微流控在二氧化碳捕集、利用与封存的研究

二氧化碳(CO₂)捕集、利用与封存(CCUS)是解决全球变暖问题的关键技术。CCUS通过捕集与封存减少大气中的CO₂含量，并利用CO₂代替化石原料的使用进一步减少CO₂的净排放。CCUS技术的实施基于微尺度下CO₂物理和化学过程的综合研究。微流控技术可以在微米甚至纳米尺度操控流体并揭示流体运动规律，在CO₂捕集、利用与封存等各个环节中均发挥了重要的作用。本文概述了微流控技术的优势，包括精确的流体操控、大比表面积和增强的传热传质能力。系统介绍了与CCUS相关的微流控研究，包括CO₂捕集吸收剂的快速筛选、配方优化和材料制备，CO₂高效转化利用的电催化反应、光催化反应、催化剂制备和光合作用检测，CO₂地质封存的流体分析和地质建模等。最后，总结了微流控技术在CCUS中所扮演的重要角色，提出了微流控技术在CCUS领域的机遇和挑战。     

钢铁高炉煤气二氧化碳捕集技术经济性分析

基于固定单一原料气量导向、固定碳捕集量导向和固定混合原料气量导向3种不同的碳捕集情景,结合不同捕集技术CO₂捕集率与CO₂产品纯度的变化,分析了CO₂捕集对于高炉煤气热值提升的间接经济效益的影响。结果表明:当CO₂捕集率和CO₂产品纯度均一定时,基于固定单一原料气量导向较基于固定碳捕集量导向情景捕集单位质量CO₂提升的热值效益更高;当CO₂捕集率一定时,随着CO₂产品纯度降低,基于固定单一原料气量导向情景与基于固定碳捕集量导向情景捕集单位质量CO₂提升的热值效益均更高;当CO₂产品纯度一定时,随着CO₂捕集率降低,基于固定单一原料气量导向情景捕集单位质量CO₂的热值提升效益越高,而基于固定碳捕集量导向情景捕集单位质量CO₂提升的热值效益降低。     

葡萄树基活性炭的制备及其CO2吸附特性

为探讨葡萄树基活性炭在碳捕集与封存领域中的潜力,分别以葡萄树枝和树皮为原料采用CO₂活化法在800℃下制备了葡萄树枝基活性炭和葡萄树皮基活性炭,根据N₂物理吸附法计算了比表面积,用二维非定域密度函数理论（2D-NLDFT）分析了孔径分布特性,并使用热重分析法表征了两种活性炭的热解特性以及30℃的CO₂吸附特性.结果表明:①葡萄树枝基活性炭具有微孔结构,微孔孔径在0.36~1.6 nm之间,孔径为0.66 nm的微孔最多;葡萄树皮基活性炭具有大量微孔和少量中孔,孔径主要集中在0.36~1.9 nm之间.②葡萄树枝基和葡萄树皮基活性炭的CO₂吸附容量分别为1.096和0.247 mmol/g.③两种活性炭的CO₂吸附以物理吸附为主,其CO₂饱和产物在45℃前释放全部CO₂,葡萄树枝基活性炭的CO₂饱和产物较葡萄树皮基活性炭的CO₂饱和产物难于释放CO₂.④两种活性炭吸附CO₂后,在热重特性上出现的微量变化表明活性炭物质结构上的变化.研究显示,葡萄树枝基活性炭是一种良好的CO₂捕集材料,但其CO₂吸附容量比其他同类活性炭低,CO₂吸附量较高的葡萄树基活性炭的制备条件和改性方法需要进一步研究.      

CO2与NO-2/NO-3电催化合成尿素研究进展

CO₂的过度排放是21世纪人类面临的最大环境问题之一，严重威胁人类社会的可持续发展。在各种实现碳捕集和转化的方法中，通过电催化方法将CO₂转化为高值附加产品能有效缓解环境保护和工业生产的压力，提高碳资源的利用率，助力实现碳中和目标。相较于在高温高压条件下实现工业尿素合成，电催化共还原CO₂与NO^-₂/NO^-₃生产尿素反应条件温和、能耗低、二次污染小，是一种具有工业化应用前景的CO₂利用方式。本论文综述了CO₂与NO^-₂/NO^-₃电催化合成尿素的研究进展，重点从催化剂的设计合成以及C—N耦合机制两方面讨论了尿素在不同催化剂上的形成过程及其内在机制。设计可以共吸附并还原CO₂与NO^-₃/NO^-₂的材料...     

二氧化碳转化制取燃料及高值化学品研究进展

二氧化碳(CO₂)的捕集及转化技术可将CO₂转化为清洁燃料和高值化学品,是未来缓解能源问题的有效途径之一。基于CO₂的转化机理,结合近几年CO₂转化技术的发展,重点介绍了催化转化、电化学还原、光化学转化、光电催化转化及生物转化技术制备CH₃OH、HCOOH、C₂H₆O、CH₃COOH等一系列高值化学品的研究进展;基于现有技术,通过进一步开发利用新型催化剂,培育优化具有CO₂转化功能的微生物等手段,将CO₂转化技术与多领域技术相结合发展,可为CO₂转化技术的大规模工业化生产及实际应用打下坚实的基础。     

沸石分子筛催化材料在二氧化碳转化中的应用

开发高效的CO₂化学转化和利用技术是推动碳捕集利用(CCU)技术快速发展的关键，对我国实现双碳战略目标具有重要意义。沸石分子筛是一种具有规整微孔结构、高结晶度以及高水热稳定性的无机材料，在CO₂化学转化领域有着广泛的应用前景。本文介绍了当前沸石分子筛催化材料在CO₂转化领域的应用研究进展，重点介绍了沸石催化剂在CO₂-CH₄干重整、CO₂加氢以及等离子体驱动CO₂转化方面的最新研究进展。理性设计并可控构筑高性能沸石分子筛催化材料以最大限度地提高CO₂转化效率和产物收率，是未来该领域的研究重点。尽管沸石分子筛催化材料在CO₂转化领域表现出良好的应用前景，但仍有很多方面值得深入开展研究：1)在CO₂直接加氢制C⁺₂碳氢化合物(如芳烃)体系中，沸石分子筛的催化性质有着非常关键的作用，如何有效合成并调控沸石的酸性位点，是提高目标产物选...     

黄土塬地区CO2驱油封存泄漏地下水监测体系研究

针对鄂尔多斯黄土塬地区CO₂驱油封存项目的监测需求,在综合辨识黄土塬地区地下水潜在的CO₂泄漏特征,剖析CO₂泄漏进入地下含水层后的空间运移及时间响应特征的基础上,结合CO₂驱油封存过程,建立了1套面向黄土塬地区CO₂驱油封存CO₂泄漏的全时空立体化地下水监测体系。研究表明:受地形地貌及土壤特点影响,黄土塬地区驱油封存的CO₂具有盖层突破、井筒侧漏、降雨反渗和地表径流补给的多源泄漏特征;CO₂泄漏进入地下含水层后具有纵向快速运移扩散、横向四周缓慢扩散并随地下水向下游运移的空间运移特征和CO₂浓度、电导率等指标上升,pH值下降以及Ca2+、Mg2+离子浓度先上升后下降的时间响应特征。基于上述特征所建立的监测体系可为该区域CO₂驱油封存示范项目的监测提供参考。     

NaOH修饰Ru/TiO2对CO2活化及甲烷化性能研究

采用溶胶-凝胶法合成NaOH修饰的Ru-TiO₂催化剂(Ru/NaOH-TiO₂),在对其详细结构表征后将其应用于CO₂甲烷化反应.活性测试结果显示,以Ru/NaOH-TiO₂催化剂进行CO₂甲烷化反应,在7 h反应时间内生成300.8μmol CH4,其产量相较于Ru/TiO₂提高了30.2%.CO₂-TPD、H2-TPR.FTIR等测试结果证实NaOH修饰能提高催化剂对CO₂的吸附和活化,从而有效提高其催化CO₂甲烷化效率.这一研究工作为提供高效CO₂转化催化剂提供了理论基础.     

基于日本苫小牧港CCS示范项目的海洋碳封存环境风险监测方法浅析

碳捕集与封存利用技术是应对全球变暖、实现温室气体CO₂大规模削减的重要技术途径。海洋碳封存技术是近年来的研究重点之一,该技术利用海下稳定岩石储层对CO₂进行储存,相比于陆地碳封存技术具有更高的安全性。以日本苫小牧港CCS示范项目为基础,系统梳理了该项目在海洋生态环境监测、CO₂泄漏事故预防监测和地震监测等方面的研究方法,分析并总结了CO₂泄漏事故判断指标pCO₂/DO值(海水中CO₂与DO分压之比)的适用性以及地震对CO₂海下注入工程的影响,并基于中国国情提出在海洋碳封存项目中增加CO₂泄漏事故预防监测系统和地震监测系统等建议,为地震多发海域今后的碳封存项目提供借鉴。     

云南省优势矿产尾矿砂捕集及矿化封存CO2潜力分析

为了解云南省尾矿库“两个清单”中保留库的碳减排潜力,使用改进的Steinour方程计算了云南省各州市不同类型尾矿砂的CO₂固定量,根据《IPCC国家温室气体列表指南》中提供的方法计算了云南省2011~2020年碳排放量.结果表明,红河州、玉溪市、昆明市尾矿砂的捕集及矿化封存CO₂的潜力较大,占云南省保留库尾矿砂CO₂矿化封存量的65.79%;铅锌矿、赤泥、锡矿的理论固碳量较高,分别为0.201, 0.173, 0.158t/t,以上3种尾矿砂的固碳量占云南省尾矿砂固碳量的79.45%;若将云南省保留库堆存的尾矿砂全部用于CO₂的矿化封存,可减少2011~2020年间云南省累积碳排放量的2.81%,工业碳累积排放量的3.16%,采矿业碳排放量的12.36%,具有较好的工业应用前景.     

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.     

加速碳酸化技术对城市垃圾焚烧飞灰重金属稳定性影响研究

对南方某城市生活垃圾焚烧厂新鲜焚烧飞灰对CO₂的吸收及其碳酸化的过程进行了研究,实验从水分添加量、CO₂的分压等因素,考察了飞灰中重金属Pb的稳定化效果,并利用X射线衍射实验(XRD)、扫描电镜实验(SEM)对反应机理进行了分析.结果表明,不添加水分时,焚烧飞灰对CO₂的吸收效果较差;当水分添加量大于10％时,焚烧飞灰对CO₂的吸收效果较好.焚烧飞灰对纯CO₂的吸收效果较好,空气中的CO₂含量较低,在反应1 d后吸收效果不是十分明显.XRD实验结果表明,CO₂的吸收会使焚烧飞灰中大量的Ca(OH)₂与CO₂反应转化为CaCO₃,从而降低焚烧飞灰的碱性;部分重金属的氧化物会被碳酸化成生相应的碳酸盐.SEM实验结果表明,经过碳酸化处理后的飞灰颗粒表面生成了片状和圆柱状的晶体物质.     

Influence of SO2 in incineration flue gas on the sequestration of CO2 by municipal solid waste incinerator fly ash

The influence of CO2 content and presence of SO2 on the sequestration of CO2 by municipal solid waste incinerator(MSWI) fly ash was studied by investigating the carbonation reaction of MSWI fly ash with different combinations of simulated flue gas.The reaction between fly ash and 100% CO2 was relatively fast;the uptake of CO2 reached 87g CO2/kg ash,and the sequestered CO2 could be entirely released at high temperatures.When CO2 content was reduced to 12%,the reaction rate decreased;the uptake fell to 41g CO2/kg ash,and 70.7% of the sequestered CO2 could be released.With 12% CO2 in the presence of SO2,the reaction rate significantly decreased;the uptake was just 17g CO2/kg ash,and only 52.9% of the sequestered CO2 could be released.SO2 in the simulated gas restricted the ability of fly ash to sequester CO2 because it blocked the pores of the ash.     

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.     

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.     

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.     

生物炭对农田土壤CO2排放的影响研究进展

生物炭是生物质在缺氧或者限氧条件下经热解后产生的富碳产物。目前,生物炭被广泛应用于农业生产领域,可改善土壤质量,提高农田土壤碳汇。生物炭还田后,使土壤物理、化学和生物学等性质发生变化进而影响土壤CO₂的排放。本文从生物炭理化特性、土壤性质以及生物炭稳定性等角度综述生物炭对土壤CO₂排放的影响。主要内容包括不同炭化温度和生物质来源的生物炭特性(pH、比表面积、孔径、挥发分和灰分等)及其对土壤CO₂排放的影响;生物炭还田土壤特性变化及其对土壤CO₂排放的影响;生物炭稳定性及其对土壤CO₂排放的影响。本文基于以上三个方面综述了生物炭对农田土壤CO₂排放的影响,并在此基础上对生物炭的固碳减排效应进行展望,以期为生物炭的合理施用、农田固碳减排等提供基础和参考。     

Two-step accelerated mineral carbonation and decomposition analysis for the reduction of CO2 emission in the eco-industrial parks

Carbon dioxide（CO2） emissions are a leading contributor to the negative effects of global warming. Globally, research has focused on effective means of reducing and mitigating CO2 emissions. In this study, we examined the efficacy of eco-industrial parks（EIPs） and accelerated mineral carbonation techniques in reducing CO2 emissions in South Korea.First, we used Logarithmic Mean Divisia Index（LMDI） analysis to determine the trends in carbon production and mitigation at the existing EIPs. We found that, although CO2 was generated as byproducts and wastes of production at these EIPs, improved energy intensity effects occurred at all EIPs, and we strongly believe that EIPs are a strong alternative to traditional industrial complexes for reducing net carbon emissions. We also examined the optimal conditions for using accelerated mineral carbonation to dispose of hazardous fly ash produced through the incineration of municipal solid wastes at these EIPs. We determined that this technique most efficiently sequestered CO2 when micro-bubbling, low flow rate inlet gas, and ammonia additives were employed.     

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.     

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.