CH_3COO~-与Ca~(2+)的络合效应对方解石溶蚀的影响
|
摘要
为探究不同温度下CH_3COO~-与Ca~(2+)的络合效应对方解石的影响以及方解石解理面的溶蚀过程,以方解石为研究对象,在静态条件下开展乙酸溶蚀方解石实验,利用Gaussian模拟软件从量子化学的角度计算络合反应的结合能,并结合SEM等表征手段,分析结合能与溶蚀量之间的关系,观测解理面上次生孔—带—锥的演化过程。结果表明:100℃时,CH_3COO~-与Ca~(2+)的络合效应最强,与溶液中离子的自由扩散以及氢质子的交换作用相结合,使得乙酸对方解石的溶蚀最为剧烈;温度升高或降低,络合反应的结合能均呈现不同程度的减小,络合效应被削弱,使得方解石的溶蚀量减少;晶体解理面上的CO_3~(2-)与Ca~(2+)在不同方向上的排列方式存在差异,造成活性位点沿各个方向的溶解速率不同,导致溶蚀晶锥的形成;晶锥只是方解石溶蚀过程中的一种阶段性产物,随着反应的进行,其规模会逐渐变小甚至消失直至裸露出下方新的晶面。
The complex effect of CH_3COO~- and Ca~(2+)on the dissolution of calcite at different temperatures and the dissolution process of cleavage plane of calcite were investigated. The calcite was corroded by acetic acid under static conditions. And the Gaussian simulation software was used to calculate the binding energy of the complex reaction from the perspective of quantum chemistry to analyze the relationship between the binding energy and the corrosion amount. The SEM as well as other characterization methods was conducted to observe the evolution of secondary pore-band-cone on cleavage plane. The results show that the complex effect between acetate and calcium ion is the strongest at 100 ℃, which is combined with the free diffusion of ions in the solution and the exchange function of hydrogen protons to make acetic acid corroding calcite most intense. Increasing or decreasing temperature reduces the binding energy of complex reaction in various extents, which weakens the complex effect and decreases the erosion amount. The arrangement of CO_3~(2-) and Ca~(2+) in different directions on crystal cleavage plane shows the difference, which results in different dissolution rates of active sites in all directions and leads to corrosion cones eventually. However, the cones were merely phased products in the dissolution process of calcite. With the progress of reaction, the scale of crystal cone would become smaller and even disappear until new crystal plane below is exposed.
The complex effect of CH_3COO~- and Ca~(2+)on the dissolution of calcite at different temperatures and the dissolution process of cleavage plane of calcite were investigated. The calcite was corroded by acetic acid under static conditions. And the Gaussian simulation software was used to calculate the binding energy of the complex reaction from the perspective of quantum chemistry to analyze the relationship between the binding energy and the corrosion amount. The SEM as well as other characterization methods was conducted to observe the evolution of secondary pore-band-cone on cleavage plane. The results show that the complex effect between acetate and calcium ion is the strongest at 100 ℃, which is combined with the free diffusion of ions in the solution and the exchange function of hydrogen protons to make acetic acid corroding calcite most intense. Increasing or decreasing temperature reduces the binding energy of complex reaction in various extents, which weakens the complex effect and decreases the erosion amount. The arrangement of CO_3~(2-) and Ca~(2+) in different directions on crystal cleavage plane shows the difference, which results in different dissolution rates of active sites in all directions and leads to corrosion cones eventually. However, the cones were merely phased products in the dissolution process of calcite. With the progress of reaction, the scale of crystal cone would become smaller and even disappear until new crystal plane below is exposed.
引文
[1] LUTTGE A,WINKLER U,LASAGA A C.Interferometric study of the dolomite dissolution:a new conceptual model for mineral dissolution [J].Geochim Cosmochim Acta,2016,67(6):1099-1116.
[2] MAST M A,DREVER J I.The effect of oxalate on the dissolution rates of oligoclase and tremolite [J].Geochimicaet Acta,2015,5(51):2559-2568.
[3] MORSE J W,ARVIDSON R S.The dissolution kinetics of major sedimentary carbonate minerals [J].EarthScience Reviews,2012,58(2):51-84.
[4] GILES M R,BOER R B.Secondary porosity:creation of enhanced porosities in the subsurface from the dissolution of carbonate cements as a result of cooling formation waters [J].Marine and Petroleum Geology,2012,6(3):261-269.
[5] LASAGA A C,BLUM A E.Surface chemistry,etch pits and mineral-water reactions[J].Geochimica et Cosmochimica Acta,2009,50(10):2363-2379.
[6] 郭春清,沈忠民,张林晔.砂岩储层中有机酸对主要矿物的溶蚀作用及机制研究综述[J].地球化学,2016,31(3):53-57.GUO Chunqing,SHEN Zhongmin,ZHANG Linye.Studies on the dissolution and mechanism of organic acids in the sandstone reservoirs[J].Geochemistry,2016,31(3):53-57.
[7] 季汉成,徐珍.深部碎屑岩储层溶蚀作用实验模拟研究[J].地质学报,2015,81(2):212-219.JI Hancheng,XU Zhen.Experimental simulation of clastic reservoirs dissolution in deep [J].Geosciences,2015,81(2):212-219.
[8] TENG H H.Controls by saturation state on etch pit formation during calcite dissolution [J].Geochimica Cosmochimica Acta,2004,68(2):253-262.
[9] FREDD C N,FOGLER H S.The kinetics of calcite dissolution in acetic acid solutions [J].Chem Eng Sci,1998,53(2):3863-3869.
[10] 杨俊杰,曹以临.碳酸盐岩溶蚀动力学模拟实验[J].中国岩溶,2012,56(1):63-69.YANG Junjie,CAO Yilin.Carbonate rock dissolution kinetics simulation experiment[J].Chinese Karst,2012,56(1):63-69.
[11] 崔振昂,鲍征宇,张天付.埋藏条件下碳酸盐岩溶解动力学实验研究[J].石油天然气学报,2007,29(3):230-233.CUI Zhen'ang,BAO Zhengyu,ZHANG Tianfu.Experimental study on dissolution kinetics of carbonate rocks under buried conditions[J].Journal of Oil and Gas Technology,2007,29(3):230-233.
[12] 佘敏,寿建峰,沈安江,等.碳酸盐岩溶蚀规律与孔隙演化实验研究[J].石油勘探与开发,2016,43(4):49-54.SHE Min,SHOU Jianfeng,SHEN Anjiang,et al.Experimental study on dissolution and pore evolution of carbonate rocks[J].Petroleum Exploration and Development,2016,43(4):49-54.
[13] 黄思静.方解石和白云石溶蚀实验热力学模型及地质意义[J].矿物岩石,2003,23(1):113-116.HUANG Sijing.Experimental thermodynamic model of calcite and dolomite dissolution and its geological significance[J].Mineralogy and Rock,2003,23(1):113-116.
[14] LARTER S R,APLIN A C,CORBETT P W M.Reservoir geochemistry:a link between reservoir geology and engineering[J].SPE Reservoir Engineering,2011,12(1):12-17.
[15] SJOBERGEL,RICKARD D.Calcite dissolution kinetics:surface speciation and the origin of the variable pH dependence[J].Chem Geol,2009,3(42):119-128.
[16] PLUMMERL N,WIGLEY T.A critical review of the kinetics of calcite dissolution and precipitation in chemical modelling of aqueous systems [J].Chem Soc,2000,14(36):538-547.
[17] 孟繁奇,李春柏,刘立.CO2-水-解石相互作用实验[J].地质科技情报,2013,32(3):1-9.MENG Fanqi,LI Chunbai,LIU Li.Experiments on the interaction between CO2 and brackish water[J].Geological Science and Technology Information,2013,32(3):1-9.
[18] 陈圆圆.碳酸盐岩溶解-沉淀热力学模型及其在塔北地区的应用[J].沉积学报,2012,30(2):219-230.CHEN Yuanyuan.Thermodynamic model of carbonate rock dissolution and precipitation and its application in Tabei area[J].Journal of Sedimentology,2012,30(2):219-230.
[19] PUTNIS C V,JIMéNEZ-LóPEZ C.An atomic force microscopy study of calcite dissolution in saline solutions:the role of magnesium ions [J].Geochimica et Cosmochimica Acta,2009,73(11):3201-3217.
[20] 寿建峰,佘敏,沈安江.深层条件下碳酸盐岩溶蚀改造效应的模拟实验研究[J].矿物岩石地球化学通报,2016,35(5):174-185.SHOU Jianfeng,SHE Min,SHEN Anjiang.Simulated experimental study on the dissolution of carbonate rocks under deep conditions[J].Bulletin of Mineral Rocks and Geochemistry,2016,35(5):174-185.
[21] 张少敏,操应长,王艳忠.牛庄洼陷西南部沙三中亚段浊积岩储层成岩作用与物性演化[J].中国石油大学学报(自然科学版),2017,4(2):17-22.ZHANG Shaomin,CAO Yingchang,WANG Yanzhong.Diagenesis and physical evolution of turbidite reservoirs in the middle third member in the southwest of Niuzhuang Depression [J].Journal of China University of Petroleum(Edition of Natural Science),2017,4(2):17-22.
[22] 朱文慧,曲希玉,邱隆伟.盐酸及乙酸介质中的碳酸盐岩溶蚀表面特征及机制:以南堡凹陷为例[J].矿物岩石地球化学通报,2015,34(3):619-625.ZHU Wenhui,QU Xiyu,QIU Longwei.Surface features and mechanism of carbonate rock erosion in hydrochloric and acetic acid media:a case study of Nanpu Sag[J].Bulletin of Mineral Rocks,2015,34(3):619-625.
[23] 梁超,吴靖,姜在兴,等.有机质在页岩沉积成岩过程及储层形成中的作用[J].中国石油大学学报(自然科学版),2017,41(6):1-8.LIANG Chao,WU Jing,JIANG Zaixing,et al.Significances of organic matters on shale deposition,diagenesis process and reservoir formation [J].Journal of China University of Petroleum(Edition of Natural Science),2017,41(6):1-8.
[2] MAST M A,DREVER J I.The effect of oxalate on the dissolution rates of oligoclase and tremolite [J].Geochimicaet Acta,2015,5(51):2559-2568.
[3] MORSE J W,ARVIDSON R S.The dissolution kinetics of major sedimentary carbonate minerals [J].EarthScience Reviews,2012,58(2):51-84.
[4] GILES M R,BOER R B.Secondary porosity:creation of enhanced porosities in the subsurface from the dissolution of carbonate cements as a result of cooling formation waters [J].Marine and Petroleum Geology,2012,6(3):261-269.
[5] LASAGA A C,BLUM A E.Surface chemistry,etch pits and mineral-water reactions[J].Geochimica et Cosmochimica Acta,2009,50(10):2363-2379.
[6] 郭春清,沈忠民,张林晔.砂岩储层中有机酸对主要矿物的溶蚀作用及机制研究综述[J].地球化学,2016,31(3):53-57.GUO Chunqing,SHEN Zhongmin,ZHANG Linye.Studies on the dissolution and mechanism of organic acids in the sandstone reservoirs[J].Geochemistry,2016,31(3):53-57.
[7] 季汉成,徐珍.深部碎屑岩储层溶蚀作用实验模拟研究[J].地质学报,2015,81(2):212-219.JI Hancheng,XU Zhen.Experimental simulation of clastic reservoirs dissolution in deep [J].Geosciences,2015,81(2):212-219.
[8] TENG H H.Controls by saturation state on etch pit formation during calcite dissolution [J].Geochimica Cosmochimica Acta,2004,68(2):253-262.
[9] FREDD C N,FOGLER H S.The kinetics of calcite dissolution in acetic acid solutions [J].Chem Eng Sci,1998,53(2):3863-3869.
[10] 杨俊杰,曹以临.碳酸盐岩溶蚀动力学模拟实验[J].中国岩溶,2012,56(1):63-69.YANG Junjie,CAO Yilin.Carbonate rock dissolution kinetics simulation experiment[J].Chinese Karst,2012,56(1):63-69.
[11] 崔振昂,鲍征宇,张天付.埋藏条件下碳酸盐岩溶解动力学实验研究[J].石油天然气学报,2007,29(3):230-233.CUI Zhen'ang,BAO Zhengyu,ZHANG Tianfu.Experimental study on dissolution kinetics of carbonate rocks under buried conditions[J].Journal of Oil and Gas Technology,2007,29(3):230-233.
[12] 佘敏,寿建峰,沈安江,等.碳酸盐岩溶蚀规律与孔隙演化实验研究[J].石油勘探与开发,2016,43(4):49-54.SHE Min,SHOU Jianfeng,SHEN Anjiang,et al.Experimental study on dissolution and pore evolution of carbonate rocks[J].Petroleum Exploration and Development,2016,43(4):49-54.
[13] 黄思静.方解石和白云石溶蚀实验热力学模型及地质意义[J].矿物岩石,2003,23(1):113-116.HUANG Sijing.Experimental thermodynamic model of calcite and dolomite dissolution and its geological significance[J].Mineralogy and Rock,2003,23(1):113-116.
[14] LARTER S R,APLIN A C,CORBETT P W M.Reservoir geochemistry:a link between reservoir geology and engineering[J].SPE Reservoir Engineering,2011,12(1):12-17.
[15] SJOBERGEL,RICKARD D.Calcite dissolution kinetics:surface speciation and the origin of the variable pH dependence[J].Chem Geol,2009,3(42):119-128.
[16] PLUMMERL N,WIGLEY T.A critical review of the kinetics of calcite dissolution and precipitation in chemical modelling of aqueous systems [J].Chem Soc,2000,14(36):538-547.
[17] 孟繁奇,李春柏,刘立.CO2-水-解石相互作用实验[J].地质科技情报,2013,32(3):1-9.MENG Fanqi,LI Chunbai,LIU Li.Experiments on the interaction between CO2 and brackish water[J].Geological Science and Technology Information,2013,32(3):1-9.
[18] 陈圆圆.碳酸盐岩溶解-沉淀热力学模型及其在塔北地区的应用[J].沉积学报,2012,30(2):219-230.CHEN Yuanyuan.Thermodynamic model of carbonate rock dissolution and precipitation and its application in Tabei area[J].Journal of Sedimentology,2012,30(2):219-230.
[19] PUTNIS C V,JIMéNEZ-LóPEZ C.An atomic force microscopy study of calcite dissolution in saline solutions:the role of magnesium ions [J].Geochimica et Cosmochimica Acta,2009,73(11):3201-3217.
[20] 寿建峰,佘敏,沈安江.深层条件下碳酸盐岩溶蚀改造效应的模拟实验研究[J].矿物岩石地球化学通报,2016,35(5):174-185.SHOU Jianfeng,SHE Min,SHEN Anjiang.Simulated experimental study on the dissolution of carbonate rocks under deep conditions[J].Bulletin of Mineral Rocks and Geochemistry,2016,35(5):174-185.
[21] 张少敏,操应长,王艳忠.牛庄洼陷西南部沙三中亚段浊积岩储层成岩作用与物性演化[J].中国石油大学学报(自然科学版),2017,4(2):17-22.ZHANG Shaomin,CAO Yingchang,WANG Yanzhong.Diagenesis and physical evolution of turbidite reservoirs in the middle third member in the southwest of Niuzhuang Depression [J].Journal of China University of Petroleum(Edition of Natural Science),2017,4(2):17-22.
[22] 朱文慧,曲希玉,邱隆伟.盐酸及乙酸介质中的碳酸盐岩溶蚀表面特征及机制:以南堡凹陷为例[J].矿物岩石地球化学通报,2015,34(3):619-625.ZHU Wenhui,QU Xiyu,QIU Longwei.Surface features and mechanism of carbonate rock erosion in hydrochloric and acetic acid media:a case study of Nanpu Sag[J].Bulletin of Mineral Rocks,2015,34(3):619-625.
[23] 梁超,吴靖,姜在兴,等.有机质在页岩沉积成岩过程及储层形成中的作用[J].中国石油大学学报(自然科学版),2017,41(6):1-8.LIANG Chao,WU Jing,JIANG Zaixing,et al.Significances of organic matters on shale deposition,diagenesis process and reservoir formation [J].Journal of China University of Petroleum(Edition of Natural Science),2017,41(6):1-8.