Improved rate-based modeling of carbon dioxide absorption with aqueous monoethanolamine solution

This paper focuses on modeling and simulation of a post-combustion carbon dioxide capture in a coal-fired power plant by chemical absorption using monoethanolamine. The aim is to obtain a reliable tool for process simulation: a customized rate-based model has been developed and implemented in the ASPEN Plus® software, along with regressed parameters for the Electrolyte-NRTL model worked out in a previous research. The model is validated by comparison with experimental data of a pilot plant and can provide simulation results very close to experimental data.     

Geometry effect on membrane absorption for CO2 capture. Part I: A hybrid modeling approach

Membrane absorption (MA) has a great prospect for CO₂ capture. In MA modeling, conventional one-dimensional (1D)- and two-dimensional (2D)-models make simplification of membrane contactor (MC) geometry. Geometry simplification allows an easy process modeling and numerical solution, however, is only reasonable for particular MCs. Here, efforts are underway to quantify the geometry effect on the MA-CO₂ performance. First, we proposed a rigorous 3D model without geometry simplification for simulating the MA-CO₂ process in real MCs and then validated it with experimental data. More importantly, we highlighted a preferable hybrid model in which two correction factors were introduced to a 2D model to make the simulation results approximately equal to the 3D simulation values. The correction factors were correlated with dimensionless fluid dynamic parameters for characterizing the geometry effects on flowing fluids. Such hybrid modeling contributes to characterizing the influence of geometry on the MA-CO₂ performance and improving computation accuracy-efficiency combinations.     

单乙醇胺吸收CO2的热力学模型和过程模拟

采用非随机双流体电解质（ENRTL）热力学模型,通过拟合单乙醇胺（MEA）的饱和蒸气压、热容数据,MEA和水（H₂O）二元体系的汽液平衡、热容、混合热数据,以及二氧化碳（CO₂）在MEA水溶液中的溶解度数据,建立了MEA吸收CO₂的热力学模型,并用核磁共振（NMR）组成数据成功地进行了验证。在此模型基础上,利用平衡级模型建立了MEA吸收/解吸CO₂的过程模拟,利用文献中中试工厂数据验证了过程模拟的准确性。对于质量分数为30%的MEA溶液,固定吸收塔CO₂去除率为90%的条件下,当吸收塔液气质量流率比值为2时,再沸器能耗最小,为3.64 GJ·（t CO₂）^-1。     

甘氨酸盐捕集二氧化碳后的矿化解吸与再生研究

矿化解吸作为低能耗的再生工艺已成为二氧化碳捕集封存（CCS）技术的关注点。为了更好地研究矿化解吸已捕集二氧化碳的吸收剂以及吸收剂再生的整个过程,采用了衰减全反射傅里叶变换红外光谱法（ATR-FTIR）指认了甘氨酸钾溶液以及其二氧化碳吸收饱和溶液的12个特征峰,再选定特有的反应物和产物的特征峰,对氧化钙矿化解吸已捕集二氧化碳以及甘氨酸钾再生过程做跟踪测量。实验结果表明,在矿化解吸二氧化碳过程中随着甘氨酸钾溶液pH的逐渐升高,溶液中质子胺（—NH₃⁺）、氨基甲酸酯（N—COO^-）和碳酸氢根（HCO₃^-）的含量在逐渐减少,溶液中的胺基（—NH₂）不断生成,甘氨酸钾吸收剂得到再生。虽然—NH₃⁺可以完全再生回—NH₂,但部分N—COO^-还保留在吸收剂溶液中。因此,氧化钙矿化解吸无法完全再生已捕集二氧化碳的甘氨酸钾吸收剂。该结果有助于进一步了解矿化解吸已捕集二氧化碳吸收剂的反应机理和反应动力学。     

胺法脱碳系统流程改进及优化模拟

采用一乙醇胺(MEA)进行燃煤电厂烟气脱碳是目前比较成熟和可行的技术,但是存在再生能耗高的严重缺陷。胺法脱碳系统流程改进及优化能有效降低再生能耗。应用Aspen Plus软件基于速率模型对传统胺法脱碳流程及其改进流程进行模拟研究。这些改进的流程包括吸收塔中间冷却流程、富液分流流程、贫液蒸汽再压缩流程、分流流程及富液分流与贫液蒸汽再压缩整合流程。研究结果表明:富液分流与贫液蒸汽再压缩整合流程节能效果最好,和传统流程相比再生能耗及等量功分别下降28.2%和11.9%。节能效果其次的是富液分流流程,再生能耗和等量功分别下降19.3%和11.8%。贫液蒸汽再压缩流程使再生能耗下降了14.1%,而等量功只下降了4.1%。吸收塔中间冷却流程和分流流程节能效果比较有限。     

基于整体煤气化联合循环的燃烧前CO2捕集工艺及系统分析

CO₂减排作为应对全球变暖的重要手段而逐渐成为国内外研究热点。为研究燃烧前CO₂捕集系统关键技术,以华能（天津）265MW级整体煤气化联合循环发电系统（IGCC）示范电站为依托,从气化装置抽出合成气约10000m³/h（标况下）,进行一氧化碳耐硫变换、甲基二乙醇胺（MDEA）硫碳共脱、PDS硫回收等技术研究,同时完成我国首套工业规模级燃烧前捕集工艺模拟、系统分析及现场测试。研究结果表明：满负荷运行工况下,每年可捕集CO₂ 7.811万吨,系统单位能耗2.35GJ/t（CO₂）,CO₂捕集率≥ 85%;模拟结果与实际运行数据相吻合。其中MDEA工段能耗占捕集能耗的93.3%,热再生部分则占MDEA工段能耗的81.61%;同时分析了捕集系统各工段CO₂损失过程,增加四段变换可使系统能耗基本不变同时捕集率增加至92.29%;考察了CO₂压缩液化工段能耗及成本。本研究结果可为燃烧前CO₂捕集的设计、工业放大及过程优化提供理论支持。     

化学吸收法CO2捕集解吸能耗的分析计算

推导出了化学吸收法CO2捕集工艺解吸总能耗的准确计算公式,根据年产量100万吨CO2的捕集工艺流程的节点参数,分析计算了解吸能耗中各项能耗的大小,并与Leites、晏水平、王海波等能耗估算公式结果进行了对比。分析表明,本文推导的能耗计算公式适用于设计后或运行时的能耗计算,在捕集工艺设计前可采用Leites、晏水平、王海波等公式估算解吸能耗。其中晏水平公式考虑了循环倍率,因此能耗估算公式的适用性强,循环倍率和比热容取值偏差不大时,估算精度较高。通过对推导出的解吸能耗公式的分析,即使吸收剂质量浓度、溶液的再生度、贫富液换热器的性能一定,仍能进一步降低解吸总能耗,并提出了进一步降低解吸总能耗的有效措施。     

Integrated adsorption and absorption process for post-combustion CO2 capture

This study explored the feasibility of integrating an adsorption and solvent scrubbing process for post-combustion CO₂ capture from a coal-fired power plant. This integrated process has two stages: the first is a vacuum swing adsorption (VSA) process using activated carbon as the adsorbent, and the second stage is a solvent scrubber/stripper system using monoethanolamine (30 wt-%) as the solvent. The results showed that the adsorption process could enrich CO₂ in the flue gas from 12 to 50 mol-% with a CO₂ recovery of >90%, and the concentrated CO₂ stream fed to the solvent scrubber had a significantly lower volumetric flowrate. The increased CO₂ concentration and reduced feed flow to the absorption section resulted in significant reduction in the diameter of the solvent absorber, bringing the size of the absorber from uneconomically large to readily achievable domain. In addition, the VSA process could also remove most of the oxygen initially existed in the feed gas, alleviating the downstream corrosion and degradation problems in the absorption section. The findings in this work will reduce the technical risks associated with the state-of-the art solvent absorption technology for CO₂ capture and thus accelerate the deployment of such technologies to reduce carbon emissions.     

笼型水合物膜分离和捕获二氧化碳研究进展

开发一种低碳、高效的分离和捕获二氧化碳方法一直是缓解温室效应的关键技术。本文首先比较了现有的5种碳捕获技术,发现相较于化学吸收、深冷分离和变压吸附,水合物法和膜分离技术具有绿色环保、操作简单的优势。随后,本文以水合物法为切入点,阐述了其分离机理和强化手段。为进一步研究更加有效的新技术,通过利用水合物法的技术优势,结合膜分离的结构,提出一种更加具有发展潜力的水合物膜分离技术。然后,根据水合物膜的成膜方式将水合物膜技术分为第一、二、三代,并重点分析了每代水合物膜技术的改进手段。最后指出未来第三代水合物膜分离技术应从以下3个方面寻求突破与创新:探索合适膜载体材料;寻找合适的添加剂;优化温度、压力、流速水合分离条件。     

Application of membrane separation technology in postcombustion carbon dioxide capture process

Membrane separation technology is a possible breakthrough in post-combustion carbon dioxide capture process. This review first focuses on the requirements for CO₂ separation membrane, and then outlines the existing competitive materials, promising preparation methods and processes to achieve desirable CO₂ selectivity and permeability. A particular emphasis is addressed on polyimides, poly (ethylene oxide), mixed-matrix membrane, thermally-rearranged polymer, fixed site carrier membrane, ionic liquid membrane and electrodialysis process. The advantages and drawbacks of each of materials and methods are discussed. Research threads and methodology of CO₂ separation membrane and the key issue in this area are concluded     

胺法脱碳系统再生能耗

胺法脱碳系统最大的缺陷是再生能耗高,流程参数优化是降低再生能耗的有效途径。为了解再生操作参数对再生能耗的影响,通过再生塔实验台对醇胺吸收剂在不同再生工艺参数下的再生特性进行实验研究。实验内容包括富液CO₂担载量、富液进料温度、再沸器温度、再生压强及胺的种类因素对再生能耗及再生速率的影响,并分析了显热、潜热的变化规律。应用Aspen Plus 基于速率模型对再生过程进行了模拟研究。研究结果表明:提高富液CO₂担载量和富液进料温度能有效降低再生能耗。增大再沸器温度及再生压强反而增大再生能耗。一乙醇胺(MEA)再生能耗较高,混入甲基二乙醇胺(MDEA)能够显著降低能耗。提高富液CO₂担载量和再沸器的温度可以加快CO₂再生速率。     

瑞典二氧化碳捕集与封存技术的研发现状

瑞典参与的二氧化碳捕集与封存(CCS)项目多是欧盟项目,与英国、德国、丹麦、挪威、法国等国一起开展技术研究和示范项目的建设。瑞典在二氧化碳的捕集、运输和封存等各个环节的技术和政策都有研究,捕集技术的实验平台和示范项目则多设在瑞典境外的大型火力发电厂,封存地则需要考虑运输、地质条件等因素。     

带循环的二阶变压吸附碳捕集工艺模拟、实验及分析

针对日益严重的温室效应及传统CO₂捕集和储存技术的不足,设计带循环的二阶四塔变压吸附装置捕集电厂烟道气中的二氧化碳,采用炭分子筛作为第一阶二塔处理装置吸附剂,采用13X作为第二阶二塔处理装置的吸附剂。建立上述工艺的数学模型,通过实验验证数学模型和模拟结果的准确性。模拟结果表明,本工艺可以将烟道气中的CO₂（15%）富集为纯度95%的产品气,收率为93.92%,工艺处理量为4.576 mol CO₂·h^-1·kg^-1,能耗为0.847 MJ·（kg CO₂）^-1,通过对比,本工艺具有处理量大、回收率高、纯度高的优点。在此基础上,根据数学模型分析二阶床层在一个周期内的压力变化、温度分布、固相和气相组成分布、能耗组成、生产能力。     

Fabrication of PEI-grafted porous polymer foam for CO2 capture

A polymer foam material with both the open-cell porous structure and the polyethylenemine (PEI)-grafted inner face was constructed for CO₂ capture. The porous poly(tert-butyl acrylate) foam was first prepared via a concentrated emulsion polymerization, and then the carboxyl groups were introduced on the interface of porous polymer after the hydrolysis reaction. Subsequently, the surface of the foam was grafted with PEI, and finally the PEI-grafted porous polymer foam designed as a CO₂ capture material was obtained. The structures of the foams were characterized by infrared spectroscopy, EDS, and SEM. The CO₂ adsorption properties were measured by adsorption/desorption cycles. As a result, the polymer foam contained a large number of amine groups (13.9 wt % N), and therefore possessed a high CO₂ adsorption capacity (5.91 mmol g⁻¹ at 40°C and 100 kPa). In addition, they also exhibited high CO₂ adsorption rate, good selectivity for CO₂-N₂ separation, and good stability according to CO₂ cyclic adsorption/desorption test. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47844.     

微通道内乙醇胺吸收CO2的过程特征（英文）

Process characteristics of CO2 absorption using aqueous monoethanolamine(MEA) in a microchannel reactor were investigated experimentally in this work.A T-type rectangular microchannel with a hydraulic diameter of 408 μm was used.Operating parameters,i.e.temperature,pressure and molar ratio of MEA to CO2 were studied.Under 3 MPa pressure,the mole fraction of CO2 in gas phase could decrease from 32.3% to 300×10?6 at least when gas hourly space velocity ranged from 14400 to 68600 h?1 and molar ratio of MEA to CO2 was kept at 2.2.In particular,the effects of temperature on CO2 absorption flux,mass transfer driving force,gas-liquid contact time and en-hancement factor were analyzed in detail and found that mass transfer enhancement by chemical reaction was a crucial factor for the process of CO2 absorption.     

面向二氧化碳捕集的过程强化技术进展

化石能源的大量燃烧在推进人类工业化进程的同时也使当今世界面临愈发严峻的气候变化和环境问题。为降低大气中日益增长的CO₂浓度并实现《巴黎协定》所设定的2℃目标,CO₂捕集技术得到了越来越广泛的关注和研究,其中部分技术已实现了小规模工业化。在持续推进节能减排的背景下,通过CO₂捕集对现有工业过程进行强化是CO₂捕集技术发展的一个新兴方向,如此不但可提高原有过程的效率和产品品质,还可大幅减少其碳排放,是具有应用前景的技术路线。本文从CO₂捕集的主流技术出发,介绍了面向CO₂捕集的过程强化技术,重点介绍CO₂捕集强化的蒸汽重整制氢过程、水气变换过程和生物质气化过程,以及耦合CO₂捕集的CO₂加氢过程、CH₄干重整过程和化学链燃烧过程,最后还对捕集后CO₂的利用与转化技术进行了简介。     

金属离子促进乙醇胺捕集二氧化碳研究

为了解决醇胺法燃烧后捕集二氧化碳再生能耗过高的问题,研究了一种向胺溶液中添加金属离子以降低其CO₂解吸能耗的方法,称之为金属离子络合物热缓冲自热利用技术。以广泛商业化应用的单乙醇胺（MEA）溶液为研究载体,并在MEA溶液中分别添加金属离子铜或镍, 通过建立含有金属离子的MEA捕集CO₂体系的化学反应模型,解释金属离子热缓冲剂效应的内在机理。机理显示在MEA-金属离子-CO₂-H₂O体系中,金属-MEA络合物作为一种有效的反应热缓冲剂,将有机胺吸收CO₂过程中释放的反应热（放热反应）存储于金属络合物的解离键能中（吸热反应）,在CO₂高温解吸中通过其络合放热反应将储存的能量释放出来用于CO₂解吸,形成自热再生低能耗CO₂捕集技术,从而降低了MEA再生的能耗。本文进行了综合的实验测定来评价金属离子对MEA溶液捕集CO₂过程的性能提升影响,包括CO₂反应热、解吸速率、吸收-解吸循环负载、汽液平衡溶解度等。实验结果表明铜离子或镍离子作为添加剂,能增加MEA的CO₂平衡循环负载14%~20%或7%~10%,同时能够降低MEA的CO₂反应热值6.6%~24%或6.0%~20%。     

Simulation of a calcium looping CO2 capture process for pressurized fluidized bed combustion

The Canadian regulations on carbon dioxide emissions from power plants aim to lower the emissions from coal-fired units down to those of natural gas combined cycle (NGCC) units. Since coal is significantly more carbon intensive than natural gas, coal-fired plants must operate at higher net efficiencies and implement carbon capture to meet the new regulations. Calcium looping (CaL) is a promising post-combustion carbon capture (PCC) technology that, unlike other capture processes, generates additional power. By capturing carbon dioxide at elevated temperatures, the energy penalty that carbon capture technologies inherently impose on power plant efficiencies is significantly reduced. In this work, the CO₂ capture performance of a calcium-based sorbent is determined via thermogravimetric analysis under relatively high carbonation and low calcination temperatures. The results are used in an aspenONE™ simulation of a CaL process applied to a pressurized fluidized bed combustion (PFBC) system at thermodynamic equilibrium. The combustion of both natural gas and coal are considered for sorbent calcination in the CaL process. A sensitivity analysis on several process parameters, including sorbent feed rate and carbonator operating pressure, is undertaken. The energy penalty associated with the capture process ranges from 6.8–11.8 percentage points depending on fuel selection and operating conditions. The use of natural gas results in lower energy penalties and solids circulation rates, while operating the carbonator at 202 kPa(a) results in the lowest penalties and drops the solids circulations rates to below 1000 kg/s.     

燃烧后CO_2捕集技术研究

对燃烧前、燃烧后CO2捕集以及富氧燃烧3种CO2捕集技术的特点,以及适用于燃煤电厂的燃烧后CO2捕集技术进行了介绍,分析了吸收分离法、吸附分离法和膜分离法的原理及优缺点。其中,化学吸收法应用最广,但再生能耗大,运行成本高;吸附法虽再生能耗小,但对CO2选择性低,吸附能力有限;膜分离法目前仍处于实验室研究阶段,但应用前景巨大。对上述技术整合形成复合技术以及对新材料进行开发将有助于克服现有CCS技术面临的困难。     

混合基质膜在碳捕集领域的研究进展

膜分离技术因其低成本、低能耗及高效率的优势被认为是最具有前景的碳捕集技术之一。混合基质膜结合了有机材料与无机材料两方面的优势,是同时提升渗透性和选择性的有效手段。本文从气体在混合基质膜中的传递机制出发,以常见的无孔型与多孔型无机填料为基础,总结了近年来混合基质膜在二氧化碳捕集领域的研究进展,介绍了不同类型的填料在高分子基质中所起到的微结构调节作用,并着重阐述了在混合基质膜制备过程中无机填料与高分子基质之间所存在的相容性问题及其解决方法。最后,提出混合基质膜应在继续致力于填料结构设计、填料分散、构效关系等方面的同时,加强二维填料、微囊填料和促进传递机制等方面的研究。