泥岩盖层的溶蚀作用机理实验——不同pH值盐水中溶蚀速率变化规律

doi:10.7623/syxb201708006

石油学报 ›› 2017, Vol. 38 ›› Issue (8): 916-924.DOI: 10.7623/syxb201708006

泥岩盖层的溶蚀作用机理实验——不同pH值盐水中溶蚀速率变化规律

周冰^1,2, 刘立³, 金之钧^1,2, 刘全有^1,2, 孟庆强^1,2, 朱东亚^1,2

1. 中国石油化工股份有限公司石油勘探开发研究院北京 100083;
2. 页岩油气富集机理与有效开发国家重点实验室北京 100083;
3. 吉林大学地球科学学院吉林长春 130061

收稿日期:2017-01-20 修回日期:2017-07-29 出版日期:2017-08-25 发布日期:2017-09-02
通讯作者: 周冰,女,1988年12月生,2010年获吉林大学资源勘查工程(油气)专业工学学士学位,2015年获吉林大学矿物学、岩石学、矿床学专业理学博士学位,现为中国石油化工股份有限公司石油勘探开发研究院博士后,主要从事含油气盆地中流体-岩石相互作用等方向的研究工作。Email:zhoubing.syky@sinopec.com
作者简介:周冰,女,1988年12月生,2010年获吉林大学资源勘查工程(油气)专业工学学士学位,2015年获吉林大学矿物学、岩石学、矿床学专业理学博士学位,现为中国石油化工股份有限公司石油勘探开发研究院博士后,主要从事含油气盆地中流体-岩石相互作用等方向的研究工作。Email:zhoubing.syky@sinopec.com
基金资助:
国家重点研发计划项目（2016YFB0600804）、国家自然科学基金青年基金项目（No.41602160）和中国博士后科学基金面上资助项目（2016M601225）资助。

Dissolution mechanism experiment of mudstone cap:the variation law of dissolution rate in different pH value brine

Zhou Bing^1,2, Liu Li³, Jin Zhijun^1,2, Liu Quanyou^1,2, Meng Qingqiang^1,2, Zhu Dongya^1,2

1. Sinopec Exploration & Production Research Institute, Beijing 100083, China;
2. State Key Laboratory of Shale Oil and Gas Enrichment Mechanisms and Effective Development, Beijing 100083, China;
3. College of Geoscience, Jilin University, Jilin Changchun 130061, China

Received:2017-01-20 Revised:2017-07-29 Online:2017-08-25 Published:2017-09-02

摘要/Abstract

摘要：

为了查明泥岩在不同性质流体环境中的溶蚀速率及随时间的变化关系，以松辽盆地南部青山口组黑色泥岩为研究对象，开展4组pH值分别为3、5、7、9的水岩相互作用实验研究，实验持续时间为153 d，泥岩粉末样品中黏土矿物含量为50%、石英和长石类矿物含量为35%、方解石为2%，还有少量菱铁矿和黄铁矿。结果分析表明，方解石在酸性流体中快速发生溶蚀溶解，Ca离子析出速率高于Mg、Si和Al离子；长石和黏土矿物溶蚀作用缓慢；在中性-碱性流体环境中形成了三水铝石片状矿物沉淀；方解石的快速溶蚀溶解消耗了酸性流体实验中的氢离子，导致溶液pH值由最初的3升高至7.5；4组实验开始的15 d内反应速率较快，反应至50 d时，各离子浓度基本保持稳定，即反应体系达到平衡状态，平衡状态下各组溶液的pH值为7~9，呈中性-弱碱性；据4组实验平衡状态下Si离子浓度计算得到的泥岩整体溶蚀速率为-13.29~-13.79 mol/（m²·s），较为接近同等条件下蒙皂石或高岭石单矿物的溶蚀速率，略高于泥岩中含量最高的伊利石单矿物溶蚀速率。实验研究表明，地层中CO₂或有机酸等酸性流体能够对泥岩盖层产生溶蚀溶解作用，而酸性流体对泥岩盖层封盖能力的破坏程度取决于长期水岩相互作用至系统平衡的过程；封闭的流体环境有利于保护泥岩盖层，泥岩中含有适量的碳酸盐矿物有利于缓冲酸性流体对泥岩盖层的溶蚀作用，起到保护盖层封闭性的作用，而碳酸盐等矿物的沉淀作用能够提高盖层的封盖能力。

关键词: 泥岩盖层, 水岩实验, 溶蚀溶解速率, 封闭流体环境, 溶蚀机理

Abstract:

To identify the dissolution rate of mudstone in different fluids and its changes with time, the black mudstone in Qingshankou Formation, southern Songliao Basin is taken as the study object to carry out four water-rock interaction experiments corresponding to the pH values of 3, 5, 7 and 9 respectively; the duration of these experiments is 150 days. In the mudstone powder samples, the content of clay mineral, quartz and feldspars, and calcite is 50%, 35%, and 2%, respectively; a small amount of siderite and pyrite exist. The results indicate that the calcite dissolves very fast in the acid fluid, and the precipitation rate of Ca ion is higher than that of Mg, Si and Al ions. The dissolution of feldspar and clay minerals are relatively slow. Gibbsite is precipitated in the medium-alkaline fluid environment. The hydrogen ion is consumed due to the fast dissolution of calcite in the acid fluid experiment, leading to the pH value of the solution raised from initial 3 to 7.5 correspondingly. In the first 15 days of four experiments, the reaction rate is relatively fast; each ion is maintained at steady state concentration when the reaction period is about 50 days, i.e., the reaction system reaches the balance state. Under such balance, the pH values of four neutral-alkaline solutions are ranged in 7-9. Through calculating the Si ion concentration under such a balance of four experiments, the overall dissolution rate of mudstone is-13.29——13.79 mol/(m²·s), approaching to the dissolution value of smectite or kaolinite in the same case, while slightly higher than that of illite with the highest content in mudstone. These experimental studies show that the CO₂, organic acid and other acid fluids in the formation can result in the corrosion and dissolution of mudstone cap, while the damage degree of acid fluid on mudstone-cap sealing ability depends on the process of long-term water-rock interaction till system balance. A confined fluid environment is favorable to the protection of mudstone cap. An appropriate content of carbonate minerals in mudstone is benefit for buffering the dissolution of acid fluid on mudstone cap, playing a protective role in cap sealing ability, while the precipitation of carbonate and other minerals can enhance the sealing ability of caps.

Key words: mudstone cap, water-rock interaction experiment, dissolution rate, confined fluid system, dissolution mechanism

中图分类号:

TE122

周冰, 刘立, 金之钧, 刘全有, 孟庆强, 朱东亚. 泥岩盖层的溶蚀作用机理实验——不同pH值盐水中溶蚀速率变化规律[J]. 石油学报, 2017, 38(8): 916-924.

Zhou Bing, Liu Li, Jin Zhijun, Liu Quanyou, Meng Qingqiang, Zhu Dongya. Dissolution mechanism experiment of mudstone cap:the variation law of dissolution rate in different pH value brine[J]. Acta Petrolei Sinica, 2017, 38(8): 916-924.

参考文献

[1] REZAEYAN A,TABATABAEI-NEJAD S A,KHODAPANAH E,et al.A laboratory study on capillary sealing efficiency of Iranian shale and anhydrite caprocks[J].Marine and Petroleum Geology,2015,66:817-828.
[2] 付广,王浩然,胡欣蕾.断裂带盖层油气封盖断接厚度下限的预测方法及其应用[J].中国石油大学学报:自然科学版,2015,39(3):30-37.FU Guang,WANG Haoran,HU Xinlei.Prediction method and application of caprock faulted-contact thickness lower limit for oil-gas sealing in fault zone[J].Journal of China University of Petroleum:Edition of Natural Science,2015,39(3):30-37.
[3] BOULIN P F,BRETONNIER P,VASSIL V,et al.Sealing efficiency of caprocks:experimental investigation of entry pressure measurement methods[J].Marine and Petroleum Geology,2013,48:20-30.
[4] 付广,吕延防,薛永超,等.泥岩盖层压力封闭的演化特征及其研究意义[J].石油学报,2000,21(3):41-44.FU Gang,LV Yanfang,XUE Yongchao,et al.Evolution characteristics of pressure sealing of mudstone caprock and its research significance[J].Acta Petrolei Sinica,2000,21(3):41-44.
[5] 胡国艺,汪晓波,王义凤,等.中国大中型气田盖层特征[J].天然气地球科学,2009,20(2):162-166.HU Guoyi,WANG Xiaobo,WANG Yifeng,et al.Cap rock characteristics of medium and large gas fields in China[J].Natural Gas Geoscience,2009,20(2):162-166.
[6] APLIN A C,LARTER S R.Fluid flow,pore pressure,wettability,and leakage in mudstone cap rocks[R].AAPG Hedberg Series,No.2,2005:1-12.
[7] LI S,DONG M,LI Z,et al.Gas breakthrough pressure for hydrocarbon reservoir seal rocks:implications for the security of long-term CO₂ storage in the Weyburn field[J].Geofluids,2005,5(4):326-334.
[8] 李双建,周雁,孙冬胜.评价盖层有效性的岩石力学实验研究[J].石油实验地质,2013,35(5):574-578.LI Shuangjian,ZHOU Yan,SUN Dongsheng.Rock mechanic experiment study of evaluation on cap rock effectiveness[J].Petroleum Geology and Experiment,2013,35(5):574-578.
[9] 袁际华,柳广弟,张英.相对盖层厚度封闭效应及其应用[J].西安石油大学学报:自然科学版,2008,23(1):34-36.YUAN Jihua,LIU Guangdi,ZHANG Ying.Thickness sealing effect of relative caprock and its application[J].Journal of Xi'an Shiyou University:Natural Science Edition,2008,23(1):34-36.
[10] 谈玉明,任来义,张洪安,等.深层气泥岩盖层封闭能力的综合评价——以东濮凹陷杜桥白地区沙河街组三段泥岩盖层为例[J].石油与天然气地质,2003,24(2):191-195.TAN Yuming,REN Laiyi,ZHANG Hong'an,et al.Comprehensive evaluation of sealing capacity of claystone in deep gas reservoir-an example of Es3 claystone caprock in Duqiaobai area in Dongpu depression[J].Oil&Gas Geology,2003,24(2):191-195.
[11] 金之钧,张刘平,杨雷,等.沉积盆地深部流体的地球化学特征及油气成藏效应初探[J].地球科学:中国地质大学学报,2002,27(6):659-665.JIN Zhijun,ZHANG Liuping,YANG Lei,et al.Primary study of geochemical features of deep fluids and their effectiveness on oil/gas reservoir formation in Sedimental Basins[J].Earth Science:Journal of China University of Geosciences,2002,27(6):659-665.
[12] 金之钧,朱东亚,孟庆强,等.塔里木盆地热液流体活动及其对油气运移的影响[J].岩石学报,2013,29(3):1048-1058.JIN Zhijun,ZHU Dongya,MENG Qingqiang,et al.Hydrothermal activites and influences on migration of oil and gas in Tarim Basin[J].Acta Petrologica Sinica,2013,29(3):1048-1058.
[13] 邸元,张园,WU Yushu.Gibbs自由能最小化法计算二氧化碳-烃-水系统相平衡[J].石油学报,2015,36(5):593-599.DI Yuan,ZHANG Yuan,WU Yushu.Phase equilibrium calculation of CO₂-hydrocarbons-water system based on Gibbs free energy minimization[J].Acta Petrolei Sinica,2015,36(5):593-599.
[14] 朱东亚,张殿伟,张荣强,等.中国南方地区灯影组白云岩储层流体溶蚀改造机制[J].石油学报,2015,36(10):1188-1198.ZHU Dongya,ZHANG Dianwei,ZHANG Rongqiang,et al.Fluid alteration mechanism of dolomite reservoirs in Dengying Formation,South China[J].Acta Petrolei Sinica,2015,36(10):1188-1198.
[15] 李凤昱,许天福,杨磊磊,等.不同碎屑矿物CO₂参与的水-岩作用效应数值模拟[J].石油学报,2016,37(9):1116-1128.LI Fengyu,XU Tianfu,YANG Leilei,et al.Numerical simulation for the water-rock interaction with the participation of CO₂ in different clastic minerals[J].Acta Petrolei Sinica,2016,37(9):1116-1128.
[16] 李宾飞,叶金桥,李兆敏,等.高温高压条件下CO₂-原油-水体系相间作用及其对界面张力的影响[J].石油学报,2016,37(10):1265-1272.LI Binfei,YE Jinqiao,LI Zhaomin,et al.Phase interaction of CO₂-oil-water system and its effect on interfacial tension at high temperature and high pressure[J].Acta Petrolei Sinica,2016,37(10):1265-1272.
[17] ORTOLEVA P J.Basin compartments and seals[M].Tulsa,Oklahoma,United States:American Association of Petroleum Geologists,1994:61.
[18] FLEURY M,PIRONON J,LE NINDRE Y M,et al.Evaluating sealing efficiency of caprocks for CO₂ storage:an overviewof the Geocarbone Integrity program and results[J].Energy Procedia,2011,4:5227-5234.
[19] ARMITAGE P J,FAULKNER D R,WORDEN R H,et al.Experimental measurement of,and controls on,permeability and permeability anisotropy of caprocks from the CO₂ storage project at the Krechba Field,Algeria[J].Journal of Geophysical Research:Solid Earth,2011,116(B12):12208.
[20] LIU Faya,LU Peng,GRIFFITH C,et al.CO₂-brine-caprock interaction:reactivity experiments on Eau Claire shale and a review of relevant literature[J].International Journal of Greenhouse Gas Control,2012,7:153-167.
[21] 康逊,胡文瑄,曹剑,等.钾长石和钠长石差异溶蚀与含烃类流体的关系——以准噶尔盆地艾湖油田百口泉组为例[J].石油学报,2016,37(11):1381-1393.KANG Xun,HU Wenxuan,CAO Jian,et al.Relationship between hydrocarbon bearing fluid and the differential corrosion of potash feldspar and albite:a case study of Baikouquan Formation in Aihu oilfield,Junggar Basin[J].Acta Petrolei Sinica,2016,37(11):1381-1393.
[22] ALKATTAN M,OELKERS E H,DANDURAND J L,et al.An experimental study of calcite and limestone dissolution rates as a function of pH from-1 to 3 and temperature from 25 to 80℃[J].Chemical Geology,1998,151(1/4):199-214.
[23] KÖHLER S J,DUFAUD F,OELKERS E H.An experimental study of illite dissolution kinetics as a function of pH from 1.4 to 12.4 and temperature from 5 to 50℃[J].Geochimica et Cosmochimica Acta,2003,67(19):3583-3594.
[24] BAUER A,BERGER G.Kaolinite and smectite dissolution rate in high molar KOH solutions at 35° and 80℃[J].Applied Geochemistry,1998,13(7):905-916.
[25] WIELAND E,STUMM W.Dissolution kinetics of kaolinite in acidic aqueous solutions at 25℃[J].Geochimica et Cosmochimica Acta,1992,56(9):3339-3355.
[26] HUERTAS F J,CHOU Lei,WOLLAST R.Mechanism of kaolinite dissolution at room temperature and pressure Part Ⅱ:kinetic study[J].Geochimica et Cosmochimica Acta,1999,63(19/20):3261-3275.
[27] CARROLL S A,WALTHER J V.Kaolinite dissolution at 25,60 and 80℃[J].American Journal of Science,1990,290(7):797-810.
[28] ZYSSET M,SCHINDLER P W.The proton promoted dissolution kinetics of K-montmorillonite[J].Geochimica et Cosmochimica Acta,1996,60(6):921-931.
[29] HUERTAS F J,CABALLERO E,DE CISNEROS C J,et al.Kinetics of montmorillonite dissolution in granitic solutions[J].Applied Geochemistry,2001,16(4):397-407.
[30] 张晓东.中国东北地区CO₂气藏成因及聚集规律分析[J].石油学报,2003,24(6):13-17.ZHANG Xiaodong.Analysis on genesis and accumulation law of carbon dioxide gas reservoirs in the northeastern areas of China[J].Acta Petrolei Sinica,2003,24(6):13-17.
[31] GILFILLAN S M V,LOLLAR B S,HOLLAND G,et al.Solubility trapping in formation water as dominant CO₂ sink in natural gas fields[J].Nature,2009,458(7238):614-618.
[32] LIU Faya,LU Peng,ZHU Chen,et al.Coupled reactive flow and transport modeling of CO₂ sequestration in the Mt.Simon sandstone formation,Midwest U.S.A.[J].International Journal of Greenhouse Gas Control,2011,5(2):294-307.
[33] 刘全有,金之钧,刘文汇,等.鄂尔多斯盆地海相层系中有机酸盐存在以及对低丰度高演化烃源岩生烃潜力评价的影响[J].中国科学:地球科学,2013,43(12):1975-1983.LIU Quanyou,JIN Zhijun,LIU Wenhui,et al.Presence of carboxylate salts in marine carbonate strata of the Ordos Basin and their impact on hydrocarbon generation evaluation of low TOC,high maturity source rocks[J].Science China:Earth Sciences,2013,56(12):2141-2149.
[34] CREDOZ A,BILDSTEIN O,JULLIEN M,et al.Experimental and modeling study of geochemical reactivity between clayey caprocks and CO₂ in geological storage conditions[J].Energy Procedia,2009,1(1):3445-3452.
[35] KASZUBA J P,JANECKY D R,SNOW M G.Experimental evaluation of mixed fluid reactions between supercritical carbon dioxide and NaCl brine:relevance to the integrity of a geologic carbon repository[J].Chemical Geology,2005,217(3/4):277-293.
[36] ALEMU B L,AAGAARD P,MUNZ I A,et al.Caprock interaction with CO₂:a laboratory study of reactivity of shale with supercritical CO₂ and brine[J].Applied Geochemistry,2011,26(12):1975-1989.
[37] KOHLER E,PARRA T,VIDAL O.Clayey cap-rock behavior in H2O-CO₂ media at low pressure and temperature conditions:an experimental approach[J].Clays and Clay Minerals,2009,57(5):616-637.
[38] LU Jiemin,MILLIKEN K,REED R M,et al.Diagenesis and sealing capacity of the middle Tuscaloosa mudstone at the Cranfield carbon dioxide injection site,Mississippi,U.S.A.[J].Environmental Geosciences,2011,18(1):35-53.

泥岩盖层的溶蚀作用机理实验——不同pH值盐水中溶蚀速率变化规律

Dissolution mechanism experiment of mudstone cap:the variation law of dissolution rate in different pH value brine

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 6

编辑推荐

Metrics

本文评价

[1]	鲁雪松, 柳少波, 田华, 马行陟, 于志超, 范俊佳, 桂丽黎, 刘强. 深层背斜圈闭中泥岩盖层完整性评价方法及其应用——以四川盆地川中地区震旦系气藏为例[J]. 石油学报, 2021, 42(4): 415-427.
[2]	史集建, 李丽丽, 杜琳, 宋宇官. 断层对盖层的动态破坏及其对油气输导的影响——以渤海湾盆地歧口凹陷港东断裂为例[J]. 石油学报, 2019, 40(8): 956-964.
[3]	王拥军　张宝民　董月霞　刘国勇　付卓文　单秀琴　张　静　刘静江. 南堡凹陷奥陶系潜山岩溶塌陷体识别、储层特征及油气勘探前景[J]. 石油学报, 2012, 33(4): 570-580.
[4]	翟光明, 何文渊. 塔里木盆地石油勘探实现突破的重要方向[J]. 石油学报, 2004, 25(1): 1-7.
[5]	付广, 吕延防, 薛永超, 杨勉. 泥岩盖层压力封闭的演化特征及其研究意义[J]. 石油学报, 2000, 21(3): 41-44.
[6]	戴贤忠, 李学田. 济阳坳陷第三系天然气藏盖层评价及其形成机理[J]. 石油学报, 1991, 12(2): 1-9.