Separation and capture of CO2 from large stationary sources and sequestration in geological formations--coalbeds and deep saline aquifers

The topic of global warming as a result of increased atmospheric CO2 concentration is arguably the most important environmental issue that the world faces today. It is a global problem that will need to be solved on a global level. The link between anthropogenic emissions of CO2 with increased atmospheric CO2 levels and, in turn, with increased global temperatures has been well established and accepted by the world. International organizations such as the United Nations Framework Convention on Climate Change (UNFCCC) and the Intergovernmental Panel on Climate Change (IPCC) have been formed to address this issue. Three options are being explored to stabilize atmospheric levels of greenhouse gases (GHGs) and global temperatures without severely and negatively impacting standard of living: (1) increasing energy efficiency, (2) switching to less carbon-intensive sources of energy, and (3) carbon sequestration. To be successful, all three options must be used in concert. The third option is the subject of this review. Specifically, this review will cover the capture and geologic sequestration of CO2 generated from large point sources, namely fossil-fuel-fired power gasification plants. Sequestration of CO2 in geological formations is necessary to meet the President's Global Climate Change Initiative target of an 18% reduction in GHG intensity by 2012. Further, the best strategy to stabilize the atmospheric concentration of CO2 results from a multifaceted approach where sequestration of CO2 into geological formations is combined with increased efficiency in electric power generation and utilization, increased conservation, increased use of lower carbon-intensity fuels, and increased use of nuclear energy and renewables. This review covers the separation and capture of CO2 from both flue gas and fuel gas using wet scrubbing technologies, dry regenerable sorbents, membranes, cryogenics, pressure and temperature swing adsorption, and other advanced concepts. Existing commercial CO2 capture facilities at electric power-generating stations based on the use of monoethanolamine are described, as is the Rectisol process used by Dakota Gasification to separate and capture CO2 from a coal gasifier. Two technologies for storage of the captured CO2 are reviewed--sequestration in deep unmineable coalbeds with concomitant recovery of CH4 and sequestration in deep saline aquifers. Key issues for both of these techniques include estimating the potential storage capacity, the storage integrity, and the physical and chemical processes that are initiated by injecting CO2 underground. Recent studies using computer modeling as well as laboratory and field experimentation are presented here. In addition, several projects have been initiated in which CO2 is injected into a deep coal seam or saline aquifer. The current status of several such projects is discussed. Included is a commercial-scale project in which a million tons of CO2 are injected annually into an aquifer under the North Sea in Norway. The review makes the case that this can all be accomplished safely with off-the-shelf technologies. However, substantial research and development must be performed to reduce the cost, decrease the risks, and increase the safety of sequestration technologies. This review also includes discussion of possible problems related to deep injection of CO2. There are safety concerns that need to be addressed because of the possibilities of leakage to the surface and induced seismic activity. These issues are presented along with a case study of a similar incident in the past. It is clear that monitoring and verification of storage will be a crucial part of all geological sequestration practices so that such problems may be avoided. Available techniques include direct measurement of CO2 and CH4 surface soil fluxes, the use of chemical tracers, and underground 4-D seismic monitoring. Ten new hypotheses were formulated to describe what happens when CO2 is pumped into a coal seam. These hypotheses provide significant insight into the fundamental chemical, physical, and thermodynamic phenomena that occur during coal seam sequestration of CO2.     

固定源氮氧化物排放及控制技术应用

固定源是氮氧化物排放的一个主要来源。通过对主要固定源氮氧化物生成机理及现有的排放控制技术进行论述，分析我国固定源氮氧化物排放的实际情况，提出我国固定源氮氧化物排放控制还处于起步阶段，氮氧化物排放标准相对宽松，氮氧化物排放控制技术有待进一步普及，并提出固定源氮氧化物排放治理的一些建议。     

Electricity from fossil fuels without CO2 emissions: assessing the costs of carbon dioxide capture and sequestration in U.S. electricity markets.

The decoupling of fossil-fueled electricity production from atmospheric CO2 emissions via CO2 capture and sequestration (CCS) is increasingly regarded as an important means of mitigating climate change at a reasonable cost. Engineering analyses of CO2 mitigation typically compare the cost of electricity for a base generation technology to that for a similar plant with CO2 capture and then compute the carbon emissions mitigated per unit of cost. It can be hard to interpret mitigation cost estimates from this plant-level approach when a consistent base technology cannot be identified. In addition, neither engineering analyses nor general equilibrium models can capture the economics of plant dispatch. A realistic assessment of the costs of carbon sequestration as an emissions abatement strategy in the electric sector therefore requires a systems-level analysis. We discuss various frameworks for computing mitigation costs and introduce a simplified model of electric sector planning. Results from a "bottom-up" engineering-economic analysis for a representative U.S. North American Electric Reliability Council (NERC) region illustrate how the penetration of CCS technologies and the dispatch of generating units vary with the price of carbon emissions and thereby determine the relationship between mitigation cost and emissions reduction.     

固定源氮氧化物排放及控制技术应用

固定源是氮氧化物排放的一个主要来源.通过对主要固定源氮氧化物生成机理及现有的排放控制技术进行论述,分析我国固定源氮氧化物排放的实际情况,提出我国固定源氮氧化物排放控制还处于起步阶段,氮氧化物排放标准相对宽松,氮氧化物排放控制技术有待进一步普及,并提出固定源氮氧化物排放治理的一些建议.     

A comprehensive multidisciplinary investigation on CO2 capture from diesel engine

Environmental Science and Pollution Research - Climate change and global warming are the visible consequences of the increased amount of carbon dioxide (CO2) in the atmosphere. Among the various...     

采空区煤层封存CO2影响因素分析

为考察不同物理化学环境对采空区煤层封存电厂烟气中CO2的影响,利用自行研制的煤大样量吸附装置,对常温常压条件下吸附体系中N2、SO2、H2O及pH影响CO2吸附的规律进行了实验研究。结果表明,改变物理化学环境可使CO2的吸附量发生变化,由于吸附亲和性差异和竞争吸附作用,N2使CO2的吸附量降低1.4%~2.1%,SO2气体使CO2吸附量降低2.3%~3.3%,煤中水分使CO2吸附量降低2.8%~3.7%;通过对煤样进行酸洗和碱洗处理发现,pH增大或减小后煤样对CO2的吸附量可增加1.5%~3.8%,并且pH减小时煤样对CO2的吸附量明显大于pH增大时煤样对CO2的吸附量。这一结果为增大CO2气体的封存量提供理论依据。     

湿法再生吸附剂制备及用于大气CO2的直接捕集

基于湿法再生吸附技术,利用强碱性季铵盐树脂材料制备了异相吸附剂薄膜,应用于大气中极低CO2的直接分离,以对抗全球变暖。通过滴定法分析吸附剂材料的电荷密度和吸附容量,利用SEM分析不同工况下制备出来的膜材料的表观结构,并对膜材料进行CO2吸附性能的测试。结果发现,热处理能够明显提高膜材料的吸附性能,还研究吸附剂制备对吸附速率,吸附量和机械强度等性能的影响,发现粒径小于43μm的树脂粉末,按60％质量分数制成的500μm厚膜材料具有较优的综合性能。     

CO2 sequestration by propagation of the fast-growing Azolla spp.

Environmental Science and Pollution Research - Azolla is a group of aquatic floating plants that can achieve very high growth rates compared to other aquatic macrophytes, with a doubling time of...     

磷石膏悬浮液强化氨法脱碳尾气微量氨吸收

以强化氨法脱碳尾气微量氨吸收为目的,提出了以磷石膏悬浮液代替清水吸收尾气微量氨的新方法。分析了磷石膏悬浮液强化吸收氨与二氧化碳过程的热力学机理,绘制了CaSO4·2H2O溶解影响下常温常压低浓度NH3-CO2-H2O体系气液平衡分压相图,并开展了模拟实验进行验证。实验结果表明,吸收过程中磷石膏悬浮液可改变吸收液的热力学性质,使吸收剂的平衡氨分压≤1 Pa,从而以较小的液气比、常温常压实现尾气氨≤10×10-6。     

Dilution-based emissions sampling from stationary sources: Part 2--Gas-fired combustors compared with other fuel-fired systems

With the recent focus on fine particle matter (PM2.5), new, self-consistent data are needed to characterize emissions from combustion sources. Such data are necessary for health assessment and air quality modeling. To address this need, emissions data for gas-fired combustors are presented here, using dilution sampling as the reference. The dilution method allows for collection of emitted particles under conditions simulating cooling and dilution during entry from the stack into the air. The sampling and analysis of the collected particles in the presence of precursor gases, SO2 nitrogen oxide, volatile organic compound, and NH3 is discussed; the results include data from eight gas fired units, including a dual-fuel institutional boiler and a diesel engine powered electricity generator. These data are compared with results in the literature for heavy-duty diesel vehicles and stationary sources using coal or wood as fuels. The results show that the gas-fired combustors have very low PM2.5 mass emission rates in the range of approximately 10(-4) lb/million Btu (MMBTU) compared with the diesel backup generator with particle filter, with approximately 5 x 10(-3) lb/MMBTU. Even higher mass emission rates are found in coal-fired systems, with rates of approximately 0.07 lb/MMBTU for a bag-filter-controlled pilot unit burning eastern bituminous coal. The characterization of PM2.5 chemical composition from the gas-fired units indicates that much of the measured primary particle mass in PM2.5 samples is organic or elemental carbon and, to a much less extent, sulfate. Metal emissions are quite low compared with the diesel engines and the coal- or wood-fueled combustors. The metals found in the gas-fired combustor particles are low in concentration, similar in concentration to ambient particles. The interpretation of the particulate carbon emissions is complicated by the fact that an approximately equal amount of particulate carbon (mainly organic carbon) is found on the particle collector and a backup filter. It is likely that measurement artifacts, mostly adsorption of volatile organic compounds on quartz filters, are positively biasing "true" particulate carbon emission results.     

Anthropogenic and natural CO2 emission sources in an arid urban environment

Recent research has shown the Phoenix, AZ metropolitan region to be characterized by a CO2 dome that peaks near the urban center. The CO2 levels, 50% greater than the surrounding non-urban areas, have been attributed to anthropogenic sources and the physical geography of the area. We quantified sources of CO2 emissions across the metropolitan region. Anthropogenic CO2 emission data were obtained from a variety of government and NGO sources. Soil CO2 efflux from the dominant land-use types was measured over the year. Humans and automobile activity produced more than 80% input of CO2 into the urban environment. Soil CO2 efflux from the natural desert ecosystems showed minimal emissions during hot and dry periods, but responded rapidly to moisture. Conversely, human maintained vegetation types (e.g. golf courses, lawns, irrigated agriculture) have greater efflux and are both temperature and soil moisture dependent. Landfills exhibited the most consistent rates, but were temperature and moisture independent. We estimate the annual CO2 released from the predominant land-use types in the Phoenix region and present a graphical portrayal of soil CO2 emissions and the total natural and anthropogenic CO2 emissions in the metropolitan region using a GIS-based approach. The results presented here do not mimic the spatial pattern shown in previous studies. Only, with sophisticated mixing models will we be able to address the total effect of urbanization on CO2 levels and the contribution to regional patterns.     

Feasibility study of using brine for carbon dioxide capture and storage from fixed sources

A laboratory-scale reactor was developed to evaluate the capture of carbon dioxide (CO2) from a gas into a liquid as an approach to control greenhouse gases emitted from fixed sources. CO2 at 5-50% concentrations was passed through a gas-exchange membrane and transferred into liquid media--tap water or simulated brine. When using water, capture efficiencies exceeded 50% and could be enhanced by adding base (e.g., sodium hydroxide) or the combination of base and carbonic anhydrase, a catalyst that speeds the conversion of CO2 to carbonic acid. The transferred CO2 formed ions, such as bicarbonate or carbonate, depending on the amount of base present. Adding precipitating cations, like Ca++, produced insoluble carbonate salts. Simulated brine proved nearly as efficient as water in absorbing CO2, with less than a 6% reduction in CO2 transferred. The CO2 either dissolved into the brine or formed a mixture of gas and ions. If the chemistry was favorable, carbonate precipitate spontaneously formed. Energy expenditure of pumping brine up and down from subterranean depths was modeled. We conclude that using brine in a gas-exchange membrane system for capturing CO2 from a gas stream to liquid is technically feasible and can be accomplished at a reasonable expenditure of energy.     

Emission estimation and congener-specific characterization of polybrominated diphenyl ethers from various stationary and mobile sources

Here we show that combustion sources, including waste incinerators, metallurgical processes, power-heating systems and so on, are also important emitters of polybrominated diphenyl ethers (PBDEs) to the atmosphere. Geometric mean PBDE concentrations in the stack flue gases of the combustion sources ranged from 8.07 to 469 ng/Nm³. The sinter plants (24.7 mg/h), electric arc furnaces (EAFs) (11.3 mg/h) and power plants (50.8 mg/h) possessed the largest PBDE emission rates, which were several orders higher than those of the other reported sources. The occurrences of the PBDEs in the flue gases of the power plants and vehicles, as well as their PBDE concentrations statistically highly correlated with combustion-originated PCDD/Fs, revealing that PBDEs should be the products of combustion. The ranking of major PBDE emission sources in Taiwanese PBDE inventory for combustion sources was power plants (30.85 kg/year), vehicles (14.9 kg/year) and metallurgical processes (5.88 kg/year).     

Dilution-based emissions sampling from stationary sources: Part 1--Compact sampler methodology and performance

This paper presents the design and performance of a compact dilution sampler (CDS) for characterizing fine particle emissions from stationary sources. The sampler is described, along with the methodology adopted for its use. Dilution sampling has a number of advantages, including source emissions that are measured under conditions simulating stack gas entry and mixing in the ambient atmosphere. This is particularly important for characterizing the semivolatile species in effluents as a part of particulate emissions. The CDS characteristics and performance are given, along with sampling methodology. The CDS was compared with a reference dilution sampler. The results indicate that the two designs are comparable for tests on gas-fired units and a diesel electrical generator. The performance data indicate that lower detection limits can be achieved relative to current regulatory methods for particulate emissions. Test data for the fine particulate matter (PM2.5) emissions are provided for comparison with U.S. Environment Protection Agency (EPA) Conditional Test Method 040 for filterable particulate matter (FPM) and the EPA Method 202 for condensable particulate matter. This comparison showed important differences between methods, depending on whether a comparison is done between in situ FPM determinations or the sum of such values with condensable PM from liquid filled impingers chilled in an ice bath. These differences are interpretable in the light of semivolatile material present in the stack effluent and, in some cases, differences in detection and quantification limits. Determination of emissions from combustors using liquid fuels can be readily achieved using 1-hr sampling with the CDS. Emissions from gasfired combustors are very low, requiring careful attention to sample volumes. Sampling volumes corresponding with 6-hr operation were used for the combined mass and broad chemical speciation. Particular attention to dilution sampler operation with clean dilution air also is essential for gas-fired sources.     

Validation of a test method for the measurement of methanol emissions from stationary sources

Title III of the 1990 Clean Air Act Amendments designated methanol as a pollutant to be regulated. The U.S. Environmental Protection Agency (EPA), through a contract with Research Triangle Institute, has developed a method for measuring methanol emissions from stationary sources. The methanol sampling train (MST) consists of a glass-lined heated probe, two condensate knockout traps, and three sorbent cartridges packed with Anasorb 747. Samples are desorbed with a 1:1 mixture of carbon disulfide (CS2) and N,N-dimethylformamide (DMF). Condensate water and CS2/ DMF samples are analyzed by gas chromatography with flame ionization detection. The MST has a practical quantitation limit of approximately 3 ppm for a 20-L sample. Samples were shown to be stable for at least two weeks after collection. Field tests of the MST and the National Council of the Paper Industry for Air and Stream Improvement (NCASI) methanol sampling method were conducted at two pulp and paper mills. Sampling and analysis procedures followed EPA Method 301 requirements. The sampling location for the first field test was the inlet vent to a softwood bleach plant scrubber, where the methanol concentration was approximately 30 ppm. The mean recovery of spike was 108.3% for the MST method and 81.6% for the NCASI method. Although neither method showed significant bias at the 95% confidence level, the between-methods bias was significantly different. A second field test was conducted at a vent from a black liquor oxidation tank where the methanol concentration was approximately 350 ppm. Mean spike recoveries were 96.6 and 94.2% for the MST and NCASI methods, respectively. The biases of the two methods and the between-methods bias were not significantly different for the second field test.     

温度对离子液体支撑膜捕集CO2的影响

传统CO2的捕集方法存在设备投资大、环境污染严重、再生能耗高等缺点,利用新型绿色工质离子液体负载于聚偏氟乙烯上制备离子液体支撑膜可以较好地解决该问题。在压力为0.2 MPa、流量为50 mL·min-1、温度在298~318 K范围内变化时,测定了CO2在1-乙基-3甲基咪唑双三氟磺酰亚胺盐（[Emim][Tf2N]）和1-乙基-3-甲基咪唑醋酸盐（[Emim][AC]）2种离子液体支撑膜中的渗透系数、溶解度和扩散系数,采用Van’t Hoff方程对溶解度数据进行关联、Arrhenius方程对渗透和扩散系数的数据进行关联。实验结果表明,CO2在2种离子液体支撑膜中的渗透和扩散系数随着温度的升高而增大,溶解度随着温度的升高而降低。[Emim][Tf2N]离子液体支撑膜对CO2的捕集性能优于[Emim][AC]支撑膜,CO2在[Emim][Tf2N]支撑膜中的溶解度最大值为0.447,在[Emim][AC]离子液体支撑膜中的最大溶解度为0.253,由此可确定离子液体支撑膜分离CO2的最佳工作温度,为其在工业应用中奠定良好的基础。     

Measurement of ultrafine particle size distributions from coal-, oil-, and gas-fired stationary combustion sources

Currently, we have limited knowledge of the physical and chemical properties of emitted primary combustion aerosols and the changes in those properties caused by nucleation, condensation growth of volatile species, and particle coagulations under dilution and cooling in the ambient air. A dilution chamber was deployed to sample exhaust from a pilot-scale furnace burning various fuels at a nominal heat input rate of 160 kW/h(-1) and 3% excess oxygen. The formation mechanisms of particles smaller than 420 nm in electrical mobility diameter were experimentally investigated by measurement with a Scanning Mobility Particle Sizer (SMPS) as a function of aging times, dilution air ratios, combustion exhaust temperatures, and fuel types. Particle formation in the dilution process is a complex mixture of nucleation, coagulation, and condensational growth, depending on the concentrations of available condensable species and solid or liquid particles (such as soot, ash) in combustion exhausts. The measured particle size distributions in number concentrations measured show peaks of particle number concentrations for medium sulfur bituminous coal, No. 6 fuel oil, and natural gas at 40-50 nm, 70-100 nm, and 15-25 nm, respectively. For No. 6 fuel oil and coal, the particle number concentration is constant in the range of a dilution air ratio of 50, but the number decreases as the dilution air ratio decreases to 10. However, for natural gas, the particle number concentration is higher at a dilution air ratio of 10 and decreases at dilution air ratios of 20-50. At a dilution air ratio of 10, severe particle coagulation occurs in a relatively short time. Samples taken at different combustion exhaust temperatures for these fuel types show higher particle number concentrations at 645 K than at 450 K. As the aging time of particles increases, the particles increase in size and the number concentrations decrease. The largest gradient of particle number distribution occurs within the first 10 sec after dilution but shows only minor differences between 10 and 80 sec. The lifetimes of the ultrafine particles are relatively short, with a scale on the order of a few seconds. Results from this study suggest that an aging time of 10 sec and a dilution air ratio of 20 are sufficient to obtain representative primary particle emission samples from stationary combustion sources.