,  Sepideh Goodarzi ,  Foo Yoong Yow ,  Branko Bijeljic ,  Martin J. Blunt

Engineering ›› 2025, Vol. 48 ›› Issue (5) : 87 -97.

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Engineering ›› 2025, Vol. 48 ›› Issue (5) : 87 -97. DOI: 10.1016/j.eng.2025.01.016
研究论文

砂岩CO2封存中的多相反应流

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Multiphase Reactive Flow During CO2 Storage in Sandstone

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摘要

CO2地质封存是极具前景的温室气体减排技术,但其核心的多相反应流动机制尚不明确。本研究使用某规划CO2封存储层的砂岩,应用X射线显微断层扫描测量稳态水-CO2相对渗透率并利用扫描电子显微镜(SEM)-能谱(EDS)分析反应前后砂岩矿物结构特征。结果表明,即使采用预先平衡的水溶液,CO2注入过程中仍存在化学反应且导致CO2相对渗透率及岩心绝对渗透率显著降低。原位孔隙尺度成像显示,绝对渗透率下降源于孔隙喉道收缩、连通性减弱以及拓扑复杂度增加。SEM-EDS分析进一步证实,矿物溶解(主要为长石、钠长石和方解石)、长石蚀变为高岭石以及微粒迁移是造成上述孔隙结构变化的关键因素。本研究首次通过原位成像揭示了化学反应对储层多相流动特性的影响规律,为矿物组成复杂砂岩中的CO2封存提供了重要参考。

Abstract

Geological CO2 storage is a promising strategy for reducing greenhouse gas emissions; however, its underlying multiphase reactive flow mechanisms remain poorly understood. We conducted steady-state imbibition relative permeability experiments on sandstone from a proposed storage site, complemented by in situ X-ray imaging and ex situ analyses using scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). Despite our use of a brine that was pre-equilibrated with CO2, there was a significant reduction in both CO2 relative permeability and absolute permeability during multiphase flow due to chemical reactions. This reduction was driven by decreased pore and throat sizes, diminished connectivity, and increased irregularity of pore and throat shapes, as revealed by in situ pore-scale imaging. Mineral dissolution, primarily of feldspar, albite, and calcite, along with precipitation resulting from feldspar-to-kaolinite transformation and fines migration, were identified as contributing factors through SEM–EDS analysis. This work provides a benchmark for storage in mineralogically complex sandstones, for which the impact of chemical reactions on multiphase flow properties has been measured.

关键词

CO2地质封存 / 多相反应流 / 化学反应 / 相对渗透率

Key words

Geological CO2 storage / Multiphase reactive flow / Geochemical reactions / Relative permeability

引用本文

引用格式 ▾
柴汝宽,马倩倩,Sepideh Goodarzi,Foo Yoong Yow,Branko Bijeljic,Martin J. Blunt. 砂岩CO2封存中的多相反应流[J]. 工程(英文), 2025, 48(5): 87-97 DOI:10.1016/j.eng.2025.01.016

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1 引言

人类活动排放的CO2占全球温室气体总量的75%以上,是加速气候变化的主要因素[1]。政府间气候变化专门委员会(IPCC)警告,若不紧急采取减排行动——2030年将全球排放量削减至2019年的43%——全球气温最快可能在2030年突破1.5 ℃的升幅阈值[2]。地质封存CO2是减缓气候变化的有效技术[34],具备永久封存数十亿吨CO2的潜力,对实现深度脱碳至关重要。砂岩构造因分布广泛、结构稳定、孔隙度高且能形成有效储盖组合,常被选作优先封存层位。然而,CO2注入过程中形成的酸性流体会与砂岩矿物发生反应[5]。数值模拟与实验研究[68]表明,此类化学反应将显著影响CO2注入性、封存容量及场址的长期封存效能等关键指标。

研究表明,CO2注入砂岩过程中的反应流动对岩石绝对渗透率的影响存在显著差异[9]。多数情况下渗透率呈下降趋势,主要归因于次生矿物沉淀[78,1011]、黏土与石英微粒迁移导致的孔喉堵塞[1214],以及岩体力学性质弱化[5]与水动力效应[15]。例如,Dávila等[16]的数值模拟研究发现钾长石、方解石和伊利石溶解时伴随着蒙脱石与沸石沉淀,导致孔隙度与渗透率同步降低。相反,Lamy-Chappuis等[17]、Zou等[18]、Tang等[19]、Sun等[20]以及Gholami与Raza [21]的研究发现,注入CO2后储层渗透率会升高,这可能因碳酸盐胶结物、碱性长石及黏土矿物溶解可提高渗透率。Sayegh等[22]则观察到渗透率动态演化现象:初期因微粒滞留封堵孔喉,导致渗透率下降;后期随微粒溶解而逐渐恢复。Al-Yaseri等[23]证实,绝对渗透率变化受砂岩矿物组成与注入水离子组成共同调控。注入低盐度CO2饱和水溶液时渗透率上升,而高盐度条件下则下降,这主要源于盐度差异对矿物溶解/沉淀及孔隙结构改造的影响。

目前,岩石-流体反应对多相渗流特性的针对性研究相对有限。Ge等[24]认为注入CO2饱和水会诱发微粒迁移与矿物反应,导致CO2相对渗透率下降,但水相相对渗透率基本不受影响。Gholami与Raza [21]发现,方解石沉淀、黏土矿物溶解及石英亲水性减弱共同作用,导致孔隙度与绝对渗透率升高,但CO2相对渗透率却降低。Kou等[25]还观察到,碳酸盐矿物溶解作用超过沉淀作用,致使孔隙度与渗透率上升、CO2润湿性增强,同时盐水相对渗透率下降而CO2相对渗透率升高。Sun等[20]提出,CO2注入过程中形成的碳酸与致密砂岩的反应提高孔隙度和渗透率,但CO2相对渗透率持续降低;注入水相对渗透率在低CO2饱和度时降低,随CO2饱和度升高而回升。这些成果凸显现有实验结论存在显著差异与不确定性,表明亟须深入探究反应流动的具体特征及内在机理。尤为关键的是,矿物成分变化对储层砂岩内相对渗透率的影响尚未被阐明。

现有大量研究利用高压釜与反应器研究CO2-水溶液-砂岩体系的反应特征。Liu等[26]将CO2注入砂岩/热水系统,观察到CO2可诱发砂岩基质溶解,同时驱动次生矿物(如硅酸铝和钙铝硅酸盐)沉淀。Kaszuba等[27]与Ilgen等[28]发现了菱镁矿沉淀,并注意到硅酸盐矿物及方解石/白云石在CO2作用下的溶解。Fu等[29]和Lu等[30]报道了大量长石溶解及次生矿物(如铁矿物和高岭石)沉淀。此外,Dawson等[31]和Pearce等[3233]发现,在含CO2的盐水中Berea砂岩内碳酸盐胶结物溶解时,低比表面积钾长石颗粒仍保持未反应状态;在含杂质CO2注入富含黏土的泥岩岩心时,他们还观察到碳酸盐与硅酸盐矿物溶解/沉淀、重晶石/含铁氧化物/黏土/石膏沉淀、富铁绿泥石中的离子浸出、黏土结构破坏以及微粒运移。Carroll等[34]提出,CO2-矿物反应以黏土溶解及次生矿物(如无定形二氧化硅和高岭石)沉淀为主。Fuchs等[35]将砂岩在CO2饱和水溶液中老化4~8周,观察到黏土胶结消失、石英与钾长石颗粒暴露增多及砂岩表面明显粗糙化。虽然这些研究为理解CO2注入过程中的矿物反应提供了重要见解,但未能定量关联矿物反应与岩石物性变化,亦未能充分揭示砂岩地层中多相反应流动的复杂性。

本文通过原位孔隙尺度成像结合稳态相对渗透率实验,耦合非原位扫描电子显微镜-能谱(SEM-EDS)分析,针对CO2注入砂岩过程中发生的化学反应及对多相流动影响开展研究。核心目标为:①在宏观尺度表征多相渗流行为;②在微观尺度识别孔隙结构演化;③在分子尺度阐明CO2-水溶液-矿物内在反应机制。

2 材料与方法

2.1 样品与流体物性

本研究样品采用枯竭气藏砂岩柱状岩心[直径为(6.03 ± 0.05) mm,长(20.05 ± 0.05) mm],其氦气孔隙度为25.0%,绝对渗透率为(185 ± 10) mD(1 mD = 0.987 × 10-11 cm2)。实验流体为含30 wt%碘化钾(KI)的水溶液[参照Lin等[36]方法以增强X射线断层扫描(CT)成像对比]和超临界CO2(50 ℃/8 MPa)。CO2和水溶液黏度分别为(0.020 ± 0.001) mPa∙s [37]与 (0.60 ± 0.05) mPa∙s [38],界面张力约为35 mN∙m-1 [39]。

2.2 实验方法

2.2.1 稳态相对渗透率实验

岩样经24 h真空烘箱干燥后,采用Viton套管封装,通过配有连接管路的端盖密封,再组装于岩心夹持器中。将岩心夹持器置于CT扫描仪(Zeiss Xradia Versa 510)内,连接水溶液/CO2注入装置、流出物接收泵、围压泵、反应器及压力传感器。如图1所示,实验采用循环水浴维持泵组温度,利用比例积分微分(PID)温控系统驱动的加热套精确控制岩心夹持器温度[4041]。为抑制实验过程中CO2与水溶液的传质,预先在反应器中对水溶液进行CO2饱和处理。

在2.0 MPa围压条件下,首先以6.5 µm分辨率对样品进行初始扫描。随后进行2.9 µm的高分辨率扫描,以表征孔隙结构、接触角及界面曲率特征。持续注入CO2 30 min以驱替样品内细颗粒物,随后对系统真空处理12 h。以0.20 mL∙min-1、0.50 mL∙min-1及1.00 mL∙min-1速度注入水溶液,同步监测压力并基于达西定律计算绝对渗透率。随后将注入流速降至0.20 mL∙min-1进行扫描,获取岩样完全饱和水溶液状态图像。采用稳态法测定相对渗透率:维持总流速为0.20 mL∙min-1,按水溶液体积分数(fw = 0.0、0.05、0.1、0.3、0.7、0.9、1.0)逐级测试。其中fw = 1.0的数据来自邻近钻取的替代岩心(具有相近孔隙度与渗透率),此替代岩心经过完全相同的实验处理。每级实验约24 h达稳态后按相同的成像方案扫描。本实验流程遵循Krevor等[42]与Gao等[43]建立的标准化方法。

全部驱替过程完成后,取出岩样,测定沿程管路压降。将实测压差数据减去管路压降后,计算绝对渗透率与相对渗透率。随后将岩样置于真空烘箱干燥24 h,再次扫描以评估孔隙结构与矿物组成的演变特征。最终按前述流程复测岩样绝对渗透率。

显微CT成像采用Zeiss XRM-510系统,设定X射线能量为80.0 keV、功率为7.0 W。单次扫描采集3201个投影,曝光时长为2 s,像素合并因子取2。进行中心漂移校正与射线硬化效应校正后,采用Zeiss Reconstructor软件实施图像重建。通过归一化处理并拼接四组图像,构建完整的样品三维数据集。以干燥样品扫描数据为空间基准,应用Lanczos算法重采样实现全周期图像空间配准,并采用非局部均值滤波技术抑制噪声、平滑图像,同时完整保留结构边缘特征。

本文采用差分成像、交互式阈值分割与交互式顶帽(top-hat)滤波分割的组合方法实施图像分割,精确识别岩相-水相-CO2相。基于原始图像与干燥图像的差分运算突出水相;基于饱和图像与原始图像的差分运算突出CO2相。通过交互式阈值分割识别水/CO2相大尺度团簇结构,同时利用交互式顶帽提取微观特征,最终融合重建完整的水相与CO2相三维分布。基于分割的全尺度岩心扫描图像定量饱和度;其余物性参数[孔隙-喉道半径分布、配位数、界面曲率、接触角、形状因子(孔隙棱角性)]则依据Raeini等[44]、AlRatrout等[45]及Sajjad等[46]建立的方法,从分割的高分辨局部图像中提取。

2.2.2 SEM和EDS分析

使用Hitachi TM4000Plus SEM-EDS在加速电压为15 kV、电子束流为10 nA、环境温度为20 ℃条件下表征CO2注入前后纳米尺度岩石矿物演化特征。基于同一岩心钻取的三个相邻样品,系统观测CO2注入前矿物共性特征;使用稳态相对渗透率实验样品,表征CO2注入后矿物特性变化。首先采用30倍低倍成像与EDS元素面分布分析组合,获取样品截面信息,识别矿物类型与空间分布[47];继而在各视场进行高倍成像,同步进行矿物中心点EDS分析,精确表征多类型矿物微观形貌与组分特征[48]。通过在多个样品中重复分析上述矿物特征,确保数据一致性与可靠性。

3 结果与讨论

3.1 反应流特性

图2为实测相对渗透率、压力梯度及含水饱和度数据[2021,24,31,4951]。图2(a)和(b)表明,fw = 0时束缚水饱和度约为0.12,对应CO2相对渗透率0.47,此低束缚水饱和度预示岩样具高CO2封存潜力[49]。fw增至0.05时,盐水饱和度骤升至0.51,CO2相对渗透率急剧衰减至0.013。这一现象归因于润湿相盐水快速占据小尺度孔喉网络,捕集CO2并阻碍CO2运移,导致含水饱和度激增与CO2相渗能力骤降。随含水饱和度持续升高,水相渗能力稳定增长,CO2相渗能力持续衰减。此过程中水形成连续流动通道,其渗流能力显著提升[49,52],同时CO2运移路径被逐步阻断[图2(e)]。

本实验结果整体趋势与同层位大尺寸岩样(直径为34 mm)稳态驱替实验的岩心分析数据(SCAL)吻合,验证了结果的复现性与测量精度。相较于无地球化学反应的砂岩研究[24,42,5051],如图2(a)所示,反应流动体系的显著特征是CO2相对渗透率降低。以Krevor等[42]研究的Tuscaloosa砂岩为例,在绝对渗透率(220 mD与本样185 mD)及孔隙度(23.6%与本样25%)相近条件下,反应体系中CO2相对渗透率仅为非反应体系的十分之一。此CO2相渗显著降低的规律与Sun等[20]和Ge等[24]的发现一致,即基于致密砂岩与Berea砂岩的稳态/非稳态渗流实验证实,注入流体-岩石相互作用可增强水相渗能力并促进CO2相捕集效应。然而,绝对渗透率变化的作用机理存在本质差异,本研究观测到CO2作用后绝对渗透率从(185 ± 10) mD下降至(110 ± 8) mD,而前人研究均报道渗透率上升现象。

CO2相对渗透率下降与绝对渗透率下降的协同作用削减了CO2注入能力及封存容量,此效应在室内实验与场地实施中均存在。需系统研究岩石物性参数演变规律,才能完整揭示此现象的深层作用机制,如下节所述。

3.2 孔隙结构分析

图3为CO2作用前后孔喉结构定量解析结果,呈现出显著的结构演化特征。图3(a)直观显示CO2注入诱发的孔隙生成/扩张与收缩现象,其定量表征结果如图3(b)所示。孔隙生成与扩张(表现为孔隙度升高)主要由矿物溶解与微粒迁移驱动[2021,24];而观测到的显著的孔隙收缩现象(伴随孔隙度下降),可能源于次生矿物沉淀与微粒运移堵塞[25]。虽然先前的研究已通过SEM表征此类矿物反应[2933],但本研究首次获得原位孔隙尺度动态演化证据。值得注意的是,尽管平均孔隙度上升,但非均质性加剧导致多相渗流受阻,体现为渗透率降低。

孔隙/喉道尺寸、配位数及形状因子可定量表征CO2注入过程孔隙空间变化特征。配位数(孔隙连通喉道数)在CO2作用后显著下降[图3(d)],表明孔隙网络连通性减弱。如图3(e)所示,CO2注入引起孔喉尺寸轻微减小,同时孤立孔隙单元数量显著增加,这意味着有效渗流通道锐减。此现象与Meng等[53]的研究结论吻合——其基于纳米孔隙中CO2封存的分子模拟,有力证实小尺度孔隙更有利于提升CO2捕集效率。图3(f)所示孔喉形状因子均降低,揭示注入后孔隙几何结构不规则性加剧[44],此变化直接导致渗流阻力上升。孔喉尺寸缩减、连通性衰减与几何不规则性加剧的协同作用,限制了有效渗流通道并导致流动阻力显著增大。此机制合理解释了平均孔隙度升高而绝对渗透率下降的表观矛盾。

既有岩石物性演化研究长期集中于孔隙度表征[14,1718,21],或采用核磁共振(NMR)分析孔径变化[20,25]。然而,孤立分析孔隙度具有误导性,即便矿物溶解显著增大孔隙空间,连通性变差仍导致绝对渗透率与相对渗透率显著降低。

图4展示接触角及水溶液-CO2界面曲率的分布特征。图4(a)和(c)定量表征两个核心特征:其一为水溶液体积分数(fw)升高导致接触角增大,主峰值从fw = 0.05时的62.5°增至fw = 0.9时的71.5°,证实体系呈弱亲水特性,并揭示CO2注入诱发的地球化学反应削弱岩石亲水性(与Gholami和Raza [21]的离位液滴形态法研究一致);其二为接触角分布范围随fw增加显著拓宽,这反映润湿性非均质性增强(弱亲水区域尤甚)。润湿性演变提升水相渗能力并强化CO2相圈闭效应(相对渗透率数据佐证),其深层机理受复杂矿物反应调控,详见下节讨论。

随水体积分数(fw)增加,CO2-水溶液界面平均曲率[图4(b)、(d)]逐渐降低,峰值从fw = 0.05时的0.046 μm-1降至fw = 0.9时的0.029 μm-1。该趋势表明界面趋于平坦光滑,与观测到的岩石亲水性减弱一致。基于Young-Laplace方程分析表明,毛细管压力从fw = 0.05时的3.2 kPa降至fw = 0.9时的2.0 kPa,符合驱替过程中毛细管压力随水相饱和度升高而降低的理论预期。相较于低fw条件,高fw下毛细管压力降低导致CO2圈闭效应减弱[25],从而提升CO2流动能力,这与接触角及相对渗透率演化规律实现相互印证。

本研究首次实现接触角与界面曲率的原位孔隙尺度表征,建立了岩石物性演化与相对渗透率变化的直接关联,为地下环境多相渗流驱动机制提供直接孔隙尺度证据。

3.3 矿物反应

图5所示SEM-EDS元素分布揭示了砂岩矿物组成及CO2作用下的矿物演变特征。未暴露于CO2时,砂岩元素以O、Si、C、Fe、Al、Ca、K、Na、S为主,如图5(a)所示。结合元素分布规律及前人研究[47],我们推测主要矿物包括石英、长石、钠长石、高岭石、方解石、石膏及菱铁矿,其中碳元素可能源于衰竭气藏残余有机质[56]。石英与长石构成主要骨架;钠长石、高岭石、方解石和石膏则作为胶结物呈分散分布。

CO2注入后元素分布[图5(b)]显示,仅检出O、Si、C、Al、K、Fe元素,表明石英、长石、高岭石及菱铁矿存在。值得注意的是,钠长石、方解石及石膏对应的Na、Ca、S元素消失,证实此类矿物在CO2作用中发生显著反应,这是驱动岩石物性、界面性质及相对渗透率演变的深层机制[32,48]。其中方解石溶解已有广泛报道[18,21,25],而钠长石、石膏等矿物的反应机制将通过后续高分辨图像深入分析。

图6揭示矿物对CO2注入的差异响应:石英反应前表面光滑完整[图6(a)],反应后出现微蚀坑[图6(b)];长石反应前虽有表面蚀变仍维持结构完整[5,51],如图6(c)所示,反应后则呈现层状通道、蚀坑及晶体破碎等显著形貌演化[图6(d)]。此形貌演变协同长石碎屑迁移效应,可能显著影响孔隙结构与渗透率。

主要胶结物高岭石在CO2作用前呈书册状结构广泛充填孔隙[图6(e)];作用后,其发生迁移聚集,堵塞小尺度孔喉[图6(f)]。这一过程加剧了储层非均质性并阻碍多相渗流,与Othman等[13]和De Silva等[14]的SEM观测结果一致。此外,观测发现长石表面新生微晶高岭石[图6(j)~(k)],这可能是长石/钠长石与CO2反应转化为高岭石所致,进一步加剧了孔喉堵塞与渗透率下降。该反应对CO2封存具有关键作用,与Wang等[57]的研究结论一致。Wang等[57]通过融合实验、非稳态试井与数值模拟,首次实现了低渗砂岩储层矿物沉淀全生命周期贡献的量化表征。初始呈板状解理晶体的钠长石[图6(g)]在CO2作用后消失,推测系其与实验盐水中过量K⁺离子反应转化为钾长石所致。

方解石具菱面体解理特征,作为胶结物固结矿物颗粒[图6(h)]。其接触CO2后的溶解现象已获充分研究,溶解作用可能促进细粒迁移[12]。石膏具有类似胶结作用,作用前已呈局部破碎[图6(i)];而CO2作用后其完全消失,这归因于持续驱替引发的破碎迁移效应。

4 结论

多相反应流在CO2注入多矿物砂岩过程中起关键控制作用,直接影响注入能力、封存容量及长期安全性。为阐明其机理与影响,本研究选取预期CO2封存储层中具复杂矿物组成的砂岩岩心,结合原位X射线成像与稳态相对渗透率实验,以及非原位扫描电镜-能谱分析技术进行研究。核心发现如下:

(1)多相反应流导致CO2相对渗透率与绝对渗透率显著下降;

(2)岩石物性变化表现为孔喉尺寸缩减、连通性下降及孔隙不规则性增加;

(3)主要机制包括矿物溶解、长石-高岭石转化诱发的沉淀及细粒迁移。

本研究首次实现了CO2注入复杂矿物组成砂岩的多相反应流的原位孔隙保证与分析,为提升CO2注入能力、优化封存容量及保障长期安全奠定了科学基础。现场实施需详尽表征矿物组成;针对复杂砂岩地层,应采用定制化方案(如前述离子调控盐水注入)以抑制不利反应。未来研究应聚焦于建立渗透率-岩石物性-地球化学反应的定量模型,进而提升非均质储层中CO2封存效率与安全性的预测精度。

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