有机胺功能化介孔固体吸附剂吸附分离CO_2性能研究

针对当前固体胺CO_2吸附剂存在吸附容量小、循环稳定性差等问题,采用高比表面积、易嫁接胺的介孔SBA-15作为载体,研究分子筛模板剂脱除方法和有机胺改性方法对制备的固体吸附剂吸附性能的影响,并采用N_2物理吸附、X射线衍射、红外光谱、热失重分析等表征技术并对样品进行表征。实验结果表明,通过嫁接和浸渍能够合成出不同有机胺负载量的胺功能化吸附剂,其中混合胺嫁接法改性的APTES-SBA(U)-T60吸附剂其吸附容量最大,在75℃下的纯CO_2气氛中吸附量达到192.05 mg/g,优于溶剂萃取和煅烧法去除模板剂。此外,混合胺嫁接法制备的样品在多次的吸/脱附操作下,CO_2吸附稳定性良好,表明混合胺修饰的吸附剂具有很好的稳定性和再生性。     

混合胺改性SBA-15的二氧化碳吸附特性

为实现廉价高效的二氧化碳捕集，新型燃烧后CO₂捕集固体吸附材料的设计和开发具有重要的研究意义。为提高CO₂吸附量，胺功能化改性吸附剂的方法主要有湿浸渍和表面嫁接。基于此，提出了“混合胺”修饰的概念，把湿浸渍和表面嫁接两种改性技术结合起来。把3-氨丙基三甲氧基硅烷（APTS）嫁接到分子筛SBA-15孔道表面，再把聚乙烯亚胺（PEI）浸渍到载体孔道的间隙，制备出高密度胺功能化的CO₂吸附剂。主要考察了不同含量的PEI和APTS功能化SBA-15的结构性能、CO₂吸附量及胺吸附效率。CO₂吸附结果表明，混合胺功能化SBA-15吸附主要依赖于动力学扩散。其中，SBA-15-（APTS-0.5-PEI-50），SBA-15-（APTS-1.0-PEI-50）和SBA-15-（APTS-2.0-PEI-30）在75℃时具有很好的吸附潜力。混合胺功能化SBA-15的胺吸附效率介于单纯嫁接和单纯浸渍的胺功能化SBA-15之间。     

吸附法碳捕集固体胺吸附剂成型技术研究进展

吸附法碳捕集技术是实现工业过程或大气中CO₂分离与脱除的重要途径之一,高性能吸附剂的开发是该技术的关键。固体胺吸附剂由于其优异的CO₂吸附量、选择性以及较低的再生能耗,近年来受到了广泛的关注,但用于工业的成型吸附剂仍面临机械强度低、稳定性差和胺流失严重等关键难题,难以在工业中大范围的推广应用。本文分析了固体胺成型吸附剂制备面临的主要难题,重点总结了近年来国内外吸附剂成型技术的研发进展,并对固体胺工业吸附剂的发展方向进行了展望。未来固体胺吸附法碳捕集技术的研发重点在于立足吸附反应机理和工业烟气的特性,创新成型固体胺吸附剂制备技术,提升吸附剂的CO₂吸附量、胺效率、机械与循环稳定性,研发低能耗的配套吸附工艺和核心装置。     

氧化镁基二氧化碳吸附剂的制备及改性研究进展

CO₂浓度的增加会引起全球变暖、海平面上升和冰川融化等环境问题，因此开发CO₂捕集技术刻不容缓。Mg O作为一种理想的CO₂吸附剂已成为研究热点。综述了Mg O基CO₂吸附剂的制备方法，探讨了不同方法对Mg O的比表面积、CO₂吸附容量和循环稳定性的影响。研究发现，采用沉淀法和溶胶-凝胶法制备的Mg O具有更大的比表面积和更多的碱性位点，有效地提高了其捕集CO₂的能力；采用熔盐掺杂改性法制备的Mg O基吸附剂对CO₂捕集能力显著提高，多次吸-脱附循环后仍保持较高的CO₂吸附容量。未来对Mg O基CO₂吸附剂的研究主要集中在MgO的改性方法、工艺条件优化和捕集机制等方面，进而推进MgO基CO₂吸附剂的工业化应用。     

H2S对铝基固态胺吸附剂吸附CO2性能的干扰机制

H₂S杂质对固态胺吸附剂吸附CO₂性能的干扰机制还缺少全面研究。以Al₂O₃为载体负载聚乙烯亚胺(PEI)制备铝基固态胺吸附剂(PEI@Al₂O₃),系统探究了H₂S对其CO₂吸附容量、吸附速率和循环吸附性能的影响规律。结果表明：H₂S与CO₂共存时,会相互抢占吸附剂上的胺基活性位点,从而发生竞争性吸附,但在模拟沼气条件(40%CO₂+59.5%CH₄+0.5%H₂S)下,H₂S的吸附竞争力远小于CO₂,H₂S吸附被抑制,且二者的最佳吸附温度不一致,在CO₂最佳吸附温度下,PEI@Al₂O₃的CO₂吸附容量和循环稳定性均不受H₂S干...     

二氧化碳固体碱吸附剂改性研究进展

结合近年来二氧化碳吸附剂主要研究状况,以CO₂固体吸附剂改性后的常用吸附压力为依据,从加压和常压角度重点对碱金属类、多孔炭类、沸石、多孔膜、有机金属框架5种较为普遍的固体吸附剂的改性进行了详细阐述,并对其应用前景进行了展望。     

黏土矿物的结构特征及其吸附二氧化碳的研究进展

天然黏土矿物资源丰富、成本低廉、具有丰富的孔隙结构和稳定的化学性质,是实现减排和碳循环的一类优良固体吸附剂基体材料。本文概述了黏土矿物适用于CO₂固体吸附剂制备的结构特征,对高岭石、埃洛石、蒙脱石、凹凸棒石、海泡石和蛭石等黏土矿物基CO₂固体吸附剂进行了综述。介绍了其在工业烟气捕集及沼气提纯技术中的应用,最后指出合成吸附容量高、选择性强、吸附温区大、适用于产业化应用的黏土矿物基CO₂固体吸附剂并建立理论吸附模型是今后的研究重点。     

液化残渣基CO2吸附剂的制备与性能优化

以煤液化残渣(CLR)为原料制备CO₂吸附剂，在实现碳减排的同时，可有效提高煤直接液化工艺的经济性和环保价值。本文采用神华煤直接液化残渣为碳源，通过预氧化、炭化活化等工艺，制备出了吸附性能较优的CO₂吸附剂。利用热重分析仪(TGA)、低温氮吸附仪(BET)、扫描电镜(SEM)以及透射电子显微镜(TEM)等分析手段对吸附材料的微观形貌、孔径结构以及吸附性能进行了表征测试。结果显示，低灰分液化残渣所制备的吸附材料具有更高的比表面积和更多的微孔结构，更有利于CO₂的吸附。以低灰分液化残渣为原料，在较优活化条件下(活化剂/原料质量比为1∶1、升温速率5℃/min、活化时间1h)制备的CO₂吸附剂表现出良好的吸附性能，在40℃、15%(体积分数) CO₂模拟烟气条件下的CO₂吸附容量为4.47%(质量分数)，在0℃、1bar (1bar=105Pa)条件下的CO₂吸附容量可高达27.70%(质量分数)，低温吸附性能优异，吸附速率快且具有良好的循...     

部分脱除模板剂对MCM-41修饰负载有机胺吸附CO_2的影响

介孔分子筛MCM-41具有单一的孔道结构和较大的比表面积。通过负载有机胺形成的介孔有机胺二氧化碳固体吸附剂比常见的固体吸附剂具有高选择性、高吸附量等特点。利用化学方法部分脱除模板剂,负载PEI制备固体吸附剂,研究了模板剂脱除率PEI负载和对二氧化碳吸附性能的影响。用XRD、FT-IR、TEM、BET等方法对吸附剂结构进行表征,利用TG/DTA方法测定了CO2吸附量。研究结果表明,使用MCM-41原粉负载50%PEI吸附量达到131.0 mg/g(即262.0 mg/gPEI),比相同负载量除去模板剂的分子筛提高了12.6%;比单一的PEI分子吸附量(80.3 mg/g)提高了3.26倍,这说明在MCM-41原粉孔道内部由于存在丝状胶束而形成的亚纳米空间结构提高了有机胺的分散和利用率,增加了对CO2的吸附量。     

四乙烯五胺改性多孔二氧化硅制备及CO2吸附性能

以十六烷基三甲基溴化铵（CTAB）为模板剂，原硅酸乙酯（TEOS）为硅源，1,3,5-三异丙基苯（TPB）为扩孔剂，制备不同孔道结构的多孔二氧化硅纳米微球（PSNs），将四乙烯五胺（TEPA）通过物理浸渍法负载到PSNs上，合成TEPA-PSNs吸附剂。利用扫描电镜、透射电镜、红外光谱、N₂吸附-脱附循环实验和热重分析对材料的结构性能和热稳定性能进行表征，成功制备了具有不同孔道结构的胺基化多孔二氧化硅。对吸附剂材料进行CO₂吸脱附实验和动力学研究，结果表明：当TPB含量增多时，吸附剂材料吸附的CO₂量也随之增大，并且TEPA-PSNs-0.5在75℃时吸附量最大，达4.70mmol/g；一阶动力学模型能较好地预测该吸附剂的CO₂吸附过程；经过5次循环，其再生性能仍然高达94.34%。因此，合成的胺基化多孔二氧化硅具有高吸附量和良好稳定性，是用于二氧化碳捕集的潜在材料。     

氨基修饰微孔/介孔复合材料AM-5A-MCM-41对CO2吸附分离的分子模拟

构建了氨基修饰微孔/介孔复合材料AM-5A-MCM-41的全原子模型,采用巨正则Monte Carlo（GCMC）方法研究了它的CO₂吸附分离性能,采用加权混合规则来描述氨基和CO₂分子的弱化学作用。模拟结果表明,CO₂分子优先吸附在复合材料介孔表面的氨基附近,CO₂纯气体的吸附量和吸附热有了显著提高,而N₂的吸附量和吸附热则基本不受影响。对于CO₂和N₂的混合气分离,由于复合材料对CO₂的弱化学吸附作用,显著提高了CO₂吸附量和吸附选择性,在573 K和100 kPa时CO₂/N₂的选择性达到了87.0。通过分子模拟研究可以从微观角度了解CO₂在氨基修饰的微孔/介孔复合材料中的吸附分离的细节和机理,为实验设计和合成高效CO₂吸附剂提供指导。     

改性活性碳纤维对CO2的吸附性能

为了进一步提高活性碳纤维的CO₂吸附量和抗水性能,采用浸渍法将活性碳纤维进行改性处理,得到一系列改性样品,并对其进行了SEM和FTIR表征。研究了活性碳纤维种类、浸渍试剂（NaOH溶液、ZnCl₂溶液及离子液体）等对吸附剂孔结构、CO₂吸附量、循环使用性和抗水性能的影响,并探讨了CO₂在改性活性碳纤维内的动力学吸附扩散行为。研究结果表明：改性活性碳纤维的CO₂吸附性能和抗水性能均显著改善,其中CO₂最高吸附量达24.4%（0.1MPa和25℃）,吸湿率减小到1.33%,且具有良好的吸附/脱附循环使用性。均相扩散模型（HSDM）描述了实时吸附数据,此模型能够较好地反映CO₂在样品内的扩散行为,改性活性碳纤维仍能保持良好的扩散速率,扩散系数D_s值数量级为10^-5m²/s,与空白活性碳纤维相当。     

Fabrication of nickel oxide functionalized zeolite USY composite as a promising adsorbent for CO2 capture

Adsorption process is considered to be the most promising alternative for the CO₂ capture to the traditional energy-intensive amine absorption process, and the development of feasible and efficient CO₂ adsorbents is still a challenge. In this work, the NiO@USY (ultrastable Y) composites with different NiO loadings were prepared for the CO₂ adsorption using Ni(NO₃)₂ as the precursor. The composites were characterized by X-ray photoelectron spectroscopy, X-ray diffraction, nitrogen adsorption–desorption test, scanning electron microscopy analysis, and thermogravimetric analysis, and were evaluated for the CO₂ adsorption capacity, CO₂/N₂ adsorption selectivity and CO₂ cycle adsorption capacity. The characterization results show that after the activation at 423 K, the Ni(NO₃)₂ species were well dispersed into the surface of zeolite USY, and after the further activation at 823 K, Ni(NO₃)₂ could be converted into highly dispersed NiO. The adsorption results show that the presence of the active component NiO plays an important role in improving the CO₂ adsorption performance, and the NiO@USY composite with a NiO loading of 1.5 mmol·g^-1 USY support displays a high adsorption capacity and adsorption selectivity for CO₂, and shows a good cycle stability. In addition, the Clausius–Clapeyron equation was used to evaluate the isosteric heat of adsorption of CO₂ on the NiO(1.5)@USY composite, and the heat of adsorption was 17.39–38.34 kJ·mol^-1.     

TEPA负载复合氧化活性炭吸附烟气中的CO2性能

以商业煤基活性炭为原料,经低浓度氧气焙烧、H₂O₂氧化改性,并以四乙烯五胺（TEPA）浸渍,得到胺负载复合氧化活性炭,用于模拟烟道气[(15%(体积)CO₂+85%(体积)N₂）+10%(体积)H₂O]中CO₂吸附。低浓度氧气焙烧后,活性炭的最大比表面积和孔体积分别为1421.82 m²/g、0.83 cm³/g。经复合氧化改性后,活性炭的介孔体积增大,表面含氧官能团增加,使得TEPA负载复合氧化活性炭的CO₂吸附性能提高。焙烧时间为4 h,H₂O₂氧化、负载40%TEPA的样品COAC-4-40TEPA,在60℃时CO₂饱和吸附量最高为2.45 mmol/g,是TEPA负载未改性活性炭AC-40TEPA的2.02倍。经过十次吸附循环后,COAC-4-40TEPA的 CO₂饱和吸附量可维持在92.24%,而TEPA的浸出量仅有0.67%。失活模型研究表明,COAC-4-40TEPA的初始吸附速率常数是AC-40TEPA的1.64倍,且失活速率常数低于AC-40TEPA。     

MER型沸石吸附分离CO2/CH4的分子模拟

MER型沸石在吸附分离CO₂/CH₄方面展现出良好的工业应用前景,受到广泛关注,但还缺乏理论基础数据。本文采用巨正则蒙特卡洛（GCMC）模拟方法,以全硅MER型沸石作为对照,模拟分析了CO₂/CH₄在Na⁺、K⁺、Cs⁺和Ca²⁺交换的MER型沸石中的吸附分离行为。结果表明：不同阳离子交换的MER型沸石对CO₂和CH₄的吸附符合Langmuir-Freundlich吸附等温线模型,平衡吸附量的大小顺序为：Ca-MER＞Na-MER＞K-MER＞Cs-MER,与沸石的自由体积和比表面积大小顺序一致,且近似成线性关系,选用高价阳离子MER型沸石可以提高吸附量;CO₂和CH₄主要分布在沸石的pau笼中,在d8R笼和ste笼中也有少量分布;骨架外阳离子与CO₂的强吸附作用和独特的八元环窗口孔径是MER型沸石对CO₂/CH₄混合组分表现出超高吸附选择性的原因,吸附选择性高达1000以上。综合吸附量、吸附热和吸附选择性分析指出,Na-MER和K-MER型沸石是优良的CO₂吸附剂。本研究为MER型沸石吸附分离CO₂/CH₄提供了理论依据和实验指导。     

Amine-immobilized HY zeolite for CO2 capture from hot flue gas

Solid amine-based adsorbents were widely studied as an alternative to liquid amine for post-combustion CO₂ capture (PCC). However, most of the amine adsorbents suffer from low thermal stability and poor cyclic regenerability at the temperature of hot flue gases. Here we present an amine loaded proton type Y zeolite (HY) where the amines namely monoethanolamine (MEA) and ethylenediamine (ED) are chemical immobilized via ionic bond to the zeolite framework to overcome the amine degradation problem. The MEA and ED of 5%, 10% and 20% (mass) concentration – immobilized zeolites were characterized by X-ray diffraction, Fourier-transform infrared spectroscopy, and N₂ -196 ℃ adsorption to confirm the structure integrity, amine functionalization, and surface area, respectively. The determination of the amine loading was given by C, H, N elemental analysis showing that ED has successfully grafted almost twice as many amino groups as MEA within the same solvent concentration. CO₂ adsorption capacity and thermal stability of these samples were measured using thermogravimetric analyser. The adsorption performance was tested at the adsorption temperature of 30, 60 and 90 ℃, respectively using pure CO₂ while the desorption was carried out with pure N₂ purge at the same temperature and then followed by elevated temperature at 150 ℃. It was found that all the amine@HY have a substantial high selectivity of CO₂ over N₂. The sample 20% ED@HY has the highest CO₂ adsorption capacity of 1.76 mmol·g^-1 at 90 ℃ higher than the capacity on parent NaY zeolite (1.45 mmol·g^-1 only). The amine@HY samples presented superior performance in cyclic thermal stability in the condition of the adsorption temperature of 90 ℃ and the desorption temperature of 150 ℃. These findings will foster the design of better adsorbents for CO₂ capture from flue gas in post-combustion power plants.     

Light-responsive adsorbents with tunable adsorbent-adsorbate interactions for selective CO2 capture

Amines in porous materials have been employed as active species for the selective CO₂ adsorption from natural gas because of their target-specific interactions. Nevertheless, it is difficult to modulate such strong interactions to reach a high efficiency in the adsorption processes. Herein, we fabricated light-responsive adsorbents with tunable adsorbent-adsorbate interactions for CO₂ capture. The adsorbents were synthesized by introducing primary and secondary amines into a mesoporous silica that had been grafted with azobenzene groups on the surfaces. The target-specific amine sites render the adsorbents significantly selective in the uptake of CO₂ over CH₄, and the azobenzene groups were used as light-responsive switches to influence the adsorbent-adsorbate interactions. The adsorbents can freely adsorb CO₂ when the azobenzene groups are in the trans state. Ultraviolet-light irradiation makes the azobenzene groups transform to the cis configuration, which greatly hinders amines in the uptake of CO₂. The caused difference of adsorption capacity can reach 34.9%. The alternative irradiation by ultraviolet- and visible-light can lead to a recyclable regulation on adsorption performance. The changes of the electrostatic potentials of amines are responsible for the light-induced regulation on adsorption.     

吸附强化蒸汽重整制氢中CO2固体吸附剂的研究进展

吸附强化蒸汽重整（SESR）制氢技术是集重整反应（H₂生产）和选择性分离（CO₂吸附）于一体的新型技术。该技术的特点为采用固体吸附剂在高温下对CO₂进行原位脱除,以改变反应的正常平衡极限,提高烃类转化率,提高H₂产量,减少CO₂排放。在整个SESR制氢技术中,吸附剂的选择与反应条件至关重要。本文探讨了CaO、水滑石、Li₂ZrO₃、Li₂SiO₃以及双功能吸附剂在SESR制氢过程中的性能,总结了提高这些吸附剂吸附性能的不同方法。确定了固体吸附剂的反应条件,如温度、压力、水蒸气量等因素的影响及相关的反应机理。分析表明,CaO基吸附剂由于其低廉的价格及较高的吸附能力,被认为是最具潜力的吸附剂,然而在SESR制氢过程中,CaO基吸附剂面临着多次循环再生后吸附能力衰减的挑战。集吸附与催化双重功能的吸附催化材料由于可以克服SESR制氢中不同固体催化剂和吸附剂的匹配问题、降低所用固体材料的成本,从而使其在吸附强化蒸汽重整制氢方面具有巨大优势,并成为该领域未来研究的一个重要方向。     

Stepwise growth of melamine-based dendrimers into mesopores and their CO2 adsorption properties

A series of CO₂ adsorbents were synthesized by functionalizing SBA-15 via stepwise growth of amine-terminated melamine-based dendrimers. The adsorbents contained very high organic loadings (up to 50.3 wt%) relative to previous reports. In addition to that, CO₂ adsorption measurements demonstrated that primary amine groups are the only active groups within these dendritic structures for CO₂ adsorption. The CO₂ adsorption capacities of these adsorbents (except for fourth generation dendrimer functionalized SBA-15) are improved relative to the unfunctionalized SBA-15. The exception is associated with the completely filled pores of this adsorbent.