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Thermal Stability of Gas Oil Hydrotreating Processes: Numerical Issues of the Matrix-Eigenvalue Approach Stabilité thermique de procédés d’hydrotraitement des gazoles : aspects numériques de l’approche par valeurs propres matricielles 天然气加氢处理过程的热稳定性:矩阵特征值方法的数值问题天然气加氢处理过程的热稳定性:矩阵特征值方法的数值问题
Pub Date : 2010-09-01 DOI: 10.2516/OGST/2010018
Schweitzer J.-M., M. Elia, C. García, U. Ehrenstein
Processes carrying out exothermic reactions must ensure safe operating conditions to avoid uncontrolled thermal excursion, also known as runaway. Therefore, a thermal stability analysis is necessary to determine the safe and productive range of operating conditions of highly exothermic processes. Hydrotreating gas oil feeds consists mainly of hydrogenation reactions; processing highly unsaturated feeds such as light cycle oils can be highly exothermic. For this reason, a thermal stability study of this complex refining is performed. Perturbations theory has already been applied to carry out a thermal stability study of this process under dynamic conditions. This method consists in the perturbation of the hydrotreating reactor model and solution of the perturbed model in the form of an eigenvalue problem. The stability condition imposes that all perturbations must tend to zero when time tends to infinity. Some methodology and numerical aspects applying this theory and the effect on stability results are tackled in this work. The formalization of the perturbed model solution as a standard eigenvalue problem or as a generalized eigenvalue problem are presented. The computation of the Jacobian by a numerical approach or with the analytical expressions is also carried out. In both cases, results are compared and their influence on the stability/instability results is presented.
进行放热反应的过程必须确保安全的操作条件,以避免不受控制的热偏移,也称为失控。因此,热稳定性分析对于确定高放热过程的安全生产范围是必要的。加氢处理气油原料主要由加氢反应组成;加工高度不饱和的饲料,如轻循环油,可以是高度放热的。为此,对该复合精炼工艺进行了热稳定性研究。微扰理论已经应用于该过程在动态条件下的热稳定性研究。该方法包括对加氢反应器模型进行扰动,并将扰动后的模型以特征值问题的形式求解。稳定性条件规定当时间趋于无穷时,所有的扰动必须趋于零。本文讨论了应用该理论的一些方法学和数值方面的问题以及对稳定性结果的影响。将扰动模型解形式化为标准特征值问题或广义特征值问题。并对雅可比矩阵进行了数值计算和解析计算。在这两种情况下,结果进行了比较,并给出了它们对稳定/不稳定结果的影响。
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引用次数: 1
Feasibility of Seismic Monitoring at a Potential CO2 Injection Test Site in the Paris Basin 巴黎盆地潜在二氧化碳注入试验场地震监测的可行性
Pub Date : 2010-07-01 DOI: 10.2516/OGST/2009033
M. Becquey, N. Lucet, F. Huguet
Seismic effects of the injection of CO2 into a partially depleted oil field have been evaluated. Seismic modelling yields small time-lapse effects, including 0.4 ms time-shifts and 4 to 6% amplitude variations at the top and bottom of the reservoir. Amplitude variations at the reservoir level should be slightly larger at large incidence angles, but wave equation modelling shows that picking these reflections will not be easy, because of the presence of shear waves generated at upper interfaces. In-situ fracturation generates azimuthal anisotropy with velocity and amplitude variations with the propagation direction. These variations bear some information about the crack density, about the relation between the fracture nets and the porous medium, and about the fluid content in the pores and fractures. All these effects are however weak and their measurement requires careful seismic data acquisition and processing.
对部分枯竭油田注入二氧化碳的地震效应进行了评价。地震模拟产生了较小的时移效应,包括0.4 ms的时移和4 - 6%的储层顶部和底部的振幅变化。在大入射角下,储层水平的振幅变化应该略大,但波动方程模型表明,由于上部界面产生的剪切波的存在,挑选这些反射并不容易。原位压裂产生方位各向异性,速度和振幅随传播方向变化。这些变化包含了裂缝密度、裂缝网与多孔介质之间的关系以及孔隙和裂缝中的流体含量等信息。然而,所有这些影响都很微弱,它们的测量需要仔细的地震数据采集和处理。
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引用次数: 6
Brine/CO2 Interfacial Properties and Effects on CO2 Storage in Deep Saline Aquifers 深盐层盐水/CO2界面特性及其对CO2储存的影响
Pub Date : 2010-07-01 DOI: 10.2516/OGST/2009061
C. Chalbaud, M. Robin, J. Lombard, H. Bertin, P. Egermann
It has been long recognized that interfacial interactions (interfacial tension, wettability, capillarity and interfacial mass transfer) govern fluid distribution and behaviour in porous media. Therefore the interfacial interactions between CO2 , brine and reservoir oil and/or gas have an important influence on the effectiveness of any CO2 storage operation. There is a lack of experimental data related to interfacial properties for all the geological storage options (oil & gas reservoirs, coalbeds, deep saline aquifers). In the case of deep saline aquifers, there is a gap in data and knowledge of brine-CO2 interfacial properties at storage conditions. More specifically, experimental interfacial tension values and experimental tests in porous media are necessary to better understand the wettability evolution as a function of thermodynamic conditions and it’s effects on fluid flow in the porous media. In this paper, a complete set of experimental values of brine-CO2 Interfaciale Tension (IFT) at pressure, temperature and salt concentration conditions representative of those of a CO2 storage operation. A correlation is derived from experimental data published in a companion paper [Chalbaud C., Robin M., Lombard J.-M., Egermann P., Bertin H. (2009) Interfacial Tension Measurements and Wettability Evaluation for Geological CO2 Storage, Adv. Water Resour. 32, 1, 1-109] to model IFT values. This paper pays particular attention to coreflooding experiments showing that the CO2 partially wets the surface in a Intermediate-Wet (IW) or Oil-Wet (OW) limestone rock. This wetting behavior of CO2 is coherent with observations at the pore scale in glass micromodels and presents a negative impact on the storage capacity of a given site.
人们早就认识到,界面相互作用(界面张力、润湿性、毛细作用和界面传质)控制着多孔介质中的流体分布和行为。因此,CO2、卤水和储层油/气之间的界面相互作用对任何CO2储存作业的有效性都有重要影响。目前缺乏与所有地质存储选项(油气储层、煤层、深盐水含水层)的界面特性相关的实验数据。在深盐水含水层的情况下,在储存条件下的盐水-二氧化碳界面特性的数据和知识存在空白。更具体地说,为了更好地理解润湿性随热力学条件的变化及其对多孔介质中流体流动的影响,有必要进行实验界面张力值和实验测试。本文给出了一套完整的盐水-CO2界面张力(IFT)在压力、温度和盐浓度条件下的实验值,代表了一次CO2封存作业。相关性来自于发表在一篇配套论文中的实验数据[Chalbaud C., Robin M., Lombard J.-M.]。[3]张建军,张建军,张建军,等。(2009)基于地层学方法的地层学研究[j] .地球科学进展,32(1):1- 9。本文特别关注了岩心注水实验,表明CO2部分润湿了中湿(IW)或油湿(OW)石灰岩的表面。CO2的这种润湿行为与玻璃微观模型在孔隙尺度上的观察一致,并对给定地点的存储容量产生负面影响。
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引用次数: 77
Development of Methods for Gaseous Phase Geochemical Monitoring on the Surface and in the Intermediate Overburden Strata of Geological CO2 Storage Sites 地质CO2封存点地表和中间覆盖层气相地球化学监测方法的发展
Pub Date : 2010-07-01 DOI: 10.2516/OGST/2009084
Z. Pokryszka, A. Charmoille, G. Bentivegna
The developments and results presented in this paper are taken from the work carried out as part of the GeoCarbon-Monitoring project, which was partly funded by the French National Research Agency (ANR). An important part of this project covers methods for gas monitoring on the surface as well as within the cap rock of geological CO2 storage sites. The work undertaken by INERIS was targeted at two specific approaches which are often recommended as essential for the monitoring of future storage sites : early detection (pre-alert), based on the sampling and analysis of gas at the bottom of the dedicated boreholes which are drilled from the surface into the intermediate cap rock strata ; the detection and quantification of the gaseous flux of CO2 released from the ground into the atmosphere. These two approaches were developed in the laboratory successively and then applied and tested in-situ, under conditions that are as close as possible to those of the future storage sites. They offer the advantage of ensuring a direct measurement as well as providing real-time information on the presence or, on the contrary, the absence of CO2 leaks. The tests undertaken on a 200 meter deep borehole have shown that the detection of CO2 leaks passing through the intermediate overburden strata was possible thanks to the continuous sampling and analysis of the composition of the gas which accumulated at the bottom of the borehole. In particular, the detection of small releases of gas emanating from the surrounding rock gave rise to a number of good results. These releases may be a precursor to a larger leak. Likewise, it has been possible to take a sample and ensure the transit of gas over long distances, up to 1000 meters from the sampling point. This was done without causing any significant deformation or dilution of the initial gaseous signal, even for low amplitude leaks. These results allow us to envisage the implementation of a relatively simple system for detecting and monitoring gas leaks through intermediate cap rock strata. This system will largely comprise conventional industrial gas sensors which are available off the shelf. The direct measurement of gas flows emanating from the ground is one of the most effective ways to monitor a storage site. The INERIS accumulation chamber method has been improved to measure low and very low CO2 flux rates. It can now be used to measure a wide range of CO2 flux rates, from very low emission levels of 0.05 to 0.2 cm3.min-1.m-2 up to extremely high flux rates of some 3000 cm3.min-1.m-2. The accuracy and operational characteristics of chamber method have been checked and validated by tests performed in a laboratory and on a test rig, as well as through field measurements taken under real conditions at sites that naturally release CO2. These tests have shown that the method has reached full technical maturity and that it can be applied on a practical level to detect and monitor CO2 and methane emissions on the ground's
本文中介绍的进展和结果来自地球碳监测项目的一部分,该项目部分由法国国家研究机构(ANR)资助。该项目的一个重要部分包括对地表以及地质CO2储存地点盖层内的气体监测方法。INERIS所进行的工作针对的是经常被建议为监测未来储存地点所必需的两种具体方法:早期探测(预警),基于对从地表钻入中间盖层的专用钻孔底部的气体取样和分析;对从地面释放到大气中的二氧化碳气体通量的检测和量化。这两种方法先后在实验室开发,然后在尽可能接近未来储存地点的条件下进行现场应用和测试。它们的优点是确保直接测量,并提供有关存在或相反,没有二氧化碳泄漏的实时信息。在一个200米深的钻孔上进行的测试表明,由于对钻孔底部积聚的气体的成分进行了连续采样和分析,可以检测到穿过中间覆盖层的二氧化碳泄漏。特别是对从围岩中释放出的少量气体的探测,产生了许多好的结果。这些泄漏可能是更大泄漏的前兆。同样,它也可以采集样本,并确保天然气在距离采样点1000米的长距离运输。这样做不会造成任何明显的变形或稀释初始气体信号,即使是低幅度泄漏。这些结果使我们能够设想实施一种相对简单的系统,用于检测和监测通过中间盖层的气体泄漏。该系统将主要由现成的传统工业气体传感器组成。直接测量从地面发出的气体流量是监测储存地点最有效的方法之一。已改进了INERIS积累室方法,以测量低和极低的CO2通量率。它现在可用于测量范围很广的二氧化碳通量率,从0.05至0.2厘米3分-1的极低排放水平。M-2高达极高的通量,约为3000厘米。通过在实验室和测试平台上进行的测试,以及在自然释放二氧化碳的现场进行的实际条件下的现场测量,检查和验证了室法的准确性和操作特性。这些试验表明,该方法在技术上已经完全成熟,可以在实际层面上用于探测和监测地面的二氧化碳和甲烷排放。经过测试的两种方法现已投入使用,并准备纳入未来二氧化碳储存场址的监测战略。它们可用于存储站点生命周期的每个阶段:站点侦察、初始状态定义、注入、注入后阶段以及站点废弃后的剩余监测。
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引用次数: 16
Préambule : Le stockage du CO2 au service de la lutte contre le changement climatique - Étude de sites géologiques dans le bassin Parisien, France 序言:为应对气候变化服务的二氧化碳储存-法国巴黎盆地地质地点的研究
Pub Date : 2010-07-01 DOI: 10.2516/OGST/2010011
J. Lecourtier
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引用次数: 1
The Géocarbone-Monitoring Project: Main Results and Recommendations for Monitoring Deep Geological CO2 Storage in the Paris Basin gsamo - carbon监测项目:监测巴黎盆地深层地质二氧化碳储存的主要结果和建议
Pub Date : 2010-07-01 DOI: 10.2516/OGST/2010003
H. Fabriol, M. Becquey, Frédéric Huguet, M. Lescanne, Gérard, Mouronval, J. Pironon, Zbigniew Pokryzska
The aim of the Geocarbone-Monitoring research project was the evaluation and testing, as far as possible, of the different monitoring methods that might be applied in the specific context of the Paris Basin. Their main objectives are to: detect and map CO2 in the reservoir rocks; detect and quantify possible leaks between the reservoir and the surface. The partners developed several thoughts and research concerning the various monitoring methods. This enabled drawing up a critical overview of existing methods and proposing leads for further work. At the end of the project, recommendations were made for the stakeholders of CO2 storage, i.e. the government departments regulating storage, decision-makers, and future site operators. In addition, a proposal was made for the general design and implementation of a monitoring programme of an injection test in the Paris Basin, within a depleted reservoir or a deep aquifer.
地球碳监测研究项目的目的是尽可能评价和测试可能适用于巴黎盆地具体情况的不同监测方法。他们的主要目标是:探测和绘制储层岩石中的二氧化碳;检测并量化储层与地表之间可能存在的泄漏。合作伙伴就各种监测方法提出了一些想法和研究。这使得能够对现有方法进行批判性概述,并为进一步的工作提出建议。在项目结束时,对二氧化碳封存的利益相关者,即监管封存的政府部门、决策者和未来的现场运营商提出了建议。此外,还建议总体设计和执行在巴黎盆地一个已枯竭的水库或深层含水层内进行注入试验的监测方案。
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引用次数: 9
Transport Properties of Lavoux Limestone at Various Stages of CO2-Like Acid-Rock Alteration 类co2酸岩蚀变不同阶段拉吾石灰岩输运特性
Pub Date : 2010-07-01 DOI: 10.2516/OGST/2009081
G. Radilla, M. Kacem, J. Lombard, M. Fourar
Since 2005, the French National Research Agency supports several scientific projects intended to select, validate and implement a geological site for CO2 storage in France. The work presented in this paper was carried out within the Geocarbone-Injectivity project, aimed to study the suitability of a carbonate deep saline aquifer located in the Paris basin for a geological CO2 storage. A geological analog to the aquifer rock was chosen in order to perform several petrophysical and transport characterizations. Measured parameters were intrinsic permeability, inertia coefficient, Klinkenberg coefficient, relative permeabilities and transport properties such as the dispersion coefficient and the stratification factor. Samples of Lavoux limestone were characterized in their original state and also after a phase of CO2 -like acid-rock alteration. Results show sensible changes in porosity, permeability and inertia coefficient and almost no change in relative permeabilities, dispersion coefficient and stratification coefficient. These results mean that the CO2 injectivity would be maintained and even enhanced during its injection in the considered Dogger formation. Nevertheless, to confirm this observation, additional experimental and modeling work should be performed, taking into account the potential fine migration. A permeability alteration could be expected due to these fine displacements.
自2005年以来,法国国家研究机构支持了几个旨在选择、验证和实施法国二氧化碳储存地质地点的科学项目。本文中介绍的工作是在gecarbonininjection项目中进行的,旨在研究位于巴黎盆地的碳酸盐深盐水含水层对地质二氧化碳储存的适用性。为了进行几种岩石物理和输运表征,选择了一种与含水层岩石相似的地质模拟物。测量参数包括固有渗透率、惯性系数、Klinkenberg系数、相对渗透率以及色散系数和分层系数等输运性质。Lavoux石灰石样品的特征是原始状态和经过CO2样酸岩蚀变阶段。结果表明,孔隙度、渗透率和惯性系数变化明显,相对渗透率、分散系数和分层系数几乎没有变化。这些结果意味着在Dogger地层中注入二氧化碳的过程中,二氧化碳的注入能力将保持甚至提高。然而,为了证实这一观察结果,需要进行额外的实验和建模工作,考虑到潜在的精细迁移。由于这些细小的位移,渗透率可能会发生变化。
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引用次数: 6
Surface Gas Geochemistry above the Natural CO2 Reservoir of Montmiral (Drôme, France), Source Tracking and Gas Exchange between the Soil, Biosphere and Atmosphere Montmiral天然CO2库(Drôme,法国)地表气体地球化学、来源追踪及土壤、生物圈和大气之间的气体交换
Pub Date : 2010-07-01 DOI: 10.2516/OGST/2009068
F. Gal, K. L. Pierrès, M. Brach, Gilles Braibant, C. Bény, A. Battani, E. Tocqué, Y. Benoit, E. Jeandel, Z. Pokryszka, A. Charmoille, G. Bentivegna, J. Pironon, P. Donato, C. Garnier, C. Cailteau, O. Barrès, G. Radilla, A. Bauer
One of the options considered to mitigate greenhouse gas concentrations in the atmosphere is underground storage of CO2 . There is a strong need for enhancing and developing methods that would help throughout the duration life of such underground storage, to ensure the safety and able to monitor the evolution of the injected CO2 plume. Among these, geochemical methods can play an important role. Here, we describe results acquired under the research programme “Geocarbone-Monitoring”, partially funded by the French National Research Agency, on the Montmiral natural analogue in South-Eastern France. Other results obtained under the same research programme in the French Massif Central are reported elsewhere in this volume.Spot sampling methods allowing a great geographical coverage and continuous measurements on selected points were undertaken in 2006 and 2007, in order to determine soil gas concentrations and fluxes as well as carbon isotope ratio determinations. One important result is that without any evidence of deep CO2 leakage, both CO2 concentrations and fluxes appear to be higher than can be explained only by biological activities. Further investigations are thus needed to understand the gas evolution better throughout the year.
减少大气中温室气体浓度的选择之一是将二氧化碳储存在地下。迫切需要加强和发展有助于这种地下储存的整个生命周期的方法,以确保安全并能够监测注入的二氧化碳羽流的演变。其中,地球化学方法可发挥重要作用。在这里,我们描述了在法国国家研究机构部分资助的“地球碳监测”研究计划下获得的关于法国东南部Montmiral自然模拟物的结果。在同一研究计划下在法国中部山区获得的其他结果在本卷的其他地方报告。为确定土壤气体浓度和通量以及碳同位素比率,2006年和2007年采取了现场抽样方法,可在很大的地理范围内对选定的点进行连续测量。一个重要的结果是,在没有任何证据表明深层二氧化碳泄漏的情况下,二氧化碳浓度和通量似乎都高于仅用生物活动所能解释的水平。因此,需要进一步的调查来更好地了解全年的气体演化。
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引用次数: 22
Evolution of the Petrophysical and Mineralogical Properties of Two Reservoir Rocks Under Thermodynamic Conditions Relevant for CO2 Geological Storage at 3 km Depth 3 km深度CO2地质封存热力学条件下两种储层岩石物理矿物学性质演化
Pub Date : 2010-07-01 DOI: 10.2516/OGST/2009071
G. Rimmelé, V. Barlet-Gouedard, François Renard
Injection of carbon dioxide (CO2 ) underground, for long-term geological storage purposes, is considered as an economically viable option to reduce greenhouse gas emissions in the atmosphere. The chemical interactions between supercritical CO2 and the potential reservoir rock need to be thoroughly investigated under thermodynamic conditions relevant for geological storage. In the present study, 40 samples of Lavoux limestone and Adamswiller sandstone, both collected from reservoir rocks in the Paris basin, were experimentally exposed to CO2 in laboratory autoclaves specially built to simulate CO2 -storage-reservoir conditions. The two types of rock were exposed to wet supercritical CO2 and CO2 -saturated water for one month, at 28 MPa and 90°C, corresponding to conditions for a burial depth approximating 3 km. The changes in mineralogy and microtexture of the samples were measured using X-ray diffraction analyses, Raman spectroscopy, scanning-electron microscopy, and energy-dispersionspectroscopy microanalysis. The petrophysical properties were monitored by measuring the weight, density, mechanical properties, permeability, global porosity, and local porosity gradients through the samples. Both rocks maintained their mechanical and mineralogical properties after CO2 exposure despite an increase of porosity and permeability. Microscopic zones of calcite dissolution observed in the limestone are more likely to be responsible for such increase. In the sandstone, an alteration of the petrofabric is assumed to have occurred due to clay minerals reacting with CO2 . All samples of Lavoux limestone and Adamswiller sandstone showed a measurable alteration when immersed either in wet supercritical CO2 or in CO2 -saturated water. These batch experiments were performed using distilled water and thus simulate more severe conditions than using formation water (brine).
将二氧化碳(CO2)注入地下,用于长期的地质储存目的,被认为是减少大气中温室气体排放的经济可行的选择。超临界CO2与潜在储层岩石之间的化学相互作用需要在与地质储存相关的热力学条件下进行深入研究。在本研究中,从巴黎盆地的储层岩石中收集了40个Lavoux石灰岩和Adamswiller砂岩样品,并在专门模拟二氧化碳储存-储层条件的实验室高压灭菌器中实验暴露于二氧化碳中。这两种岩石分别暴露在湿超临界CO2和CO2饱和水中1个月,温度为28 MPa,温度为90℃,对应埋深约为3 km的条件。利用x射线衍射分析、拉曼光谱、扫描电子显微镜和能量色散光谱显微分析测量了样品的矿物学和显微结构的变化。通过测量样品的重量、密度、力学性能、渗透率、整体孔隙度和局部孔隙度梯度来监测岩石物理性质。尽管孔隙度和渗透率增加,但两种岩石在CO2暴露后仍保持其力学和矿物学性质。在石灰石中观察到的方解石溶解的微观区域更可能是造成这种增加的原因。在砂岩中,假定由于粘土矿物与二氧化碳反应,岩石组构发生了变化。Lavoux石灰岩和Adamswiller砂岩的所有样品在浸入潮湿的超临界二氧化碳或二氧化碳饱和水中时都显示出可测量的变化。这些批量实验使用蒸馏水进行,因此比使用地层水(盐水)模拟更恶劣的条件。
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引用次数: 75
CO2 Injectivity in Geological Storages: an Overview of Program and Results of the GeoCarbone-Injectivity Project 地质储层的二氧化碳注入性:地质碳注入性项目的计划和结果概述
Pub Date : 2010-07-01 DOI: 10.2516/OGST/2010013
J. Lombard, M. Azaroual, J. Pironon, D. Broseta, P. Egermann, Gilles Munier, G. Mouronval
The objective of the GeoCarbone-Injectivity project was to develop a methodology to study the complex phenomena involved in the near wellbore region during CO2 injection. This paper presents an overview of the program and results of the project, and some further necessary developments. The proposed methodology is based on experiments and simulations at the core scale, in order to understand (physical modelling and definition of constitutive laws) and quantify (calibration of simulation tools) the mechanisms involved in injectivity variations: fluid/rock interactions, transport mechanisms, geomechanical effects. These mechanisms and the associated parameters have then to be integrated in the models at the wellbore scale. The methodology has been applied for the study of a potential injection of CO2 in the Dogger geological formation of the Paris Basin, in collaboration with the other ANR GeoCarbone projects.
gecarbone - injectivity项目的目标是开发一种方法来研究近井区域在二氧化碳注入过程中涉及的复杂现象。本文概述了该项目的方案和成果,并提出了一些必要的进一步发展。所提出的方法是基于核心尺度的实验和模拟,以理解(物理建模和本构定律的定义)和量化(模拟工具的校准)涉及注入变化的机制:流体/岩石相互作用,运输机制,地质力学效应。然后,这些机制和相关参数必须集成到井筒尺度的模型中。该方法已与其他ANR GeoCarbone项目合作,用于研究巴黎盆地Dogger地质地层中潜在的二氧化碳注入。
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引用次数: 23
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