Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.
Los Alamos National Laboratory , Los Alamos, New Mexico 87545, United States.
Environ Sci Technol. 2017 Jan 3;51(1):692-698. doi: 10.1021/acs.est.6b03290. Epub 2016 Dec 21.
Mineral reactions during CO sequestration will change the pore-size distribution and pore surface characteristics, complicating permeability and storage security predictions. In this paper, we report a small/wide angle scattering study of wellbore cement that has been exposed to carbon dioxide for three decades. We have constructed detailed contour maps that describe local porosity distributions and the mineralogy of the sample and relate these quantities to the carbon dioxide reaction front on the cement. We find that the initial bimodal distribution of pores in the cement, 1-2 and 10-20 nm, is affected differently during the course of carbonation reactions. Initial dissolution of cement phases occurs in the 10-20 nm pores and leads to the development of new pore spaces that are eventually sealed by CaCO precipitation, leading to a loss of gel and capillary nanopores, smoother pore surfaces, and reduced porosity. This suggests that during extensive carbonation of wellbore cement, the cement becomes less permeable because of carbonate mineral precipitation within the pore space. Additionally, the loss of gel and capillary nanoporosities will reduce the reactivity of cement with CO due to reactive surface area loss. This work demonstrates the importance of understanding not only changes in total porosity but also how the distribution of porosity evolves with reaction that affects permeability.
CO2 封存过程中的矿物反应将改变孔径分布和孔表面特性,从而使渗透率和储存安全性预测变得复杂。在本文中,我们报告了对暴露于二氧化碳中长达三十年的井筒水泥进行小/广角散射研究的结果。我们构建了详细的等高线图,描述了样品的局部孔隙分布和矿物学,并将这些量与水泥上的二氧化碳反应前沿相关联。我们发现,水泥中最初的双峰分布的孔,1-2nm 和 10-20nm,在碳酸化反应过程中受到不同的影响。水泥相的初始溶解发生在 10-20nm 的孔隙中,并导致新的孔隙空间的形成,最终这些空间被 CaCO3 沉淀所封闭,从而导致凝胶和毛细纳米孔的损失、更平滑的孔表面和孔隙率的降低。这表明,在井筒水泥的广泛碳酸化过程中,由于孔隙空间内的碳酸盐矿物沉淀,水泥的渗透率降低。此外,凝胶和毛细纳米孔隙的损失将由于反应表面积的损失而降低水泥与 CO2 的反应性。这项工作表明,不仅要理解总孔隙率的变化,还要理解孔隙率分布如何随反应而演变,这对于渗透率具有重要意义。