循环捕集CO2后煅烧石灰石的硫化特性

ZEC(zero emission coal)系统中,粗煤气进入碳酸化/重整炉前需先脱除H₂S,提出利用经过多次碳酸化/煅烧捕集CO₂循环的煅烧石灰石(CaO)脱除H₂S,并研究循环碳酸化/煅烧次数、硫化温度、H₂S浓度和微观结构对循环CaO硫化特性的影响。结果表明,多次循环碳酸化/煅烧捕集CO₂后CaO仍具有较高H₂S吸收性能。前20次循环,CaO硫化转化率随循环次数增加迅速降低;20次循环后,CaO硫化转化率缓慢下降。硫化120 min后,未循环CaO的硫化转化率接近100%,而经历1、20和100次循环后CaO的硫化转化率分别为94%、81%和74%。H₂S浓度对循环CaO硫化性能影响较大。硫化温度(800～1000℃)对循环CaO的硫化性能影响较小,最佳硫化温度为900℃。随循环次数增加,CaO颗粒发生高温烧结,导致比表面积降低和20～150 nm内孔隙减少,而这是与H₂S吸收密切相关的孔隙,导致CaO硫化转化率降低。     

间歇氯化对电石渣循环捕集CO2性能的影响

提出在碳酸化气氛中间歇加入HCl（间歇氯化）提高电石渣在循环煅烧/碳酸化反应中捕集CO₂性能的新思路。在双固定床反应器上,在不同循环次数加入HCl、碳酸化温度、CO₂/HCl体积比等条件下,研究HCl间歇加入对电石渣循环碳酸化特性的影响。结果表明,在循环煅烧/碳酸化反应中间歇加入HCl使电石渣间歇氯化能提高其循环捕集CO₂性能。在前N次循环碳酸化时加入0.1% HCl,当N=4时能使电石渣获得最优CO₂捕集性能,第10个循环时的CO₂吸收量比无HCl时提高了51%。HCl与CaCO₃发生氯化反应,破坏致密产物层对CO₂扩散的阻碍,提高了电石渣的碳酸化转化率。在碳酸化气氛加入HCl时,最佳碳酸化温度仍为700℃。随CO₂/HCl体积比增大,HCl对电石渣捕集CO₂性能的促进作用减弱。     

钙基热化学储能体系装备与系统研究进展

近年来,由于可持续发展的需要,太阳能等清洁可再生能源的大规模应用被提上日程。为解决太阳能受天气、昼夜等因素影响造成的不能持续稳定供能的问题,许多学者提出将储能系统整合至太阳能发电中,将太阳能热量以某种方式存储起来,需要时释放,从而使系统能持续运转。其中,热化学储能由于能量密度高,材料能够长期稳定储存与运输等优势,成为储能领域中新兴的研究热点。在众多的热化学储能材料中,基于CaCO₃/CaO与Ca(OH)₂/CaO体系的钙基热化学储能系统材料安全性高,成本较低且易于获得,十分具有发展潜力。本文对这两种钙基热化学储能体系的原理与材料进行了简单介绍,综述了该领域先进反应器设计与系统集成控制方面的国内外发展状况,探讨了目前研究面临的挑战与机遇,提出了钙基热化学储能技术的今后研究与发展方向的建议。     

利用蛭石增强石灰石对CO2的循环捕集效率

天然石灰石经高温煅烧分解后所得CaO可以作为捕集CO2的吸收剂,用来捕集水泥、煤电等工业烟气中的CO2.但是由于烧结现象导致钙基吸收剂的循环碳酸化率在多次循环之后会发生迅速衰减,基于此,我们提出利用具有天然纳米片层结构的蛭石对石灰石颗粒表面进行修饰改性,以便提高石灰石颗粒的抗烧结能力及其循环捕集CO2的能力.利用TGA以及SEM对蛭石改性的石灰石进行了表征.试验结果表明:蛭石对石灰石改性有效果,当其添加量为1 wt％时,可以使石灰石的第一次循环碳酸化率提高8.21％.     

固废源CaO基CO2捕集材料的制备与捕集性能研究进展

CO₂捕集技术是当前应对全球气候变化、缓解温室效应的重要途径。利用含钙固体废弃物制备高效CaO基CO₂捕集材料有利于实现固废资源高值化利用、以废治废和清洁生产,具有重要的环境效益、经济效益和社会效益。基于固废源高效廉价CaO基CO₂捕集材料的良好应用前景,本文介绍了工业废渣、生物质和其他含钙固体废弃物的产生与资源化利用现状,综述了CaO基吸附剂的捕集原理、碳酸化动力学过程和CO₂捕集性能,对比了以不同含钙固体废弃物为前驱体制备CaO基吸附剂的吸附-脱附循环性能和不同改性方法对其吸附稳定性的影响,从经济角度分析了固废源CaO基吸附剂在钢铁厂、燃煤电厂和生物制氢中的应用潜力,展望了固废源CaO基CO₂捕集材料的应用前景和发展方向。该文旨在为固废源CaO基吸附剂前驱体的选择、吸附性能的提高和固废吸附材料的工业应用提供帮助。     

镁负载CaO基吸附剂捕集CO2性能及抗烧结机理

复合钙基吸附剂制备成本过高是限制其工业化应用的主要瓶颈问题。本文以不可溶的CaCO₃和Ca(OH)₂作为钙源,通过燃烧合成法制备钙镁复合吸附剂,在双固定床反应器上研究了其循环捕集CO₂性能。结果显示：制备得到的钙镁复合吸附剂具有更发达的孔隙结构,吸附剂表面Ca和Mg分散均匀,MgO均匀分布于CaO晶粒之间,有效提高了钙镁复合吸附剂的抗烧结特性,因此钙镁复合吸附剂循环反应过程中具有高捕集CO₂活性。以Ca(OH)₂作为钙源时,燃烧合成过程中Ca和Mg均匀同时析出,分散更加均匀,有效避免了CaCO₃作为钙源时Mg的团聚问题,因此得到的钙镁复合吸附剂循环捕集CO₂性能最优。最佳的Ca/Mg摩尔比为(8∶2)~(7.5∶2.5)。本研究以不可溶钙源制备得到高活性钙镁复合吸附剂,有效控制了吸附剂成本,具有更好的工程应用前景。     

基于钙基吸收剂循环煅烧/碳酸化反应捕集CO2的试验

利用钙基吸收剂循环煅烧/碳酸化反应(CCCR)吸收CO2是一种新型、廉价、有效的CO2捕集方法.采用热重分析仪研究了吸收剂的矿物组成、颗粒粒径、煅烧温度和碳酸化温度对CCCR快速反应阶段吸收剂循环碳酸化率(XN)的影响.结果表明:吸收剂的碳酸化反应由快速化学反应控制阶段、过渡阶段和缓慢产物层扩散控制阶段组成;白云石具有良好的抗烧结能力,白云石的XN高于石灰石;随着颗粒粒径的增大,吸收剂的XN逐渐降低;当煅烧温度超过950℃时,随着循环反应次数的增加,吸收剂的XN严重降低;吸收剂在725℃碳酸化温度时的XN最高.     

CO2捕集的研究现状及钙基吸收剂的应用

温室气体CO2是当今世界环境恶化的主要原因之一,近年来针对CO2的捕集技术也相继被研究.磷石膏是湿法冶炼磷酸的副产物,具有产量大、微辐射性等特点,严重危害自然环境和人类健康.本文阐述二氧化碳捕集与封存(CCS)以及燃烧后捕集的三大方法的具体技术原理与特点,着重分析利用钙基吸收剂捕集CO2的技术特点和优势,提出CO2捕集技术的探索方向并指出利用磷石膏分解渣作钙基吸收剂矿化捕集CO2的思路.当前对CO2捕集的研究多停留在吸收剂捕集方面,单纯吸收剂虽吸收效果较好,但其成本较高.磷石膏分解渣作钙基吸收剂不仅有着良好的捕集效果,且解决了成本问题,实现了"以废制废"的思路.     

利用凹凸棒改性石灰石增强CO2循环捕集效率

石灰石作为天然的CO2吸收剂,可有效的捕集烟气中的CO2,但随着循环反应次数的增加,石灰石颗粒表面会发生严重的烧结,使其酸化率迅速发生衰减.本文中利用自然界储量丰富的凹凸棒石对石灰石颗粒进行改性来减缓这一现象的发生,从而提高其CO2的循环捕集效率.凹凸棒石具有的天然纳米纤维状结构可有效的减少石灰石颗粒之间的相互接触,延缓石灰石的烧结团聚现象,从而提高其碳酸化率.实验结果表明:凹凸棒石原矿和提纯后的凹凸棒石均可作为添加剂提高石灰石对CO2的捕集效率,其中经过提纯处理后的凹凸棒石的改性效果最好;通过比较凹凸棒石改性前后的钙基吸收剂经过多次CO2捕集循环后的颗粒微观形貌的变化,可以发现经过凹凸棒石改性后的石灰石颗粒表面仍留有较多的孔道,使其抗烧结能力得到大幅的提高.     

H2O对钙基吸收剂循环捕集CO2性能影响的研究进展

总结了钙循环技术中在煅烧过程、碳酸化过程、煅烧-碳酸化过程以及水合化处理过程中H_2O对钙基吸收剂捕集CO_2性能影响的研究,详细介绍了在钙循环各过程中H_2O对吸收剂性能的影响以及作用机理,分别提出了目前面临的技术问题,为实际应用以及进一步的研究指出方向。     

Simultaneous CO2 capture and thermochemical heat storage by modified carbide slag in coupled calcium looping and CaO/Ca(OH)2 cycles

The simultaneous CO_2 capture and heat storage performances of the modified carbide slag with by-product of biodiesel were investigated in the process coupled calcium looping and CaO/Ca(OH)_2 thermochemical heat storage using air as the heat transfer fluid. The modified carbide slag with by-product of biodiesel exhibits superior CO_2 capture and heat storage capacities in the coupled calcium looping and heat storage cycles. The hydration conversion and heat storage density of the modified carbide slag after 30 heat storage cycles are 0.65 mol·mol~(-1) and 1.14 GJ·t~(-1), respectively, which are 1.6 times as high as those of calcined carbide slag. The negative effect of CO_2 in air as the heat storage fluid on the heat storage capacity of the modified carbide slag is overcome by introducing CO_2 capture cycles. In addition, the CO_2 capture reactivity of the modified carbide slag after the multiple calcium looping cycles is enhanced by the introduction of heat storage cycles. By introducing 10 heat storage cycles after the 10 th and 15 th CO_2 capture cycles, the CO_2 capture capacities of the modified carbide slag are subsequently improved by 32%and 43%, respectively. The porous and loose structure of modified carbide slag reduces the diffusion resistances of CO_2 and steam in the material in the coupled process. The formed CaCO_3 in the modified carbide slag as a result of air as the heat transfer fluid in heat storage cycles decomposes to regenerate CaO in calcium looping cycles, which improves heat storage capacity. Therefore, the modified carbide slag with by-product of biodiesel seems promising in the coupled calcium looping and CaO/Ca(OH)_2 heat storage cycles.     

Experimental investigation of a circulating fluidized‐bed reactor to capture CO2 with CaO

Calcium looping processes for capturing CO₂ from large emissions sources are based on the use of CaO particles as sorbent in circulating fluidized‐bed (CFB) reactors. A continuous flow of CaO from an oxyfired calciner is fed into the carbonator and a certain inventory of active CaO is expected to capture the CO₂ in the flue gas. The circulation rate and the inventory of CaO determine the CO₂ capture efficiency. Other parameters such as the average carrying capacity of the CaO circulating particles, the temperature, and the gas velocity must be taken into account. To investigate the effect of these variables on CO₂ capture efficiency, we used a 6.5 m height CFB carbonator connected to a twin CFB calciner. Many stationary operating states were achieved using different operating conditions. The trends of CO₂ capture efficiency measured are compared with those from a simple reactor model. This information may contribute to the future scaling up of the technology. © 2010 American Institute of Chemical Engineers AIChE J, 57: 000–000, 2011     

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。     

氯化锰/氨热化学吸附储热的特性

热化学吸附储热具有储热损失小、储热密度高、可实现冷热复合储存等优点,近年来得到了广泛的关注。本文以MnCl₂/NH₃作为吸附储热工质对,基于热化学吸附技术构建了热化学吸附储热实验平台,对MnCl₂/NH₃热化学吸附系统的储热性能进行了理论分析和实验研究。结果表明：在解吸充热温度、吸附放热温度、冷凝/蒸发温度分别为162℃、45℃和25℃的运行条件下,试验获得的吸附储热密度最大,其值为1296.36kJ/kg MnCl₂或1101.90kJ/kg固化复合吸附剂。当放热温度从45℃增大到85℃时,热化学吸附储热系统的吸附储热效率从38.98%降低至24.08%。由于传热传质、化学反应动力学等因素的影响,相同运行工况下吸附储热系统实际所获得的储热性能要低于理论值。     

Sulfation rates of cycled CaO particles in the carbonator of a Ca‐looping cycle for postcombustion CO2 capture

Calcium looping is an energy‐efficient CO₂ capture technology that uses CaO as a regenerable sorbent. One of the advantages of Ca‐looping compared with other postcombustion technologies is the possibility of operating with flue gases that have a high SO₂ content. However, experimental information on sulfation reaction rates of cycled particles in the conditions typical of a carbonator reactor is scarce. This work aims to define a semiempirical sulfation reaction model at particle level suitable for such reaction conditions. The pore blocking mechanism typically observed during the sulfation reaction of fresh calcined limestones is not observed in the case of highly cycled sorbents (N > 20) and the low values of sulfation conversion characteristic of the sorbent in the Ca‐looping system. The random pore model is able to predict reasonably well, the CaO conversion to CaSO₄ taking into account the evolution of the pore structure during the calcination/carbonation cycles. The intrinsic reaction parameters derived for chemical and diffusion controlled regimes are in agreement with those found in the literature for sulfation in other systems. © 2011 American Institute of Chemical EngineersAIChE J, 2012     

Reactivity stabilization and capacity study of fabricated alumina and zirconia-supported CaO-based sorbents for high-temperature CO2 capture in a fixed-bed reactor

Calcium looping process is a promising approach for CO₂ capture from the flue gas of fossil fuel power plants and the cement industry. Even though the advantages of calcium-based sorbents are low cost and high uptake capacity, they suffer from low durability during cycles. Modified sorbents were fabricated by adding alumina and zirconia and the mixture of alumina and zirconia to calcium oxide via the co-precipitation method. The performance of synthesized sorbents in terms of stability and CO₂ capture capacity were evaluated using a fixed bed reactor in various CO₂ sorption/desorption cycles. The sorbents were fabricated by a co-precipitation methodology using 10% binders (alumina and/or silica). X-ray diffraction (XRD), BET/BJH, and scanning electron microscopy (SEM) were conducted for characterization of synthesized sorbents. CaO-10% ZrO₂ showed the best performance among the fabricated sorbents in terms of stability during 5 cycles and CO₂ capacity (14 mmol CO₂/g sorbent). The formation of CaZrO₃ with a perovskite structure and high-temperature resistance could be attributed to well performance of zirconia-supported sorbent. On the other hand, no sign of aluminum zirconate formation was approved in XRD analysis for the fabricated sorbent using mixed binders of zirconia and alumina to enhance its stability during cycles.     

废弃蛋壳源高性能钙基吸收剂的制备及其碳捕集性能

基于食品工业废弃蛋壳,本文利用不同有机酸反应制取乙酸钙、柠檬酸钙及葡萄糖酸钙共三种蛋壳源有机钙。在高温固定床反应器及热重分析仪上研究了不同前体所制成钙基吸收剂的碳循环捕集性能及碳酸化特性。进一步通过XRD分析了不同钙基吸收剂的物相组成,通过N₂吸附仪及SEM分析了循环前后钙基吸收剂结构特性及微观形貌的变化。结果表明,在三种蛋壳源有机钙中,葡萄糖酸钙所制成的钙基吸收剂具有较高的反应活性和相对最佳的碳捕集性能,首次碳酸化转化率高达85.33%,其钙基吸收剂相比其他吸收剂晶粒更小,20~100nm孔径范围内的孔隙较为发达,具有相对较强的抗烧结能力。经过20次循环实验发现,随着循环次数的增加,几种钙基吸收剂小颗粒均团聚烧结成大颗粒,造成孔隙结构缺失,孔隙率降低,影响其后续碳捕集性能。