操作条件对Zr掺杂钙基CO2吸附剂吸附性能的影响研究

寻找简便有效的方法对CO₂进行捕集和封存,是未来实现“双碳”目标、保障能源安全和实现可持续发展的重要手段。钙基吸附剂因具有高CO₂吸附容量、价格低、脱碳效率高、对设备污染少等优点,在高温吸附领域显示出广阔的应用前景,但在多次吸附、再生循环过程中容易烧结、循环稳定性差。针对稳定性良好的Zr掺杂改性钙基吸附剂,探究操作温度和操作气氛等操作条件对吸附性能的影响。利用热重分析仪(TGA)进行了5种操作条件下吸附性能评价,同时采用SEM、CO₂-TPD、XRD等进行表征。结果表明：吸附温度在650℃,脱附温度为700℃,吸附氛围为30%CO₂/70%N₂时改性吸附剂性能最好,且经过20次吸脱附循环后没有明显变化。在其他操作条件一定的情况下,随着脱附温度的升高,吸附性能降低,烧结现象更显著;随着CO₂浓度的增加,评价后样品的粒径逐渐增大。与CaO相比,Zr掺杂改性吸附剂的中强碱性位更强。     

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。     

燃烧后CO2捕集材料研究进展

简要阐述全球和我国的化石能源及CO2排放现状,针对燃烧后捕集化石燃料电厂烟道气中的CO2气体,以溶液吸收、吸附、膜分离、生物固定4种捕集方法为线索,讨论了各类CO2燃烧后捕集材料的最新进展。     

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.     

钙基材料捕集CO2强化煤水蒸气气化制氢研究进展

煤炭大规模燃烧产生的CO₂加剧了全球气候变暖和温室效应,钙基材料强化煤气化制氢技术能在捕集CO₂的同时获得较高浓度的H₂,工业应用前景良好。基于国内外钙基材料强化煤气化制氢技术的研究进展,论述了钙基材料强化煤气化制氢技术的系统流程,综述了钙基材料在系统中的CO₂捕集和强化制氢反应特性和活性降低机理,总结了改善钙基材料循环稳定性、CO₂捕集性能和催化制氢性能的方法,介绍了钙基材料强化煤气化过程中碱金属等微量元素的迁移路径,论述了微量元素对钙基材料在煤气化过程中脱碳/强化制氢活性的影响特性,分析了流态化和超临界气化条件下钙基材料对煤气化制氢特性的影响,介绍了基于热力学模拟的系统能量和经济性计算,归纳了钙基材料强化煤气化制氢系统和其他可再生能源系统的耦合性能及其对制氢特性的影响。基于当前钙基材料强化煤气化制氢技术的研究进展和潜在挑战,对未来可能的研究方向进行展望,认为筛选添加剂能多方位提高钙基材料的反应性能,采用解耦气化和煤/生物质共气化技术能实现更高的制氢性能和气化转化率,研究煤中...     

失活石灰石自活化增强循环捕集CO2特性

钙循环工艺是一种低成本高效率捕集CO₂技术,运行过程需不断补充新鲜吸收剂并排出失活吸收剂,实现失活钙基吸收剂原位资源化利用具有重要意义。为研究颗粒状石灰石失活后自活化特性,运用双固定床反应器制备了失活石灰石,分析了自活化后石灰石碳酸化转化率随循环次数的变化规律,采用XRD、SEM、N₂吸附等分析测试手段探究了自活化提高失活石灰石循环捕集CO₂性能机理。结果表明,失活石灰石置于环境中可吸收空气中水分生成Ca(OH)₂,吸水率φ达100%后,继续吸水生成氢氧化钙水合物,极限吸水率为130%。不同程度自活化后的石灰石循环捕集CO₂性能均有不同程度提高,随吸水率变化呈线性升高趋势。与分析纯CaCO₃相比,失活石灰石对吸水率变化更敏感,随吸水率升高其循环捕集CO₂性能提高更快。吸水率为130%时,自活化后石灰石循环捕集CO₂性能甚至优于新鲜石灰石。微观结构分析结果显示：新鲜石灰石因高温烧结而失活过程中,CaO晶粒尺寸由41...     

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。     

CO2捕集及工业应用研究进展

碳捕集纯化技术中吸收剂和吸收工艺的开发以及二氧化碳(CO₂)的高效利用是该领域的研究热点。本文从CO₂捕集吸收剂、吸收工艺、工业应用及生产市场方面进行了详细综述和分析,总结了我国当前CO₂产业的发展情况和研究进展,探讨了CO₂吸收剂研制、工艺开发以及CO₂利用技术开发的发展方向,并对我国CO₂市场进行了展望。     

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.     

热电厂CO2捕集与利用技术进展

2020年全球二氧化碳排放量约为320亿吨,大气中CO₂含量正在以每年1 ppm的速度上升,CO₂的捕集利用技术正受到越来越多的关注。本文全面介绍了CO₂捕集和利用技术,重点对燃烧后捕集技术进行了详细综述和客观评价。认为膜吸收CO₂捕集方法具有装填密度高、气液接触面积大,操作弹性大,运行成本低优势,具有良好的发展前景;CO₂的生物转化利用因具有反应条件温和、过程碳排放极小等优点,使其在CO₂资源化利用方面表现出优异的应用前景。     

Theoretical and experimental study on the fluidity performance of hard-to-fluidize carbon nanotubes-based CO2 capture sorbents

Carbon nanotubes-based materials have been identified as promising sorbents for efficient CO₂ capture in fluidized beds, suffering from insufficient contact with CO₂ for the high-level CO₂ capture capacity. This study focuses on promoting the fluidizability of hard-to-fluidize pure and synthesized silica-coated amine-functionalized carbon nanotubes. The novel synthesized sorbent presents a superior sorption capacity of about 25 times higher than pure carbon nanotubes during 5 consecutive adsorption/regeneration cycles. The low-cost fluidizable-SiO₂ nanoparticles are used as assistant material to improve the fluidity of carbon nanotubes-based sorbents. Results reveal that a minimum amount of 7.5 and 5 wt% SiO₂ nanoparticles are required to achieve an agglomerate particulate fluidization behavior for pure and synthesized carbon nanotubes, respectively. Pure carbon nanotubes + 7.5 wt% SiO₂ and synthesized carbon nanotubes + 5 wt% SiO₂ indicates an agglomerate particulate fluidization characteristic, including the high-level bed expansion ratio, low minimum fluidization velocity (1.5 and 1.6 cm·s^–1), high Richardson−Zakin index (5.2 and 5.3 > 5), and low Π value (83.2 and 84.8 < 100, respectively). Chemical modification of carbon nanotubes causes not only enhanced CO ₂ uptake capacity but also decreases the required amount of silica additive to reach a homogeneous fluidization behavior for synthesized carbon nanotubes sorbent.     

CO2 uptake of modified calcium-based sorbents in a pressurized carbonation-calcination looping

This study focuses on enhancing CO₂ uptake by modifying limestone with acetate solutions under pressurized carbonation condition. The multicycle tests were carried out in an atmospheric calcination/pressurized carbonation reactor system at different temperatures and pressures. The pore structure characteristics (BET and BJH) were measured as a supplement to the reaction studies. Compared with the raw limestone, the modified sorbent showed a great improvement in CO₂ uptake at the same reaction condition. The highest CO₂ uptake was obtained at 700 °C and 0.5 MPa, by 88.5% increase over the limestone at 0.1 MPa after 10 cycles. The structure characteristics of the sorbents on N₂ absorption and SEM confirm that compared with the modified sorbent, the effective pores of limestone are greatly driven off by sintering, which hinders the easy access of CO₂ molecules to the unreacted-active sites of CaO. The morphological and structural properties of the modified sorbent did not reveal significant differences after multiple cycles. This would explain its superior performance of CO₂ uptake under pressurized carbonation. Even after 10 cycles, the modified sorbent still achieved a CO₂ uptake of 0.88.     

Experimental evaluation of Mg- and Ca-based synthetic sorbents for CO2 capture

Hydrogen with high purity can be directly derived from fossil and renewable energy sources, like natural gas, coal and biomass, by the so-called sorption-enhanced reforming (SER) and water gas shift (SEWGS) processes characterized by simultaneous CO₂ capture.     

用于燃烧后CO2捕集系统的胺基固态吸附材料研究进展

随着工业化的发展和大量化石燃料的消耗,大量的CO₂气体排放到大气中并引发了一系列严重的环境问题,而采用燃烧后CO₂捕集技术可以有效地应对这一问题。寻找一种高效吸附、稳定、价格低廉的固态吸附材料对于开展燃烧后CO₂捕集系统的研究具有重要的实际意义。近年来,胺基固态吸附材料因其高CO₂吸附能力和高吸附选择性成为研究的热点。本文综述了近年来国内外学者对不同胺基固态吸附材料在合成方法、载体材料选择以及性能测试等方面进行的研究,重点讨论了以沸石分子筛、介孔硅分子筛、多孔碳和金属有机骨架为载体的胺基固态吸附材料对CO₂的吸附行为,并指出多孔载体材料的结构改进及有机胺和促进剂的合理选择将会成为未来胺基固态吸附材料的重点研究方向。     

氨基修饰复合型钠基吸收剂的脱碳特性

为弥补常规钠基吸收剂活性差、脱碳量低的不足,制备了多种表面氨基修饰的新型复合型钠基吸收剂并研究其脱碳特性。通过比较氨基流失率和实际脱碳量,选定二氧化硅的前驱物正硅酸乙酯为载体前驱物,以碳酸钠为活性成分,分别以3-氨基丙基三甲氧基硅烷(APS)、3-氨基丙基三乙氧基硅烷(APTES)、二乙烯三胺(DETA)、三乙烯四胺(TETA)为氨基前驱物,制备得到多种表面氨基修饰的复合型钠基吸收剂。探究各种吸收剂的孔隙结构与脱碳特性,结果表明,APS、APTES修饰后吸收剂孔隙特性较差,脱碳量较低,DETA、TETA修饰后吸收剂孔隙结构得到改善,脱碳量较高。     

The maximum capture efficiency of CO2 using a carbonation/calcination cycle of CaO/CaCO3

The use of natural calcium carbonates as regenerable CO₂ sorbents in industrial processes is limited by the rapid decay of the carbonation conversion with the number of cycles carbonation/calcination. However, new processes are emerging to capture CO₂ using these cycles, that can take advantage of the intrinsic benefits of high temperature separations in energy systems. This work presents an analysis of a general carbonation/calcination cycle to capture CO₂, incorporating a fresh feed of sorbent to compensate for the decay in activity during sorbent re-cycling. A general design equation for the maximum CO₂ capture efficiency is obtained by incorporating to the cycle mass balances a simple but realistic equation to estimate the decay in sorbent activity with the number of cycles.     

复合钙基CO2吸收剂的反应性能及显微结构

采用溶胶-凝胶法制备了掺杂La3+、Mg2+的复合钙基CO2吸收剂,并在固定床反应器上进行了多循环的煅烧/碳化实验,对其CO2吸收活性及循环反应稳定性进行了研究.实验结果表明,掺杂La3、Mg2+的复合钙基吸收剂可以显著提高吸收剂在多循环煅烧/碳化过程中的反应活性和循环稳定性.在XRD分析的基础上,计算和比较了不同钙基...     

Metal-organic framework-based CO2 capture: from precise material design to high-efficiency membranes

A low-carbon economy calls for CO₂ capture technologies. Membrane separations represent an energy-efficient and environment-friendly process compared with distillations and solvent absorptions. Metal-organic frameworks (MOFs), as a novel type of porous materials, are being generated at a rapid and growing pace, which provide more opportunities for high-efficiency CO₂ capture. In this review, we illustrate a conceptional framework from material design and membrane separation application for CO₂ capture, and emphasize two importance themes, namely (i) design and modification of CO₂-philic MOF materials that targets secondary building units, pore structure, topology and hybridization and (ii) construction of crack-free membranes through chemical epitaxy growth of active building blocks, interfacial assembly, ultrathin two-dimensional nanosheet assembly and mixed-matrix integration strategies, which would give rise to the most promising membrane performances for CO₂ capture, and be expected to overcome the bottleneck of permeability-selectivity limitations.     

钙基碳载体造粒的捕集CO特性及力学性能

采用挤出滚圆法对钙基碳载体Ca（OH）₂进行造粒。在双固定床反应器上研究了黏结剂、支撑体和造孔剂对造粒后钙基碳载体循环捕集CO₂性能的影响,并提出采用多孔Al₂O₃球粉作为新型支撑体。结果表明,选择聚乙烯吡咯烷酮为颗粒黏结剂时最佳添加量为2%。高铝水泥和多孔Al₂O₃球粉均可作为支撑体造粒。多孔Al₂O₃球粉作为支撑体造粒后碳载体的循环捕集CO₂性能更高,其10次循环后CO₂吸收量为0.23g/g,是添加高铝水泥造粒碳载体的1.35倍。微晶纤维素作为造孔剂显著提高了造粒碳载体的循环捕集CO₂性能。多孔Al₂O₃球粉作为支撑体造粒后碳载体的抗压强度略高于高铝水泥作为支撑体。多孔Al₂O₃球粉造粒钙基碳载体拥有大量30~100nm孔隙,其比孔容高于高铝水泥造粒碳载体,这有利于CO₂捕集。     

Evaluation of solid sorbents as a retrofit technology for CO2 capture

Processes based upon solid sorbents are currently under consideration for post-combustion CO₂ capture. Twenty-four different sorbent materials were examined on a laboratory scale in a cyclic temperature swing adsorption/regeneration CO₂ capture process in simulated coal combustion flue gas. Ten of these materials exhibited significantly lower theoretical regeneration energies compared to the benchmark aqueous monoethanolamine, supporting the hypothesis that CO₂ capture processes based upon solids may provide cost benefits over solvent-based processes. The best performing materials were tested on actual coal-fired flue gas. The supported amines exhibited the highest working CO₂ capacities, although they can become poisoned by the presence of SO₂. The carbon-based materials showed excellent stability but were generally categorized as having low CO₂ capacities. The zeolites worked well under dry conditions, but were quickly poisoned by the presence of moisture. Although no one type of material is without concerns, several of the materials tested have theoretical regeneration energies significantly lower than that of the industry benchmark, warranting further development research.