Study on the failure mechanism of potassium-based sorbent for CO2 capture and the improving measure

With thermogravimetric apparatus (TGA), X-ray diffraction (XRD) and barium sulfate gravimetric methods, the carbonation reactivities of K₂CO₃ and K₂CO₃/Al₂O₃ in the simulated flue gases with SO₂ are investigated and the reaction equations are inferred. Results show that there are KHCO₃ and K₂SO₃ generated. The generation K₂SO₃ reduces the utilization ratio of the sorbent. H₂O may accelerates the sulfation reaction of AR K₂CO₃ as K₄H₂(CO₃)₃·1.5H₂O is generated in the reaction among K₂CO₃, SO₂ and H₂O. K₂SO₃ is directly generated from sulfation reaction of K₂CO₃/Al₂O₃, because there are K₂CO₃·1.5H₂O and K₂SO₃ generated in the reaction among K₂CO₃/Al₂O₃, SO₂ and H₂O. K₂CO₃·1.5H₂O does not react with SO₂, and K₂CO₃·1.5H₂O/Al₂O₃ reacts with SO₂ slowly. Compare with the reaction process without H₂O pretreatment, the reaction rates of KAl30 increased after H₂O pretreatment and the failure ratio is about a half of that without H₂O pretreatment. So, K₂CO₃/Al₂O₃ shows good carbonation and anti-sulfation characteristic after H₂O pretreatment.     

Model prediction on the rise of pCO2 in uniform flows by leakage of CO2 purposefully stored under the seabed

A numerical study was conducted to predict pCO₂ change in the ocean on a continental shelf by the leakage of CO₂, which is originally stored in the aquifer under the seabed, in the case that a large fault connects the CO₂ reservoir and the seabed by an earthquake or other diastrophism. The leakage rate was set to be 6.025 × 10⁻⁴ kg/m²/sec from 2 m × 100 m fault band, which corresponds to 3800 t-CO₂/year, referring to the monitored seepage rate from an existing EOR field. The target space in this study was limited to the ocean above the seabed, the depth of which was 200 or 500 m. The computational domain was idealistically rectangular with the seabed fault-band perpendicular to the uniform flow. The CO₂ takes a form of bubbles or droplets, depending on the depth of water, and their behaviour and dissolution were numerically simulated during their rise in seawater flow. The advection–diffusion of dissolved CO₂ was also simulated. As a result, it was suggested that the leaked CO₂ droplets/bubbles all dissolve in the seawater before spouting up to the atmosphere, and that the increase in pCO₂ in the seawater was smaller than 500 μ atm.     

Corrosion and polarization behavior of carbon steel in MEA-based CO2 capture process

This work reveals levels of corrosion rate and polarization behavior of carbon steel immersed in aqueous solutions of monoethanolamine (MEA) used in the absorption-based carbon dioxide (CO₂) capture process for greenhouse gas reduction from industrial flue gas streams. Such information was obtained from electrochemical-based corrosion experiments under a wide range of the CO₂ capture process conditions. The corrosion of carbon steel was evaluated in respect to process parameters including partial pressure of oxygen (O₂), CO₂ loading in solution, solution velocity, solution temperature, MEA concentration and metal surface condition. Results show that the aqueous MEA solution containing CO₂ provides a favorable condition for the corrosion of carbon steel to proceed. Corrosion rate is increased by all tested process parameters. These parametric effects were explained by the electrochemical kinetic data obtained from polarization curves and by the thermodynamic data obtained from Pourbaix diagram.     

基于产业链分析的长三角地区CO2与大气污染物排放研究

长三角地区作为我国大气污染较为严重区域之一,如何在保持经济增长的同时减少CO₂与大气污染物的排放已成为一个重要挑战。本研究基于2007年与2012年长三角区域间投入产出表,定量分析了长三角地区省市间贸易引致的二氧化碳和大气污染物排放转移特征和变化趋势。同时,运用产业关联系数法,从前向关联与后向关联双重视角分析了长三角地区减缓CO₂和大气污染物排放的关键行业。研究结果表明,长三角的SO₂、PM_2.5排放总量表现为消费端大于生产端,CO₂、NO_x排放总量表现为生产端大于消费端。安徽省总体呈现为长三角地区贸易的SO₂、NO_x与PM_2.5排放净调出地,而上海与浙江表现为多数污染物排放净调入地。CO₂与大气污染物协同前向减排的关键行业为江苏省、浙江省和安徽省的电力、热力的生产和供应业,安徽省的煤炭开采和洗选业等,可以通过生产端技术革新和能源结构优化来促进减排;CO₂与大气污染物后向协同减排的关键行业为江苏省、浙江省和安徽省的建筑业等,对于这些行业,调整消费结构是有效的减排措施。为更好地制定长三角地区减排与污染防治政策,应当综合考虑行业减排、协同减排等,以确保经济持续增长的同时达到减排目标。     

基于CEEMDAN的多时间尺度的北京市PM2.5浓度影响因素研究

研究PM_2.5浓度的主要影响因素,对提升北京市空气质量具有重要意义。与以往仅限于原始时间尺度的研究不同,本文基于CEEMDAN方法考察了多时间尺度下年平均风速、城市绿化、人口密度、产业结构和能源强度对北京市PM_2.5浓度波动的影响,并与原始时间尺度的主导因素进行对比。研究发现：原始尺度的北京市PM_2.5浓度影响因素是不同时间尺度内影响因素合力作用结果,不同时间尺度下影响因素不同。城市绿化、人口密度、产业结构和能源强度在多时间尺度中起到短期增强波动的作用,城市绿化和产业结构是贯穿于各个时间尺度的具有趋势性,决定北京市PM_2.5浓度基本走势的影响因素。     

The impact of heterogeneity on the distribution of CO2: Numerical simulation of CO2 storage at Ketzin

Numerical modelling of multiphase flow is an essential tool to ensure the viability of long-term and safe CO₂ storage in geological formations. Uncertainties arising from the heterogeneity of the formation and lack of knowledge of formation properties need to be assessed in order to create a model that can reproduce the data available from monitoring. In this study, we investigated the impact of unknown spatial variability in the petrophysical properties within a sandy channel facies of a fluviatile storage formation using stochastic methods in a Monte Carlo approach. The stochastic method has been applied to the Ketzin test site (CO₂SINK), and demonstrates that the deterministic homogeneous model satisfactorily predicts the first CO₂ arrival time at the Ketzin site. The equivalent permeability was adjusted to the injection pressure and is in good agreement with the hydraulic test. It has been shown that with increasing small-scale heterogeneity, the sharpness of the CO₂ front decreases and a greater volume of the reservoir is affected, which is also seen in an increased amount of dissolved CO₂. Increased anisotropy creates fingering effects, which result in higher probabilities for earlier arrival times. Generally, injectivity decreases with increasing heterogeneity.     

Legal and regulatory challenges in the implementation of CO2 geological storage: An Alberta and Canadian perspective

Alberta is the province with the largest CO₂ emissions in Canada, with approximately two-thirds of emissions originating from large stationary sources. Due to the fortuitous association of large CO₂ sources with the storage capacity offered by the underlying Alberta basin, it is expected that large-scale CO₂ geological storage in Canada will occur in Alberta first, and both levels of governments are contemplating measures to facilitate implementation. A review of the current provincial and federal legislation and regulations presented in this paper indicates that the existing legal and regulatory regime is reasonably sufficient, with some modifications, to accommodate the active injection phase of CO₂ capture and storage (CCS) operations, and the early takers of this new technology. However, governments in Alberta and Canada, and likely everywhere, need to address several pressing issues dealing mainly with the CCS post-operational phase. These issues, reviewed in this paper from an Alberta and Canadian perspective, fall into several categories: jurisdictional, property (ownership), regulatory and liability. Because Alberta is a landlocked province, matters relating to CO₂ storage under the seabed will not be addressed here except when discussing matters of jurisdiction and CO₂ classification. Possible models for post-injection liability transfer to the state are also presented. Although this review is focused on western Canada conditions, the issues are broad enough to be of interest in other jurisdictions, which may also adopt parts of the legal and regulatory framework that is quite well developed in Alberta.     

The influence of the precursor and synthesis method on the CO2 capture capacity of carpet waste-based sorbents

Adsorption is one of the most promising technologies for reducing CO₂ emissions and at present several different types of sorbents are being investigated. The use of sorbents obtained from low-cost and abundant precursors (i.e. solid wastes) appears an attractive strategy to adopt because it will contribute to a reduction not only in operational costs but also in the amount of waste that is dumped and burned in landfills every year. Following on from previous studies by the authors, in this work several carbon-based adsorbents were developed from different carpet wastes (pre-consumer and post-consumer wastes) by chemical activation with KOH at various activation temperatures (600–900 °C) and KOH:char impregnation ratios (0.5:1 to 4:1). The prepared materials were characterised by chemical analysis and gas adsorption (N₂, −196 °C; CO₂, 0 °C), and tested for CO₂ adsorption at temperatures of 25 and 100 °C. It was found that both the type of precursor and the conditions of activation (i.e. impregnation ratios, and activation temperatures), had a huge influence on the microporosity of the resultant samples and their CO₂ capture capacities. The carbon-based adsorbent that presented the maximum CO₂ capture capacities at 25 and 100 °C (13.8 wt.% and 3.1 wt.%, respectively), was prepared from a pre-consumer carpet waste and was activated at 700 °C using a KOH:char impregnation ratio of 1:1. This sample showed the highest narrow microporosity volume (0.47 cm³ g⁻¹), thus confirming that only pores of less than 1 nm are effective for CO₂ adsorption at atmospheric pressure.     

基于后向轨迹模式对北京市PM2.5来源的探讨

近年来中国经历了数次大范围雾霾天气,北京等多个城市更是遭遇连续雾霾。造成雾霾天气的主要污染物PM_2.5又称细颗粒物。为了进一步治理北京雾霾,为制定政策提供依据,须了解北京地区PM_2.5的来源。本文基于后向轨迹模式并结合PM_2.5浓度计算了2015年9月1日0：00至2016年8月31日23：00以北京为起始点,向后推算48小时的轨迹,并结合轨迹聚类分析法、潜在源贡献因子法（PSCF）、浓度权重轨迹分析法（CWT）等,探讨北京地区PM_2.5的来源。结果表明：模拟的后向轨迹经过聚类分析可分为6类,其中来自内蒙古西部的轨迹最多,来自西北、北西北方向的轨迹次之,来自西西北方向且在京津冀地区停留一段时间的轨迹占比最小,来自河北、山东、河南的交接地区及河北的沿海地区的轨迹占比也较小。其中来自内蒙古西部地区及河北、山东、河南交界地区的两类轨迹对北京的空气质量有较大的影响,是北京PM_2.5污染的主要潜在源区;来自北西北方向及河北的沿海地区两类轨迹的气团最为清洁,为北京带来良好的天气;来自西北及西西北方向的部分轨迹对应的PM_2.5浓度严重超标,说明来自此方向的气团对北京的空气质量也有一定的影响。     

Viscosities, thermal conductivities and diffusion coefficients of CO2 mixtures: Review of experimental data and theoretical models

Accurate experimental data on the thermo-physical properties of CO₂-mixtures are pre-requisites for development of more accurate models and hence, more precise design of CO₂ capture and storage (CCS) processes. A literature survey was conducted on both the available experimental data and the theoretical models associated with the transport properties of CO₂-mixtures within the operation windows of CCS. Gaps were identified between the available knowledge and requirements of the system design and operation. For the experimental gas-phase measurements, there are no available data about any transport properties of CO₂/H₂S, CO₂/COS and CO₂/NH₃; and except for CO₂/H₂O(/NaCl) and CO₂/amine/H₂O mixtures, there are no available measurements regarding the transport properties of any liquid-phase mixtures. In the prediction of gas-phase viscosities using Chapman–Enskog theory, deviations are typically <2% at atmospheric pressure and moderate temperatures. The deviations increase with increasing temperatures and pressures. Using both the Rigorous Kinetic Theory (RKT) and empirical models in the prediction of gas-phase thermal conductivities, typical deviations are 2.2–9%. Comparison of popular empirical models for estimation of gas-phase diffusion coefficients with newer experimental data for CO₂/H₂O shows deviations of up to 20%. For many mixtures relevant for CCS, the diffusion coefficient models based on the RKT show predictions within the experimental uncertainty. Typical reported deviations of the CO₂/H₂O system using empirical models are below 3% for the viscosity and the thermal conductivity and between 5 and 20% for the diffusion coefficients. The research community knows little about the effect of other impurities in liquid CO₂ than water, and this is an important area to focus in future work.     

CO2SINK—From site characterisation and risk assessment to monitoring and verification: One year of operational experience with the field laboratory for CO2 storage at Ketzin, Germany

The CO₂SINK pilot project at Ketzin is aimed at a better understanding of geological CO₂ storage operation in a saline aquifer. The reservoir consists of fluvial deposits with average permeability ranging between 50 and 100 mDarcy. The main focus of CO₂SINK is developing and testing of monitoring and verification technologies. All wells, one for injection and two for observation, are equipped with smart casings (sensors behind casing, facing the rocks) containing a Distributed Temperature Sensing (DTS) and electrodes for Electrical Resistivity Tomography (ERT). The in-hole Gas Membrane Sensors (GMS) observed the arrival of tracers and CO₂ with high temporal resolution. Geophysical monitoring includes Moving Source Profiling (MSP), Vertical Seismic Profiling (VSP), crosshole, star and 4-D seismic experiments. Numerical models are benchmarked via the monitoring results indicating a sufficient match between observation and prediction, at least for the arrival of CO₂ at the first observation well. Downhole samples of brine showed changes in the fluid composition and biocenosis. First monitoring results indicate anisotropic flow of CO₂ coinciding with the “on-time” arrival of CO₂ at observation well one (Ktzi 200) and the later arrival at observation well two (Ktzi 202). A risk assessment was performed prior to the start of injection. After one year of operations about 18,000 t of CO₂ were injected safely.     

Screening and selection of sites for CO2 sequestration based on pressure buildup

This paper presents a simple methodology for estimating pressure pressure buildup due to the injection of supercritical CO₂into a saline formation, and the limiting pressure at which the formation starts to fracture. Pressure buildup is calculated using the approximate solution of Mathias et al. [Mathias, S.A., Hardisty, P.E., Trudell, M.R., Zimmerman, R.W., 2009. Approximate solutions for pressure buildup during CO₂ injection in brine aquifers. Transp. Porous Media. doi:10.1007/s11242-008-9316-7], which accounts for two-phase Forchheimer flow (of supercritical CO₂ and brine) in a compressible porous medium. Compressibility of the rock formation and both fluid phases are also accounted for. Injection pressure is assumed to be limited by the pressure required to fracture the rock formation. Fracture development is assumed to occur when pore pressures exceed the minimum principal stress, which in turn is related to the Poisson’s ratio of the rock formation. Detailed guidance is also offered concerning the estimation of viscosity, density and compressibility for the brine and CO₂. Example calculations are presented in the context of data from the Plains CO₂ Reduction (PCOR) Partnership. Such a methodology will be useful for screening analysis of potential CO₂ injection sites to identify which are worthy of further investigation.     

Monitoring of the microbial community composition in saline aquifers during CO2 storage by fluorescence in situ hybridisation

This study reveals the first analyses of the composition and activity of the microbial community of a saline CO₂ storage aquifer. Microbial monitoring during CO₂ injection has been reported. By using fluorescence in situ hybridisation (FISH), we have shown that the microbial community was strongly influenced by the CO₂ injection. Before CO₂ arrival, up to 6 × 10⁶ cells ml⁻¹ were detected by DAPI staining at a depth of 647 m below the surface. The microbial community was dominated by the domain Bacteria that represented approximately 60% to 90% of the total cell number, with Proteobacteria and Firmicutes as the most abundant phyla comprising up to 47% and 45% of the entire population, respectively. Both the total cell counts as well as the counts of the specific physiological groups revealed quantitative and qualitative changes after CO₂ arrival. Our study revealed temporal outcompetition of sulphate-reducing bacteria by methanogenic archaea. In addition, an enhanced activity of the microbial population after five months CO₂ storage indicated that the bacterial community was able to adapt to the extreme conditions of the deep biosphere and to the extreme changes of these atypical conditions.     

Derivation of correlations to evaluate the impact of retrofitted post-combustion CO2 capture processes on steam power plant performance

When integrating a post-combustion CO₂ capture process and CO₂ compression into a steam power plant, the three interface quantities heat, electricity and cooling duty must be satisfied by the power plant, leading to a loss in net efficiency. The heat duty shows to be the largest contributor to the overall net efficiency penalty of the power plant. Additional energy penalty results from the cooling and electric power duty of the capture and compression units.In this work, the dependency of the energy penalty on the quantity and quality of the heat duty is analyzed and quantified for a state-of-the-art hard coal fired power plant. Furthermore, the energy penalty attributed to the additional cooling and power duty is quantified. As a result correlations are provided which enable to predict the impact of the heat, cooling and electricity duty of post-combustion CO₂ capture processes on the net output of a steam power plant in a holistic approach.     

Assessing the potential of yield improvements, through process scrap reduction, for energy and CO2 abatement in the steel and aluminium sectors

Targets to cut 2050 CO₂ emissions in the steel and aluminium sectors by 50%, whilst demand is expected to double, cannot be met by energy efficiency measures alone, so options that reduce total demand for liquid metal production must also be considered. Such reductions could occur through reduced demand for final goods (for instance by life extension), reduced demand for material use in each product (for instance by lightweight design) or reduced demand for material to make existing products. The last option, improving the yield of manufacturing processes from liquid metal to final product, is attractive in being invisible to the final customer, but has had little attention to date. Accordingly this paper aims to provide an estimate of the potential to make existing products with less liquid metal production.Yield ratios have been measured for five case study products, through a series of detailed factory visits, along each supply chain. The results of these studies, presented on graphs of cumulative energy against yield, demonstrate how the embodied energy in final products may be up to 15 times greater than the energy required to make liquid metal, due to yield losses. A top-down evaluation of the global flows of steel and aluminium showed that 26% of liquid steel and 41% of liquid aluminium produced does not make it into final products, but is diverted as process scrap and recycled. Reducing scrap substitutes production by recycling and could reduce total energy use by 17% and 6% and total CO₂ emissions by 16% and 7% for the steel and aluminium industries respectively, using forming and fabrication energy values from the case studies. The abatement potential of process scrap elimination is similar in magnitude to worldwide implementation of best available standards of energy efficiency and demonstrates how decreasing the recycled content may sometimes result in emission reductions.Evidence from the case studies suggests that whilst most companies are aware of their own yield ratios, few, if any, are fully aware of cumulative losses along their whole supply chain. Addressing yield losses requires this awareness to motivate collaborative approaches to improvement.     

Numerical investigation concerning the impact of CO2 geologic storage on regional groundwater flow

Large-scale storage of carbon dioxide in saline aquifers may cause considerable pressure perturbation and brine migration in deep rock formations, which may have a significant influence on the regional groundwater system. With the help of parallel computing techniques, we conducted a comprehensive, large-scale numerical simulation of CO₂ geologic storage that predicts not only CO₂ migration, but also its impact on regional groundwater flow. As a case study, a hypothetical industrial-scale CO₂ injection in Tokyo Bay, which is surrounded by the most heavily industrialized area in Japan, was considered, and the impact of CO₂ injection on near-surface aquifers was investigated, assuming relatively high seal-layer permeability (higher than 10 microdarcy). A regional hydrogeological model with an area of about 60 km × 70 km around Tokyo Bay was discretized into about 10 million gridblocks. To solve the high-resolution model efficiently, we used a parallelized multiphase flow simulator TOUGH2-MP/ECO2N on a world-class high performance supercomputer in Japan, the Earth Simulator. In this simulation, CO₂ was injected into a storage aquifer at about 1 km depth under Tokyo Bay from 10 wells, at a total rate of 10 million tons/year for 100 years. Through the model, we can examine regional groundwater pressure buildup and groundwater migration to the land surface. The results suggest that even if containment of CO₂ plume is ensured, pressure buildup on the order of a few bars can occur in the shallow confined aquifers over extensive regions, including urban inlands.     

Integration of counter-current relative permeability in the simulation of CO2 injection into saline aquifers

Carbon dioxide (CO₂) injection into saline aquifers is one of the promising options to sequester large amounts of CO₂ in geological formations. During as well as after injection of CO₂ into an aquifer, CO₂ migrates towards the top of the formation due to density differences between the formation brine and the injected CO₂. The time scales of CO₂ migration towards the top of an aquifer and the fraction of CO₂ that is trapped as residual gas depends strongly on the driving forces that are acting on the injected CO₂.When CO₂ migrates to the top of an aquifer, brine may be displaced downwards in a counter-current flow setting particularly during the injection period. A majority of the published work on counter-current flow settings have reported significant reductions in the associated relative permeability functions as compared to co-current measurements. However, this phenomenon has not yet been considered in the simulation of CO₂ storage into saline aquifers.In this paper we study the impact of changes in mobility for the two-phase brine/CO₂ system as a result of transitions between co- and counter-current flow settings. We have included this effect in a simulator and studied the impact of the related mobility reduction on the saturation distribution and residual saturation of CO₂ in aquifers over relevant time scales. We demonstrate that the reduction in relative permeability in the vertical direction changes the plume migration pattern and has an impact on the amount of gas that is trapped as a function of time. This is to our best knowledge the first attempt to integrate counter-current relative permeability into the simulation of injection and subsequent migration of CO₂ in aquifers. The results and analysis presented in this paper are directly relevant to all ongoing activities related to the design of large-scale CO₂ storage in saline aquifers.     

A method for quick assessment of CO2 storage capacity in closed and semi-closed saline formations

Saline aquifers of high permeability bounded by overlying/underlying seals may be surrounded laterally by low-permeability zones, possibly caused by natural heterogeneity and/or faulting. Carbon dioxide (CO₂) injection into and storage in such “closed” systems with impervious seals, or “semi-closed” systems with non-ideal (low permeability) seals, is different from that in “open” systems, from which the displaced brine can easily escape laterally. In closed or semi-closed systems, the pressure buildup caused by continuous industrial-scale CO₂ injection may have a limiting effect on CO₂ storage capacity, because geomechanical damage caused by overpressure needs to be avoided. In this research, a simple analytical method was developed for the quick assessment of the CO₂ storage capacity in such closed and semi-closed systems. This quick-assessment method is based on the fact that native brine (of an equivalent volume) displaced by the cumulative injected CO₂ occupies additional pore volume within the storage formation and the seals, provided by pore and brine compressibility in response to pressure buildup. With non-ideal seals, brine may also leak through the seals into overlying/underlying formations. The quick-assessment method calculates these brine displacement contributions in response to an estimated average pressure buildup in the storage reservoir. The CO₂ storage capacity and the transient domain-averaged pressure buildup estimated through the quick-assessment method were compared with the “true” values obtained using detailed numerical simulations of CO₂ and brine transport in a two-dimensional radial system. The good agreement indicates that the proposed method can produce reasonable approximations for storage–formation–seal systems of various geometric and hydrogeological properties.