Oxygen isotope exchange between H2O and CO2 at elevated CO2 pressures: Implications for monitoring of geological CO2 storage

Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on δ¹³C values of CO₂ to trace the migration of injected CO₂ in the subsurface. More recently the use of δ¹⁸O values of both CO₂ and reservoir fluids has been proposed as a method for quantifying in situ CO₂ reservoir saturations due to O isotope exchange between CO₂ and H₂O and subsequent changes in δ¹⁸O_H2O values in the presence of high concentrations of CO₂. To verify that O isotope exchange between CO₂ and H₂O reaches equilibrium within days, and that δ¹⁸O_H2O values indeed change predictably due to the presence of CO₂, a laboratory study was conducted during which the isotope composition of H₂O, CO₂, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50 °C and up to 19 MPa) and varying CO₂ pressures. Conditions typical for the Pembina Cardium CO₂ Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that δ¹⁸O values of CO₂ were on average 36.4 ± 2.2‰ (1σ, n = 15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5‰ for the experimental temperatures of 50 °C. By using ¹⁸O enriched water for the experiments it was demonstrated that changes in the δ¹⁸O values of water were predictably related to the fraction of O in the system sourced from CO₂ in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO₂ is related to the total volumetric saturation of CO₂ and water as a fraction of the total volume of the system, it is concluded that changes in δ¹⁸O values of reservoir fluids can be used to calculate reservoir saturations of CO₂ in CCS settings given that the δ¹⁸O values of CO₂ and water are sufficiently distinct.     

火山岩吸附CO2气的成藏潜力及实例分析

火山岩的脱气实验和对昌德东CO2气藏气源的分析结果表明加热火山岩到250℃时,脱出挥发分总量为0.0299～0.0790mL/g,其中CO2脱出量为0.0218～0.0706mL/g(0.429～1.387wt%);挥发组分以CO2为主,还含有H2、CO、CH4等还原性气体,以及少量低碳烷烃,CO2含量和总烃呈现反比关系;基性岩的CO2脱出量、脱出率高于中、酸性岩;CO2脱出量与岩石碱质含量正相关.松辽盆地北部昌德东CO2气藏成藏模式为"自生自储",成藏CO2气主要来自深部被火山岩吸附的气.随岩浆上升,在岩浆冷凝成火山岩的过程中被吸附于火山岩的节理、劈理和晶体位错之中的CO2气,连同火山岩包体中的残留气,成为高纯CO2气藏的主要补给源,并非地幔气体沿大断裂上来直接充注成藏.     

Selection of coals of different maturities for CO2 Storage by modelling of CH4 and CO2 adsorption isotherms

CO₂ injection in unmineable coal seams could be one interesting option for both storage and methane recovery processes. The objective of this study is to compare and model pure gas sorption isotherms (CO₂ and CH₄) for well-characterised coals of different maturities to determine the most suitable coal for CO₂ storage. Carbon dioxide and methane adsorption on several coals have been investigated using a gravimetric adsorption method. The experiments were carried out using both CO₂ and CH₄ pure gases at 25 °C from 0.1 to 5 MPa (1 to 50 bar). The experimental results were fitted using Temkin's approach but also with the corrected Langmuir's and the corrected Tóth's equations. The two last approaches are more accurate from a thermodynamical point of view, and have the advantage of taking into account the fact that experimental data (isotherms) correspond to excess adsorption capacities. These approaches allow better quantification of the adsorbed gas. Determined CO₂ adsorption capacities are from 0.5 to 2 mmol/g of dry coal. Modelling provides also the affinity parameters of the two gases for the different coals. We have shown these parameters determined with adsorption models could be used for classification and first selection of coals for CO₂ storage. The affinity ratio ranges from a value close to 1 for immature coals to 41 for high rank coals like anthracites. This ratio allows selecting coals having high CO₂ adsorption capacities. In our case, the modelling study of a significant number of coals from various ranks shows that anthracites seem to have the highest CO₂ storage capacities. Our study provides high quality affinity parameters and values of CO₂ and CH₄ adsorption capacities on various coals for the future modelling of CO₂ injection in coal seams.     

Mitigation of asphaltics deposition during CO2 flood by enhancing CO2 solvency with chemical modifiers

CO₂ injected in the reservoir of McElroy Field, TX, for a CO₂ flood was in the supercritical state. Supercritical CO₂ fluid is capable of extracting light and intermediate hydrocarbons from rocks but is unable to extract heavy hydrocarbons and asphaltics. Therefore, plugging of asphaltics in reservoir rocks and a consequent reduction in injectivity and recovery may result when CO₂ only is used in enhanced oil recovery. By adding common solvents as chemical modifiers, the flooding fluid shows marked improvement in solvency for heavy components of crudes due to its increased density and polarity. Numerous supercritical CO₂ fluid extractions of dolomite rock from the Grayburg Formation containing known amount of spiked McElroy crude oil have been carried out to evaluate extraction efficiencies of CO₂ and CO₂ with chemical modifiers at various temperatures and pressures. All experiments show that extraction efficiency increases with increasing CO₂ pressure but decreases with increasing temperature. Addition of chemical modifiers to CO₂ also shows improved extraction efficiency and reduced asphaltic deposits. Under the pressure and temperature similar to McElroy reservoir conditions; chemically modified CO₂ yielded almost 3 times as much oil extracts as those in extractions with CO₂ only. It also reduced the asphaltics content in extracted rocks to nearly one half; indicating its potential for mitigating asphaltics plugging of formation rocks     

Melting relationships in the systems CaOCO2 and MgOCO2 to 33 kilobars

The melting temperatures of calcite and magnesite in the presence of excess CO₂ have been measured using Ag₂C₂O₄ in sealed capsules m a piston-cylinder apparatus. At 27 kbar, 11.5 wt % CO₂ dissolves in molten CaCO₂, depressing the freezing temperature from 1610 to 1505°C; and 6.5 wt % CO₂ dissolves in molten MgCO₃, depressing the freezing temperature from 1590 to 1510°C. The eutectic between calcite and lime was located at 1385°C at 27 kbar. These and other new results, combined with previously published data, permit completion of PT diagrams for the systems CaO-CO₂ and MgO-CO₂ from 1 bar to 35 kbar. The dissociation curve for each carbonate terminates at an invariant point where melting begins, at 40 bars and 1230°C for CaO-CO₂ and 23 kbar and 1550°C for MgO-CO₂ The differences between the two systems are explained by the different solubilities of CO₂ in the invariant liquids consequent upon the large pressure difference between the locations of these two invariant points. The results show that the temperatures for the beginning of melting of carbonates in the asthenosphere are lowered by about 100°C in the presence of CO₂.     

CO2 solubility in dacitic melts equilibrated with H2O-CO2 fluids: Implications for modeling the solubility of CO2 in silicic melts

The solubility of CO₂ in dacitic melts equilibrated with H₂O-CO₂ fluids was experimentally investigated at 1250°C and 100 to 500 MPa. CO₂ is dissolved in dacitic glasses as molecular CO₂ and carbonate. The quantification of total CO₂ in the glasses by mid-infrared (MIR) spectroscopy is difficult because the weak carbonate bands at 1430 and 1530 cm⁻¹ can not be reliably separated from background features in the spectra. Furthermore, the ratio of CO_2,mol/carbonate in the quenched glasses strongly decreases with increasing water content. Due to the difficulties in quantifying CO₂ species concentrations from the MIR spectra we have measured total CO₂ contents of dacitic glasses by secondary ion mass spectrometry (SIMS).At all pressures, the dependence of CO₂ solubility in dacitic melts on x^fluid_CO2,total shows a strong positive deviation from linearity with almost constant CO₂ solubility at x_CO2fluid > 0.8 (maximum CO₂ solubility of 795 ± 41, 1376 ± 73 and 2949 ± 166 ppm at 100, 200 and 500 MPa, respectively), indicating that dissolved water strongly enhances the solubility of CO₂. A similar nonlinear variation of CO₂ solubility with x_CO2fluid has been observed for rhyolitic melts in which carbon dioxide is incorporated exclusively as molecular CO₂ (Tamic et al., 2001). We infer that water species in the melt do not only stabilize carbonate groups as has been suggested earlier but also CO₂ molecules.A thermodynamic model describing the dependence of the CO₂ solubility in hydrous rhyolitic and dacitic melts on T, P, f_CO2 and the mol fraction of water in the melt (x_water) has been developed. An exponential variation of the equilibrium constant K₁ with x_water is proposed to account for the nonlinear dependence of x_CO2,totalmelt on x_CO2fluid. The model reproduces the CO₂ solubility data for dacitic melts within ±14% relative and the data for rhyolitic melts within 10% relative in the pressure range 100-500 MPa (except for six outliers at low x_CO2fluid). Data obtained for rhyolitic melts at 75 MPa and 850°C show a stronger deviation from the model, suggesting a change in the solubility behavior of CO₂ at low pressures (a Henrian behavior of the CO₂ solubility is observed at low pressure and low H₂O concentrations in the melt). We recommend to use our model only in the pressure range 100-500 MPa and in the x_CO2fluid range 0.1-0.95. The thermodynamic modeling indicates that the partial molar volume of total CO₂ is much lower in rhyolitic melts (31.7 cm³/mol) than in dacitic melts (46.6 cm³/mol). The dissolution enthalpy for CO₂ in hydrous rhyolitic melts was found to be negligible. This result suggests that temperature is of minor importance for CO₂ solubility in silicic melts.     

Atmospheric CO2 consumption by chemical weathering in North America

CO₂ consumption by chemical weathering is an integral part of the boundless carbon cycle, whose spatial patterns and controlling factors on continental scale are still not fully understood. A dataset of 338 river catchments throughout North America was used to empirically identify predictors of bicarbonate fluxes by chemical weathering and interpret the underlying controlling factors. Detailed analysis of major ion ratios enables distinction of the contributions of silicate and carbonate weathering and thus quantifying CO₂ consumption. Extrapolation of the identified empirical model equations to North America allows the analysis of the spatial patterns of the CO₂ consumption by chemical weathering.Runoff, lithology and land cover were identified as the major predictors of the riverine bicarbonate fluxes and the associated CO₂ consumption. Other influence factors, e.g. temperature, could not be established in the models. Of the distinguished land cover classes, artificial surfaces, dominated by urban areas, increase bicarbonate fluxes most, followed by shrubs, grasslands, managed lands, and forests. The extrapolation results in an average specific bicarbonate flux of 0.3 Mmol km⁻² a⁻¹ by chemical weathering in North America, of which 64% originates from atmospheric CO₂, and 36% from carbonate mineral dissolution. Chemical weathering in North America thus consumes 50 Mt atmospheric CO₂-C per year. About half of that originates from 10% of the area of North America.The estimated strength of individual predictors differs from previous studies. This highlights the need for a globally representative set of regionally calibrated models of CO₂ consumption by chemical weathering, which apply very detailed spatial data to resolve the heterogeneity of earth surface processes.     

GEOCARBSULF: A combined model for Phanerozoic atmospheric O2 and CO2

A model for the combined long-term cycles of carbon and sulfur has been constructed which combines all the factors modifying weathering and degassing of the GEOCARB III model [Berner R.A., Kothavala Z., 2001. GEOCARB III: a revised model of atmospheric CO₂ over Phanerozoic time. Am. J. Sci. 301, 182-204] for CO₂ with rapid recycling and oxygen dependent carbon and sulfur isotope fractionation of an isotope mass balance model for O₂ [Berner R.A., 2001. Modeling atmospheric O₂ over Phanerozoic time. Geochim. Cosmochim. Acta65, 685-694]. New isotopic data for both carbon and sulfur are used and new feedbacks are created by combining the models. Sensitivity analysis is done by determining (1) the effect on weathering rates of using rapid recycling (rapid recycling treats carbon and sulfur weathering in terms of young rapidly weathering rocks and older more slowly weathering rocks); (2) the effect on O₂ of using different initial starting conditions; (3) the effect on O₂ of using different data for carbon isotope fractionation during photosynthesis and alternative values of oceanic δ¹³C for the past 200 million years; (4) the effect on sulfur isotope fractionation and on O₂ of varying the size of O₂ feedback during sedimentary pyrite formation; (5) the effect on O₂ of varying the dependence of organic matter and pyrite weathering on tectonic uplift plus erosion, and the degree of exposure of coastal lands by sea level change; (6) the effect on CO₂ of adding the variability of volcanic rock weathering over time [Berner, R.A., 2006. Inclusion of the weathering of volcanic rocks in the GEOCARBSULF model. Am. J. Sci.306 (in press)]. Results show a similar trend of atmospheric CO₂ over the Phanerozoic to the results of GEOCARB III, but with some differences during the early Paleozoic and, for variable volcanic rock weathering, lower CO₂ values during the Mesozoic. Atmospheric oxygen shows a major broad late Paleozoic peak with a maximum value of about 30% O₂ in the Permian, a secondary less-broad peak centered near the Silurian/Devonian boundary, variation between 15% and 20% O₂ during the Cambrian and Ordovician, a very sharp drop from 30% to 15% O₂ at the Permo-Triassic boundary, and a more-or less continuous rise in O₂ from the late Triassic to the present.     

Caprock interaction with CO2: A laboratory study of reactivity of shale with supercritical CO2 and brine

Crushed rock from two caprock samples, a carbonate-rich shale and a clay-rich shale, were reacted with a mixture of brine and supercritical CO₂ (CO₂–brine) in a laboratory batch reactor, at different temperature and pressure conditions. The samples were cored from a proposed underground CO₂ storage site near the town of Longyearbyen in Svalbard. The reacting fluid was a mixture of 1 M NaCl solution and CO₂ (110 bar) and the water/rock ratio was 20:1. Carbon dioxide was injected into the reactors after the solution had been bubbled with N₂, in order to mimic O₂-depleted natural storage conditions. A control reaction was also run on the clay-rich shale sample, where the crushed rock was reacted with brine (CO₂-free brine) at the same experimental conditions. A total of 8 batch reaction experiments were run at temperatures ranging from 80 to 250 °C and total pressures of 110 bar (∼40 bar for the control experiment). The experiments lasted 1–5 weeks.Fluid analysis showed that the aqueous concentration of major elements (i.e. Ca, Mg, Fe, K, Al) and SiO₂ increased in all experiments. Release rates of Fe and SiO₂ were more pronounced in solutions reacted with CO₂–brine as compared to those reacted with CO₂-free brine. For samples reacted with the CO₂–brine, lower temperature reactions (80 °C) released much more Fe and SiO₂ than higher temperature reactions (150–250 °C). Analysis by SEM and XRD of reacted solids also revealed changes in mineralogical compositions. The carbonate-rich shale was more reactive at 250 °C, as revealed by the dissolution of plagioclase and clay minerals (illite and chlorite), dissolution and re-precipitation of carbonates, and the formation of smectite. Carbon dioxide was also permanently sequestered as calcite in the same sample. The clay-rich shale reacted with CO₂–brine did not show major mineralogical alteration. However, a significant amount of analcime was formed in the clay-rich shale reacted with CO₂-free brine; while no trace of analcime was observed in either of the samples reacted with CO₂–brine.     

CO2-water-basalt interaction. Numerical simulation of low temperature CO2 sequestration into basalts

The interaction between CO₂-rich waters and basaltic glass was studied using reaction path modeling in order to get insight into the water-rock reaction process including secondary mineral composition, water chemistry and mass transfer as a function of CO₂ concentration and reaction progress (ξ). The calculations were carried out at 25-90 °C and pCO₂ to 30 bars and the results were compared to recent experimental observations and natural systems. A thermodynamic dataset was compiled from 25 to 300 °C in order to simulate mineral saturations relevant to basalt alteration in CO₂-rich environment including revised key aqueous species for mineral dissolution reactions and apparent Gibbs energies for clay and carbonate solid solutions observed to form in nature. The dissolution of basaltic glass in CO₂-rich waters was found to be incongruent with the overall water composition and secondary mineral formation depending on reaction progress and pH. Under mildly acid conditions in CO₂ enriched waters (pH <6.5), SiO₂ and simple Al-Si minerals, Ca-Mg-Fe smectites and Ca-Mg-Fe carbonates predominated. Iron, Al and Si were immobile whereas the Mg and Ca mobility depended on the mass of carbonate formed and water pH. Upon quantitative CO₂ mineralization, the pH increased to >8 resulting in Ca-Mg-Fe smectite, zeolites and calcite formation, reducing the mobility of most dissolved elements. The dominant factor determining the reaction path of basalt alteration and the associated element mobility was the pH of the water. In turn, the pH value was determined by the concentration of CO₂ and extent of reaction. The composition of the carbonates depended on the mobility of Ca, Mg and Fe. At pH <6.5, Fe was in the ferrous oxidation state resulting in the formation of Fe-rich carbonates with the incorporation of Ca and Mg. At pH >8, the mobility of Fe and Mg was limited due to the formation of clays whereas Ca was incorporated into calcite, zeolites and clays. Competing reactions between clays (Ca-Fe smectites) and carbonates at low pH, and zeolites and clays (Mg-Fe smectites) and carbonates at high pH, controlled the availability of Ca, Mg and Fe, playing a key role for low temperature CO₂ mineralization and sequestration into basalts. Several problems of the present model point to the need of improvement in future work. The determinant factors linking time to low temperature reaction path modeling may not only be controlled by the primary dissolving phase, which presents challenges concerning non-stoichiometric dissolution, the leached layer model and reactive surface area, but may include secondary mineral precipitation kinetics as rate limiting step for specific reactions such as retrieved from the present reaction path study.     

Carbon isotope evidence implying high O2/CO2 ratios in the Permo-Carboniferous atmosphere

Theoretical models predict a marked increase in atmospheric O₂ to ∼35% during the Permo-Carboniferous (∼300 Ma) occurring against a low (∼0.03%) CO₂ level. An upper O₂ value of 35%, however, remains disputed because ignition data indicate that excessive global forest fires would have ensued. This uncertainty limits interpretation of the role played by atmospheric oxygen in Late Paleozoic biotic evolution. Here, we describe new results from laboratory experiments with vascular land plants that establish that a rise in O₂ to 35% increases isotopic fractionation (Δ¹³C) during growth relative to control plants grown at 21% O₂. Despite some effect of the background atmospheric CO₂ level on the magnitude of the increase, we hypothesize that a substantial Permo-Carboniferous rise in O₂ could have imprinted a detectable geochemical signature in the plant fossil record. Over 50 carbon isotope measurements on intact carbon from four fossil plant clades with differing physiological ecologies and ranging in age from Devonian to Cretaceous reveal a substantial Δ¹³C anomaly (5‰) occurring between 300 and 250 Ma. The timing and direction of the Δ¹³C excursion is consistent with the effects of a high O₂ atmosphere on plants, as predicted from photosynthetic theory and observed in our experiments. Preliminary calibration of the fossil Δ¹³C record against experimental data yields a predicted O₂/CO₂ mixing ratio of the ancient atmosphere consistent with that calculated from long-term models of the global carbon and oxygen cycles. We conclude that further work on the effects of O₂ in the combustion of plant materials and the spread of wildfire is necessary before existing data can be used to reliably set the upper limit for paleo-O₂ levels.     

Laboratory study of self-potential signals during releasing of CO2 and N2 plumes

Carbon Capture Sequestration (CCS) projects require, for safety reasons, monitoring programmes focused on surveying gas leakage on the surface. Generally, these programmes include detection of chemical tracers that, once on the surface, could be associated with CO₂ degassing. We take a different approach by analysing feasibility of applying electrical surface techniques, specifically Self-Potential. A laboratory-scale model, using water-sand, was built for simulating a leakage scenario being monitored with non-polarisable electrodes. Electrical potentials were measured before, during and after gas injection (CO₂ and N₂) to determine if gas leakage is detectable. Variations of settings were done for assessing how the electrical potentials changed according to size of electrodes, distance from electrodes to the gas source, and type of gas. Results indicated that a degassing event is indeed detectable on electrodes located above injection source. Although the amount of gas could not be quantified from signals, injection timespan and increasing of injection rate were identified. Even though conditions of experiments were highly controlled contrasting to those usually found at field scale, we project that Self-Potential is a promising tool for detecting CO₂ leakage if electrodes are properly placed.     

深部咸含水层CO2注入下压力抬升与流体迁移的大尺度模拟研究:以松辽盆地为例

地下深部封存CO2已经被公认是人类削减温室气体排放的一条有效而又科学的途径。深部咸含水层CO2地质封存因封存潜力巨大,技术可行,且已有实际的工程运行,因而备受关注。松辽盆地是中国潜在的CO2储存场地之一,选择松辽盆地为大尺度模拟研究对象,选取姚家组砂岩层为储层,选取嫩江组泥岩为盖层,运用TOUGH-MP并行计算代码建立了覆盖整个松辽盆地的三维地质模型,在中央凹陷区开展大尺度CO2注入模拟研究,包括CO2运移、储存、地层压力提升以及储存安全性等问题。模拟结果表明:持续注入100a后形成的CO2羽远小于产生的压力积聚区影响范围。注入产生的压力抬升将在注入停止后迅速消散,不会对区域地层压力和浅层地下水系统产生显著影响。在千年之内注入的CO2将随着时间持续,逐渐溶解于水中,而不会因盖层微弱的渗透性而逃逸。     

Carbon-13 exchange between CO2 and CH4 under geothermal conditions

On the basis of recently reported data on the kinetics of carbon-13 exchange between CO₂ and CH₄ at temperatures above 500°C, first order rate constants $\text{log k = 11.16?10,190/T}$ were derived allowing variations in Δ, the difference in the isotopic composition of coexisting CO₂ and CH₄, to be evaluated as a function of initial composition and cooling rate of the rising geothermal fluid. Observed Δ-values in geothermal discharges are likely to represent frozen in compositions attained after minimum residence times of 20 ka at 400°C or 10 Ma at 300°C. The carbon-13 contents of any biogenic gases are unlikely to have been affected by thermal re-equilibration at temperatures below 200°C. The chemical equilibrium involving CO₂ and CH₄ can be expected to proceed about a hundred times faster than isotopic equilibration.     

不同含水性无烟煤CO2吸附行为及其对地质封存的启示

深部煤层CO₂地质封存是助力“碳达峰碳中和”战略的重要途径,煤层含水性对以CO₂吸附封存为主的深部煤层CO₂地质封存能力影响显著。以无烟煤为例,开展了45℃下干燥、平衡水、饱和水煤样高压CO₂等温吸附实验,校正了饱和水煤样过剩吸附曲线,利用改进的D-R吸附模型拟合得到三者吸附能力与吸附热,对比了不同含水条件下CO₂绝对吸附曲线,阐释了饱和水增强无烟煤吸附能力的微观作用机理。结果表明:(1)干燥、平衡水、饱和水煤样CO₂吸附能力分别为56.72、45.19和48.36 cm3/g,吸附热分别为29.42、26.23和27.24 kJ/mol。(2) CO₂密度小于0.16 g/cm3(6.48 MPa)时,无烟煤CO₂绝对吸附量大小顺序为干燥煤样、饱和水煤样和平衡水煤样,而CO₂进入超临界状态后,顺序变为饱和水煤样、干燥煤样和平衡水煤样。(3)水分子优先占据高能吸附位是平衡水煤样吸附能力减弱的主要原因,而煤?水体系与CO₂相互作用强于CO₂与H₂O竞争吸附下的煤?CO₂相互作用是饱和水煤样在CO₂超临界阶段吸附能力高于干燥煤样的根本原因。(4)吸附封存是煤层CO₂地质封存的主要形式,深部煤储层条件下,煤层饱和水对超临界CO₂增储作用更为明显,高压注水是提高深部煤层CO₂地质封存潜力,改善煤储层渗透性的有效手段。      

The rise of trees and their effects on Paleozoic atmospheric CO2 and O2

The rise of large vascular plants during the mid-Paleozoic brought about a major increase in the rates of weathering of silicate minerals that induced a drop in the level of atmospheric CO₂ and contributed, via the atmospheric greenhouse effect, to global cooling and the initiation of the most long lived and a really extensive glaciation of the past 550 million years. Sedimentary burial of the microbiologically resistant remains of the plants resulted during the Permo-Carboniferous in both further lowering of CO₂ and in elevation of atmospheric O₂. Evidence of changes in CO₂ and O₂ are provided by mathematical models, studies of paleosols, fossil plants, fossil insects, and the effects of modern plants on silicate weathering, and by laboratory studies of the effects of changes in O₂ on plants and insects. To cite this article: R.A. Berner, C. R. Geoscience 335 (2003).     

Key Problems and Countermeasures in CO2 Flooding and Storage

Based on literature research in combination with the practice of CO₂ flooding and storage in Jilin Oilfield, this study assesses the key problems in CO₂ flooding and storage, proposing the corresponding countermeasures from five aspects of CO₂ gas source condition, namely geological condition evaluation, scheme design incoordination with other production methods, economic and effectiveness evaluation, together with dynamic monitoring and safety evaluation. The re...     

Behavior of molybdenum in alkali silicate melts: Effects of excess SiO2 and CO2

The effects of excess SiO₂ and CO₂ on the solubility of molybdenite in hydrous sodium disilicate melts were experimentally determined at 680 bars and 650°C. The molybdenite solubility decreases with increasing SiO₂ and CO₂. Under the experimental conditions, the MoS₂ content of the vapor-saturated liquid decreases from 10 wt.% to 2.5 wt.% at SiO₂ saturation. In the presence of CO₂, the solubility decreases to 4.6 wt.% MoS₂ and becomes negligible at high P_CO2. These results are explained as deriving from the increased polymerization and hence decreased NBO/Si ratio of the melt with increasing SiO₂ content and CO₂, respectively. Sulfur dissolves principally as SO₄^?2 at the relatively high fo₂ of the experiments. Consequently, the effect of sulfur is to lower the Mo solubility by effectively decreasing the NBO/Si ratio of the melt. Sulfur saturation is, therefore, likely to be a limiting factor in the Mo content of alkali silicate melts because of the chalcophile affinities of molybdenum.     

Characteristics of high heating rate biomass chars prepared under N2 and CO2 atmospheres

Partial substitution of coal by biomass in combustion systems in conjunction with advanced technologies for CO₂ capture and storage may result in a significant reduction of greenhouse gases emissions. This study investigates three biomass chars produced from rice husk, forest residuals and wood chips under N₂ and CO₂ atmospheres using a drop tube furnace (DTF) heated at 950 °C. The char constitutes an unburned residue which has been devolatilized under conditions resembling in thermal history those in full scale boilers. Higher weight losses were achieved under N₂ than under CO₂ for each type of biomass, and the highest weight loss was that of wood chips biomass, followed by forest residuals and then rice husk. The results indicate significant morphological differences between the biomass chars produced. The wood chips yielded thick-walled chars with a cenospheric shape very similar to those of low-rank vitrinite. The forest residual chars were angular in shape and often had a tenuinetwork structure, while the rice husk chars retained their vegetal structure. Overall, the studied biomass chars can be described as microporous solids. However, in the case of the rice husk, the silica associated to the char walls was essentially mesoporous, increasing the adsorption capacity of the rice husk chars. The atmosphere in the DTF affects the development of porosity in the chars. The pore volumes of the rice husk and forest residual chars prepared under a CO₂ atmosphere were higher than those of chars prepared under a N₂ atmosphere, whereas the opposite was the case with the wood chip chars. The chars that experienced the most drastic devolatilization were those with the lowest intrinsic reactivity. This indicates a more efficient reorganization of the chemical structure that reduces the number of active sites available for oxygen attack. Overall a similar morphology, optical texture, specific surface area and reactivity were found for the biomass chars generated under N₂ and CO₂, which is a similar result to that obtained for coal chars.     

鄱阳湖流域岩石化学风化特征及CO2消耗量估算

岩石风化过程中所产生的碳汇是全球碳循环的重要组成部分,该领域受到研究全球变化科学家们的普遍关注。文中通过对鄱阳湖流域河水系统的样品采集和化学成分分析,研究了河水化学成分来源及流域岩石风化所产生的碳汇效应。以大气降水、蒸发岩、硅酸岩和碳酸盐岩为4个端员,计算出它们对河水中溶解质的贡献率分别为10．4％、21．9％、30．...