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。     

改性钙基材料吸附CO2性能研究

温室气体CO2的大量排放是全球气候变暖的主要影响因素,对于CO2的捕集再利用研究已引起了学界和工业界的广泛关注.石灰石循环煅烧/碳酸化法捕集工业CO2气体已经被大量报道,但石灰石在循环捕集过程当中其表面容易被烧结而降低了其捕集性能,基于此,我们提出了利用耐高温氧化物(如MgO、Fe2O3、SiO2)微粒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CO2捕集特性并利用TGA和SEM对改性实验进行了捕集性能测试和颗粒形貌表征.试验结果表明,金属氧化物微粒对石灰石改性有效果,其中添加1 wt％ MgO微粒时可以使石灰石捕集CO2的性能提高7％～8％,且吸收剂颗粒孔隙结构得以改善.     

成型方法对Ni-CaO双功能材料CO2吸附与催化转化一体化性能的影响

CO₂捕集-转化一体化工艺是实现碳中和的关键负排放技术,而兼具吸附和催化活性的双功能材料(DFMs)构筑是关键。采用挤压法、挤压滚圆法和压片法构筑了柱状、球形和片状的Ni-CaO DFMs,探究了成型方法对Ni-CaO DFMs的结构和CO₂吸附-催化一体化性能的影响。研究发现,成型方法会破坏Ni-CaO DFMs的孔隙结构,对其CO₂体相扩散和吸附产生不利影响。在首次循环中,Ni-CaO粉体在650℃和体积分数为10%CO₂气氛下的吸附容量高达11.77 mmol CO₂/g,在体积分数为5%H₂气氛下原位逆水煤气变换的CO产量达4.81 mmol CO/g;而成型Ni-CaO DFMs的CO₂吸附容量降至9.67～10.33 mmol CO₂/g,CO₂催化转化率得到明显提升。成型方法有利于提升Ni-CaO DFMs的CO₂吸附循环稳定性。在12次循环后,未成型Ni...     

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。     

Preparation and Application of the Sol-Gel Combustion Synthesis-Made CaO/CaZrO3 Sorbent for Cyclic CO2 Capture Through the Severe Calcination Condition

abstract Calcium looping method has been considered as one of the efficient options to capture CO2 in the combustion flue gas. CaO-based sorbent is the basis for application of calcium looping and shou...     

A kinetic model of nano‐CaO reactions with CO2 in a sorption complex catalyst

This article describes the reactive kinetics of nano‐CaO with CO₂ in a sorption complex catalyst. Based on an observation of nano‐CaO reaction with CO₂ has a fast surface reaction regime and followed by a slow diffusion‐controlled regime, a criterion has been proposed to divide the fast surface reaction regime and the slow diffusion‐controlled reaction regime. The kinetics of the fast surface reaction was studied, and a new ion reaction mechanism was proposed. A surface reaction‐controlled kinetic model with a Boltzmann equation, X = X_u?X_u/[1+exp((t?t₀)k/X_u)], was developed. Experiments using nano‐CaO to react with CO₂ in a fast surface reaction regime within a sorption complex catalyst were performed using thermogravimetric analysis at 773–873 K under a N₂ atmosphere with 0.010–0.020 MPa CO₂. The activation energy of the kinetic model for carbonation is 30.2 kJ/mol, and the average relative deviation of the sorption ratio is less than 9.8%. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

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.     

Synthetic Ca‐based solid sorbents suitable for capturing CO2 in a fluidized bed

Coprecipitation and hydrolysis of CaO have been employed to produce Ca‐based synthetic sorbents suitable for capturing CO₂ in a fluidized bed. Their composition, CO₂ uptake, volume in small pores (2–200 nm) and resistance to attrition were measured and compared to those of limestone and dolomite. Sorbents produced by hydrolysis showed the highest uptake and resistance to attrition. After 20 cycles of carbonation and calcination, two sorbents exceeded the uptake of both limestone and dolomite, when subjected to the same regimes of reaction. A sorbent's uptake of CO₂ was shown to be determined by the volume in pores narrower than ～200 nm.     

碳酸酐酶和甲酸脱氢酶的稳定性研究进展

化石燃料的大量燃烧使温室气体CO₂的排放量不断增加,对环境造成恶劣影响,将CO₂捕集并转化为高附加值化学品是实现节能减排和变废为宝的一种双赢策略。酶催化CO₂捕集和转化具有高效、高选择性、反应条件温和、环境友好等优点。碳酸酐酶（CA）可大大加速CO₂水合反应,而甲酸脱氢酶（FDH）可催化CO₂还原为甲酸,二者协同可增强CO₂还原动力学。但酶促反应的工业化应用过程中,酶所处环境的温度、酸碱度以及其他离子的种类和浓度等因素均可能导致酶失活,因此,酶的稳定性研究至关重要。本文从热稳定性、酸碱稳定性和离子稳定性的角度,综述了CA和FDH的稳定性研究进展。改善酶稳定性的手段包括使用极端微生物、酶分子设计与改造、固定化等,重点讨论了固定化对酶稳定性的提升效果,为未来的工业化应用提供参考。     

等离子体辅助快速合成磁性Fe3O4/NaA复合材料及其CO2吸附性能

吸附法是捕集分离CO₂等温室气体的重要方法,磁性复合材料能实现气固相快速分离而备受关注。本文利用介质阻挡放电等离子体处理方法,分别对磁性Fe₃O₄和分子筛前体进行处理,再通过水热法快速制备了Fe₃O₄/NaA复合材料。利用X射线衍射、红外光谱、扫描电镜和元素扫描等技术进行了表征,并考察了复合材料中Fe₃O₄/NaA含量比对CO₂吸附性能和磁性能的影响。结果显示,当Fe₃O₄的质量分数为23.2％时,Fe₃O₄/NaA复合材料既具有优异CO₂吸附能力（2.10mmol/g）,又具有较好的磁性（25.92emu/g）,同时CO₂吸附-脱附循环稳定性高,是一种新型磁性CO₂吸附剂。在采用流化床吸附捕集CO₂技术中,有望实现气固高效磁分离。     

纳米K2CO3/CaO催化大豆油制备生物柴油

以K2CO3、纳米CaCO3(自制)为原料,K2CO3的负载质量分数为50%,在750℃焙烧3 h得到纳米K2CO3/CaO固体碱催化剂,并通过XRD、FT-IR及TG-DSC等手段进行确认.再用该催化剂催化制备生物柴油,结果表明:制备生物柴油的最佳条件为温度70℃,质量分数3%的纳米K2CO3/CaO,醇油摩尔比12...     

二氧化碳捕集技术及应用分析

分析了CO2捕集技术及现状。CO2捕集是CCS的关键技术单元之一,针对不同的CO2气源,国内外研究开发了多种技术。许多CO2捕集技术已经工业化,其中燃烧后烟气中CO2的捕集技术主要是以一乙醇胺(MEA)为基础的胺法;燃烧前的CO2捕集技术主要应用于IGCC电厂,一般需要对煤气中CO进行部分变换,变换后脱碳可采用成熟技术,如Selexol(NHD)等。富氧燃烧则是在中试成功的基础上,进行更大规模的工业示范。国内外大型煤制油化工项目主要采用低温甲醇洗脱除CO2,如果设置CO2产品塔,则可以获得体积分数98%以上的CO2。天然气脱碳主要采用MDEA技术。另外还有低温法、PSA、膜分离等CO2捕集技术及化学链燃烧等一些正在研发的技术。     

金属有机骨架用于CO2的吸附和转化

近年来,大气中CO2的迅速增加威胁着人类社会和自然环境.通过催化剂将CO2转化为高附加值化学品的碳转化技术是解决该问题的有效途径.金属有机骨架(metal-organic framework,MOF)是一种比表面积大,孔结构高度有序,拓扑类型多样,稳定性好的材料.MOF材料的特性使其具有广阔的应用前景,包括气体吸附、存...     

掺杂Ce、Zr对CO2钙基吸附剂循环特性的影响

利用湿法混合-煅烧法将元素Ce、Zr掺杂到CO₂钙基吸附剂中,利用热重分析仪(TGA)研究了24种改性钙基吸附剂吸附CO₂的循环特性。研究发现:CeO₂散布在CaO晶粒之间可抑制晶粒融合,对吸附剂烧结有一定的阻碍作用;CeO₂可明显提高吸附剂在扩散控制阶段对CO₂的吸附速率,原因在于CeO₂中丰富的氧空位可促进CO₂以离子迁移的方式穿过表面产物层到达内部与CaO反应;吸附剂中CeO₂含量越高,稳定性越强;ZrO₂与CaO高温化合成具有高塔曼温度的CaZrO₃,均匀分散在CaO晶粒间,构成稳固的支撑骨架,有效抑制了吸附剂烧结。