粉煤灰用于碳捕集、利用及封存的研究进展

总结了国内外粉煤灰用于CO₂捕集、利用和封存的不同技术研究进展,同时对今后的研究和机遇进行了展望.粉煤灰自身可通过直接干式、半干式、湿式和间接方法对CO₂进行矿化捕集封存,在CO₂矿化的同时降低粉煤灰自身重金属的浸出,并且矿化后的粉煤灰因有效降低游离CaO和MgO的含量而更适合于制作混凝土添加剂.粉煤灰也可制成活性炭、沸石和多孔二氧化硅等产品,并对CO₂进行物理吸附捕集,制成产品的类型主要取决于粉煤灰自身的成分组成和理化性质.在CO₂利用方面,粉煤灰除了可拓展建材的利用途径外,还可制作CO₂多种化学工艺所需催化剂或催化剂载体,以及制作新型材料拟薄水铝石等.我国“双碳”目标的提出及燃煤电厂粉煤灰自身的理化特性为粉煤灰提供了一条新的综合利用途径.     

The oxycoal process with cryogenic oxygen supply

Due to its large reserves, coal is expected to continue to play an important role in the future. However, specific and absolute CO₂ emissions are among the highest when burning coal for power generation. Therefore, the capture of CO₂ from power plants may contribute significantly in reducing global CO₂ emissions. This review deals with the oxyfuel process, where pure oxygen is used for burning coal, resulting in a flue gas with high CO₂ concentrations. After further conditioning, the highly concentrated CO₂ is compressed and transported in the liquid state to, for example, geological storages. The enormous oxygen demand is generated in an air-separation unit by a cryogenic process, which is the only available state-of-the-art technology. The generation of oxygen and the purification and liquefaction of the CO₂-enriched flue gas consumes significant auxiliary power. Therefore, the overall net efficiency is expected to be lowered by 8 to 12 percentage points, corresponding to a 21 to 36% increase in fuel consumption. Oxygen combustion is associated with higher temperatures compared with conventional air combustion. Both the fuel properties as well as limitations of steam and metal temperatures of the various heat exchanger sections of the steam generator require a moderation of the temperatures during combustion and in the subsequent heat-transfer sections. This is done by means of flue gas recirculation. The interdependencies among fuel properties, the amount and the temperature of the recycled flue gas, and the resulting oxygen concentration in the combustion atmosphere are investigated. Expected effects of the modified flue gas composition in comparison with the air-fired case are studied theoretically and experimentally. The different atmosphere resulting from oxygen-fired combustion gives rise to various questions related to firing, in particular, with regard to the combustion mechanism, pollutant reduction, the risk of corrosion, and the properties of the fly ash or the deposits that form. In particular, detailed nitrogen and sulphur chemistry was investigated by combustion tests in a laboratory-scale facility. Oxidant staging, in order to reduce NO formation, turned out to work with similar effectiveness as for conventional air combustion. With regard to sulphur, a considerable increase in the SO₂ concentration was found, as expected. However, the H₂S concentration in the combustion atmosphere increased as well. Further results were achieved with a pilot-scale test facility, where acid dew points were measured and deposition probes were exposed to the combustion environment. Besides CO₂ and water vapour, the flue gas contains impurities like sulphur species, nitrogen oxides, argon, nitrogen, and oxygen. The CO₂ liquefaction is strongly affected by these impurities in terms of the auxiliary power requirement and the CO₂ capture rate. Furthermore, the impurity of the liquefied CO₂ is affected as well. Since the requirements on the liquid CO₂ with regard to geological storage or enhanced oil recovery are currently undefined, the effects of possible flue gas treatment and the design of the liquefaction plant are studied over a wide range.     

我国城市生活垃圾处理温室气体排放特征

CH₄和CO₂是大气中主要的温室气体,研究我国城市生活垃圾处理过程中二者的排放情况,对制订温室气体减排政策和应对气候变化有着至关重要的意义. 利用IPCC(政府间气候变化专门委员会)提供的废弃物处理排放CH₄和CO₂的计算方法,对1979—2011年我国城市生活垃圾处理CH₄和CO₂排放量(不含港澳台数据)进行统计分析. 结果表明:①2011年我国城市生活垃圾人均清运量为0.46 t,比2000年增加了53.3%. ②1979—2011年,我国城市生活垃圾处理仍以填埋为主,焚烧和堆肥处理方式相对较少,但近年来焚烧处理量呈逐年增加趋势,其中2011年焚烧处理量是2001年的16.8倍. ③我国城市生活垃圾处理产生的CH₄和CO₂排放量均呈逐年增长趋势,至2011年,二者分别达到7 024.03×104 (以CO₂当量计,下同)和706.22×104 t;其中,2011年CH₄排放量是1990年的20.0倍,CO₂排放量是2001年的16.8倍. ④城市生活垃圾产生的温室气体排放具有明显的地域特性,其中华东地区CH₄和CO₂排放总量高达2 570.98×104 t;西北地区最小,仅为482.3×104 t. 该差异与城市发展规模、人们生活习惯和城市化进程等影响因子紧密相关.      

CO2泡沫混凝土碳封存潜力分析

CO₂捕集、利用与封存是碳中和技术体系的重要组成部分,混凝土在大规模吸收CO₂方面具有巨大的发展潜力.为了掌握CO₂泡沫混凝土的碳封存潜力,分析了CO₂泡沫混凝土的固碳机制,建立了CO₂泡沫混凝土固碳能力的数学模型,估算了CO₂泡沫混凝土的固碳和储碳能力.结果表明,CO₂泡沫混凝土碳封存能力的99%以上是由混凝土骨架的化学碳化方式完成的,而泡孔的储碳能力较弱;按照30%碳化率估算,我国每年生产的混凝土在全生命周期内的碳封存量平均为2.18亿t,超过大兴安岭林区森林1 a的碳汇;近5年,我国CO₂泡沫混凝土的碳封存潜力为5.80亿t ·a^-1,在煤电一体化矿区的固废和废气资源化利用方面具有很好的应用前景.CO₂泡沫混凝土在凝固前的稳定性是下一步要重点解决的技术难题.     

中国水泥行业通过CCUS技术的减排潜力评估

中国水泥行业面临巨大的碳达峰与碳中和压力.CO₂捕集利用与封存（CCUS）技术是能够实现化石资源低碳利用的碳减排技术.在中国水泥企业数据基础上,采用全流程CCUS系统模型（ITEAM-CCUS）评估CCUS的碳减排潜力对水泥企业碳中和非常重要.模型从源汇匹配距离、捕集率、CCUS技术和技术水平这4个方面设置了10种情景,完成了水泥行业的企业筛选、场地筛选、CCUS技术经济评估和源汇匹配,初步回答了水泥企业结合CCUS的封存场地、减排规模、成本范围和优先项目分布等关键问题.在250 km匹配距离、85%净捕集率、CO₂-EWR技术和当前技术水平情景,44%的水泥企业可以利用CO₂强化地下水开采（CO₂-EWR）技术开展碳减排,累计年碳减排量为6.25亿t,平准化成本为290~1838元·t^-1;具有全流程CO₂-EWR早期示范优势的地区为新疆、内蒙古、宁夏、河南和河北等.水泥企业开展全流程CCUS项目技术可行,可以实现大规模CO₂减排,低成本项目具有早期示范机会.研究结果可为水泥行业低碳发展和CCUS商业化部署提供定量参考.     

以粉煤灰为原料制备低温CO2吸附剂的工艺参数优化

利用高铝粉煤灰预脱硅液作为载体原料,通过使用胺基化合物对载体改性制备低温CO_2吸附剂.应用6 sigma中的工具,对制备工艺进行优化,得到理想的吸附剂,并对吸附剂样品进行表征.结果表明制备的CO_2吸附剂表现出良好的CO_2吸附性能.此类CO_2吸附剂具有吸附容量高(160 mg·g~(-1))、吸附速率快、对设备腐蚀低、成本低廉等特点,是一种极具工业应用潜力的CO_2吸附剂.     

Probing the potential of polyester for CO2 capture

Global warming, the major environmental issue confronted by humanity today, is caused by rising level of green house gases. Carbon capture and storage technologies offer potential for tapering CO2 emission in the atmosphere. Adsorption is believed to be a promising technology for CO2 capture. For this purpose, a polyester was synthesized by polycondensation of1,3,5-benzenetricarbonyl trichloride and cyanuric acid in pyridine and dichloromethane mixture. The polymer was then characterized using FT-IR, TGA, BET surface area and pore size analysis, FESEM and CO2 adsorption measurements. The CO2 adsorption capacities of the polyester were evaluated at a pressure of 1 bar and two different temperatures（273 and 298 K）.The performance of these materials to adsorb CO2 at atmospheric pressure was measured by optimum CO2 uptake of 0.244 mmol/g at 273 K. The synthesized polyester, therefore, has the potential to be exploited as CO2 adsorbent in pre-combustion capture process.     

Development of a hybrid photo-bioreactor and nanoparticle adsorbent system for the removal of CO2 , and selected organic and metal co-pollutants

Fossil fuel combustion and many industrial processes generate gaseous emissions that contain a number of toxic organic pollutants and carbon dioxide (CO₂) which contribute to climate change and atmospheric pollution. There is a need for green and sustainable solutions to remove air pollutants, as opposed to conventional techniques which can be expensive, consume additional energy and generate further waste. We developed a novel integrated bioreactor combined with recyclable iron oxide nano/micro-particle adsorption interfaces, to remove CO_2, and undesired organic air pollutants using natural particles, while generating oxygen. This semi-continuous bench-scale photo-bioreactor was shown to successfully clean up simulated emission streams of up to 45% CO₂ with a conversion rate of approximately 4% CO₂ per hour, generating a steady supply of oxygen (6 mmol/hr), while nanoparticles effectively remove several undesired organic by-products. We also showed algal waste of the bioreactor can be used for mercury remediation. We estimated the potential CO₂ emissions that could be captured from our new method for three industrial cases in which, coal, oil and natural gas were used. With a 30% carbon capture system, the reduction of CO₂ was estimated to decrease by about 420,000, 320,000 and 240,000 metric tonnes, respectively for a typical 500 MW power plant. The cost analysis we conducted showed potential to scale-up, and the entire system is recyclable and sustainable. We further discuss the implications of usage of this complete system, or as individual units, that could provide a hybrid option to existing industrial setups.     

Assessment of GHG inventories from the LUCF sector of Annex-I countries

Reporting of CO₂ emissions and removals from the landuse change and forestry (LUCF) sector is assessed in this paper based onthe National GHG inventories and the National Communications submittedby the Annex-I countries. LUCF sector is a net sink for 27 countries outof 31 countries and a source for Australia, Estonia, Lithuania and UnitedKingdom. LUCF sector for Annex-I countries, as a group is a net sink of2035 Tg CO₂ (555 Tg Carbon). The sink feature is largely due toCO₂ removal by the existing forests, plantations and other trees.Forest and grassland conversion (deforestation) is not a major source ofCO₂ in the Annex-I countries. Many Annex-I countries have notfully adopted the reporting format of IPCC limiting the comparability andtransparency. Several Annex-I countries have modified the CO₂emission/removal estimates for 1990, but have not explained the reasons.Reporting of uncertainty is very limited. The methods adopted andparticularly reporting is inadequate to meet the requirements foroperationalising the Kyoto Protocol articles relevant to LUCF;comparability, transparency and verifiability.     

CO2泄漏对稻田水基础水质指标的影响研究

碳捕集与封存（CCS）技术是当前抑制大气中CO₂过快增长的有效方法,但在CCS项目实施过程中仍存在CO₂泄漏而影响地表环境及生态的风险.本研究以龙粳31号和龙稻18号为实验对象,模拟研究地质封存CO₂以不同速率泄漏对稻田水环境基础水质指标D_CO2、pH、DO和ORP的影响,探讨稻田水对地质封存CO₂泄漏的响应规律.结果表明：CO₂泄漏对稻田水的D_CO2、pH、DO和ORP长期影响显著,不同CO₂泄漏速率对稻田水质指标的影响差异显著.在各指标平衡后,稻田水各水质指标均呈现明显的日变化规律,其中D_CO2呈早晚高、午间低的先减后增规律,而pH、DO和ORP均呈早晚低、午间高的先增后减规律.根据各指标差异性分析,建议将稻田水D_CO2作为稻田系统CO₂泄漏监测的主要指标,将pH、DO、ORP作为CO₂泄漏监测的辅助指标.     

CO2封存泄漏的稻田土壤细菌监测指标筛选研究

为研究CO₂地质封存过程中CO₂泄漏对水稻及稻田土壤的风险影响,利用CO₂模拟泄漏平台,研究了不同CO₂泄漏速率下水稻生长、稻田土壤性质与土壤细菌组成及多样性的变化特征.结果表明：随着CO₂泄漏速率的增加,稻田土壤pH显著降低,电导率显著增加,水稻生长受到明显抑制;稻田土壤细菌的丰富度指数和多样性指数均有增加,均匀度指数有所降低.CO₂泄漏显著改变了稻田土壤细菌组成,稻田土壤的优势菌门中变形菌门、拟杆菌门与绿弯菌门的相对丰度总体降低,而酸杆菌门与放线菌门的相对丰度总体升高;稻田土壤优势菌属中RB41、MND1、厌氧粘菌属及鞘脂单胞菌属的丰度总体升高,而硝化螺旋菌属的丰度总体降低;稀有细菌中CO₂泄漏下全部出现的有粘胶球形菌门、柔膜菌门及双头菌属、硫杆菌属,CO₂泄漏后全部消亡的为假单胞菌属.建议将变形菌门的减少和酸杆菌门的增加,以及RB41、MND1及厌氧粘菌属的增加作为稻田土壤CO₂泄漏监测的推荐指标.     

The adequacy of GWPs as indicators of damage costsincurred by global warming

This article looks at the ability of Global Warming Potentials (GWPs) towork as indicators of equivalence for temperature development and damagecosts. We look at two abatement scenarios that are equivalent when using100-year GWPs: one scenario reduces short-lived gases, mainly methane(CH₄); the other scenario reduces carbon dioxide (CO₂).Despite their equivalence in terms of CO₂ equivalents, the scenariosdo not result in equal rates or levels of temperature change. The disparitiescontinue as we move further down the chain of causality toward damagecosts, measured either in terms of rate of climate change or level of climatechange. Compared to the CH₄ mitigation scenario, the CO₂mitigation scenario gives present value costs 1.3 and 1.5 times higher forlevel- and rate-dependent damage costs, respectively, assuming a discountrate of 3%. We also test the GWPs for other time horizons and theconclusions remain the same; using GWP as an index to reflect equivalentclimate effects and damage costs from emissions is questionable.     

中国水泥碳排放测算的影响因素分析与不确定度计算

作为水泥生产大国和CO_2排放大户,中国水泥行业的CO_2排放在国际上受到越来越广泛的重视,然而不同的研究结果之间存在不同程度的差异.为了定量研究中国水泥碳排放测算的影响因素,对碳排放因子的测算、运营边界的界定及水泥熟料或水泥成品的产量这3个影响因素做了详细分析,并对碳排放因子的不确定度做了定量计算.结果发现,影响中国水泥碳排放测算的最主要因素是碳排放因子,而该因素又与生产工艺、燃料和熟料水泥比等密切相关.本研究结果比IPCC、EDGAR、CDIAC和WBCSD/CSI等研究结果均低,并且差异逐年显著,以水泥碳排放来自碳酸盐分解的部分为例,2000年相差约65 Mt,而2012年差值接近450 Mt.计算表明,中国水泥碳排放不确定度为12%~22%.因此,水泥碳排放测算的影响因素较多,在计算中国水泥碳排放量时不可照搬国外研究的参数.     

深部储层中CO2沿断层泄漏量的影响因素

CGS（CO₂地质储存）是CO₂减排的重要手段之一,天然裂隙的存在则是CGS的潜在风险.CO₂地质储存过程中储层上覆盖层及其浅部含水层是防止CO₂泄漏的天然屏障,为了探究深部咸水层中CO₂沿断层的泄漏过程并获得断层渗透率及储层中超临界CO₂流体初始条件（初始饱和度、初始泄漏压力）对CO₂沿断层泄漏速率和泄漏量的影响程度,依据鄂尔多斯CO₂灌注工程示范区资料,使用多相、多组分溶质运移数值模拟软件TOUGH2建立了2D概念模型.结果表明,深部咸水层中的CO₂在压力差和浓度差的作用下沿断层发生泄漏,到达浅部含水层后开始发生侧向运移,100 a内运移了约200 m的水平距离;由于浮力的作用,CO₂集中在含水层顶板处,有效地防止了CO₂向外泄漏.影响因素分析表明,100 a内断层渗透性能为低渗、中渗和高渗条件时,CO₂累积泄漏量分别为0、1 050和3 000 t;CO₂初始饱和度分别为0.20、0.50和0.99时,CO₂累积泄漏量分别为550、1 050和1 650 t;初始泄漏压力分别为17.3、17.6和18.1 MPa时,CO₂累积泄漏量则分别为900、1 050和1 400 t.除此之外,断层渗透性、CO₂初始气体饱和度和初始泄漏压力对CO₂泄漏的影响还体现在泄漏发生时间和平均泄漏速率上.研究显示,各因素对CO₂沿断层泄漏过程的影响程度表现为断层渗透性能> CO₂初始饱和度> CO₂初始泄漏压力.      

Low-carbon transition of iron and steel industry in China: Carbon intensity, economic growth and policy intervention

As the biggest iron and steel producer in the world and one of the highest CO₂ emission sectors, China's iron and steel industry is undergoing a low-carbon transition accompanied by remarkable technological progress and investment adjustment, in response to the macroeconomic climate and policy intervention. Many drivers of the CO₂ emissions of the iron and steel industry have been explored, but the relationships between CO₂ abatement, investment and technological expenditure, and their connections with the economic growth and governmental policies in China, have not been conjointly and empirically examined. We proposed a concise conceptual model and an econometric model to investigate this crucial question. The results of regression, Granger causality test and impulse response analysis indicated that technological expenditure can significantly reduce CO₂ emissions, and that investment expansion showed a negative impact on CO₂ emission reduction. It was also argued with empirical evidence that a good economic situation favored CO₂ abatement in China's iron and steel industry, while achieving CO₂ emission reduction in this industrial sector did not necessarily threaten economic growth. This shed light on the dispute over balancing emission cutting and economic growth. Regarding the policy aspects, the year 2000 was found to be an important turning point for policy evolution and the development of the iron and steel industry in China. The subsequent command and control policies had a significant, positive effect on CO₂ abatement.     

Equal Opportunity for Biomass in Greenhouse Gas Accounting of CO2 Capture and Storage: A Step Towards More Cost-Effective Climate Change Mitigation Regimes

Carbon dioxide capture and permanent storage (CCS) is one of the most frequently discussed technologies with the potential to mitigate climate change. The natural target for CCS has been the carbon dioxide (CO₂) emissions from fossil energy sources. However, CCS has also been suggested in combination with biomass during recent years. Given that the impact on the earth's radiative balance is the same whether CO₂ emissions of a fossil or a biomass origin are captured and stored away from the atmosphere, we argue that an equal reward should be given for the CCS, independent of the origin of the CO₂. The guidelines that provide assistance for the national greenhouse gas (GHG) accounting under the Kyoto Protocol have not considered CCS from biomass (biotic CCS) and it appears that it is not possible to receive emission credits for biotic CCS under the first commitment period of the Kyoto Protocol, i.e., 2008–2012. We argue that it would be unwise to exclude this GHG mitigation alternative from the competition with other GHG mitigation options. We also propose a feasible approach as to how emission credits for biotic CCS could be included within a future accounting framework.     

Low-carbon transition of iron and steel industry in China: Carbon intensity,economic growth and policy intervention

As the biggest iron and steel producer in the world and one of the highest CO₂ emission sectors, China's iron and steel industry is undergoing a low-carbon transition accompanied by remarkable technological progress and investment adjustment, in response to the macroeconomic climate and policy intervention. Many drivers of the CO₂ emissions of the iron and steel industry have been explored, but the relationships between CO₂ abatement, investment and technological expenditure, and their connections with the economic growth and governmental policies in China, have not been conjointly and empirically examined. We proposed a concise conceptual model and an econometric model to investigate this crucial question. The results of regression, Granger causality test and impulse response analysis indicated that technological expenditure can significantly reduce CO₂ emissions, and that investment expansion showed a negative impact on CO₂ emission reduction. It was also argued with empirical evidence that a good economic situation favored CO₂ abatement in China's iron and steel industry, while achieving CO₂ emission reduction in this industrial sector did not necessarily threaten economic growth. This shed light on the dispute over balancing emission cutting and economic growth. Regarding the policy aspects, the year 2000 was found to be an important turning point for policy evolution and the development of the iron and steel industry in China. The subsequent command and control policies had a significant, positive effect on CO₂ abatement.     

Toward rational design of amines for CO2 capture: Substituent effect on kinetic process for the reaction of monoethanolamine with CO2

Amines have been considered as promising candidates for post-combustion CO₂ capture. A mechanistic understanding for the chemical processes involved in the capture and release of CO₂ is important for the rational design of amines. In this study, the structural effects of amines on the kinetic competition among three typical products (carbamates, carbamic acids and bicarbonate) from amines + CO₂ were investigated, in contrast to previous thermodynamic studies to tune the reaction of amines with CO₂ based on desirable reaction enthalpy and reaction stoichiometry. We used a quantum chemical method to calculate the activation energies (E_a) for the reactions of a range of substituted monoethanolamines with CO₂ covering three pathways to the three products. The results indicate that the formation of carbamates is the most favorable, among the three considered products. In addition, we found that the E_a values for all pathways linearly correlate with pK_a of amines, and more importantly, the kinetic competition between carbamate and bicarbonate absorption pathways varies with pK_a of the amines, i.e. stronger basicity results in less difference in E_a. These results highlight the importance of the consideration of kinetic competition among different reaction pathways in amine design.     

利用高通量测序对封存CO2泄漏情景下土壤细菌的研究

全球CO2浓度不断升高的背景下,地质封存CO2为控制大气CO2浓度上升提供了全新的思路,但封存CO2潜在的泄漏风险也对生态系统产生重大威胁.土壤微生物与土壤健康密切联系.鉴于目前地质封存CO2泄漏对土壤微生物影响的研究鲜有报道,本研究通过模拟地质封存CO2泄漏情景,利用Miseq平台Illumina第二代高通量测序土壤细菌16S rRNA基因,结合相关生物信息学分析,初步探讨了封存CO2泄漏情景下农田土壤细菌群落丰富度、多样性和群落结构的变化.试验共获得15个土壤样本的43 017个OTU共486 645条读数,生物学分析结果表明,封存CO2泄漏通量和时间不同的情景下,农田土壤细菌丰富度和细菌群落多样性的变化存在差异,初步推测CO2泄漏量增大和泄漏时间持续更长的情景下,土壤细菌丰富度和多样性下降幅度较大,土壤细菌群落中优势菌群向若干细菌集中,其中土壤酸杆菌门细菌相对增多可能作为地质封存CO2泄漏对土壤生态系统影响的生物监测指标.     

CO2 adsorption using TiO2 composite polymeric membranes: A kinetic study

CO₂ is the main greenhouse gas which causes global climatic changes on larger scale. Many techniques have been utilised to capture CO₂. Membrane gas separation is a fast growing CO₂ capture technique, particularly gas separation by composite membranes. The separation of CO₂ by a membrane is not just a process to physically sieve out of CO₂ through the controlled membrane pore size. It mainly depends upon diffusion and solubility of gases, particularly for composite dense membranes. The blended components in composite membranes have a high capability to adsorb CO₂. The adsorption kinetics of the gases may directly affect diffusion and solubility. In this study, we have investigated the adsorption behaviour of CO₂ in pure and composite membranes to explore the complete understanding of diffusion and solubility of CO₂ through membranes. Pure cellulose acetate (CA) and cellulose acetate-titania nanoparticle (CA-TiO₂) composite membranes were fabricated and characterised using SEM and FTIR analysis. The results indicated that the blended CA-TiO₂ membrane adsorbed more quantity of CO₂ gas as compared to pure CA membrane. The high CO₂ adsorption capacity may enhance the diffusion and solubility of CO₂ in the CA-TiO₂ composite membrane, which results in a better CO₂ separation. The experimental data was modelled by Pseudo first-order, pseudo second order and intra particle diffusion models. According to correlation factor R², the Pseudo second order model was fitted well with experimental data. The intra particle diffusion model revealed that adsorption in dense membranes was not solely consisting of intra particle diffusion.