改性硅胶吸附分离N2/CO2的研究

目前,人类在能源系统中产生大量CO2并直接排放,导致了大气温室效应和地球变暖。因此从环境保护和节约能源角度考虑,对排放的N2/CO2混合气进行回收和利用是非常必要的。选择高沸点的N-甲基二乙醇胺（MDEA）作为涂渍液,用不同浓度的涂渍液对粗孔微球硅胶进行预处理,并分别进行了N2/CO2混合气的穿透实验研究,实验结果表明：以粗孔微球硅胶为担体涂渍35%MDEA的吸附剂,在操作压力为0.4MPa时,对N2/CO2混合气分离效果最好。     

介孔SBA-15的孔径尺寸对小牛血清蛋白和溶菌酶蛋白吸附的影响(英文)

In this paper,the effects of pore-size of SBA-15 on the adsorption kinetics and equilibrium of large protein molecules Bovine serum albumin(BSA)and lysozyme(LYS)have been investigated.The mesoporous molecular sieve SBA-15 with six different pore sizes were synthesized with P123 triblock copolymer as the template agent,and 1,3,5-trimethylbenzene(TMB)and isopropyl alcohol as the pore-expanding agent.The samples were characterized by N2 adsorption/desorption,Scanning Electron Microscopy(SEM),Transmission Electron Microscopy(TEM)and X-Ray Diffraction(XRD).It is found that BSA and LYS were adsorbed rapidly on SBA-15 materials with large pores.The BSA adsorption capacity of sieve with the pore diameter of 21.4 nm reached 500 mg·g-1 within 25 minutes.However,if the pore diameter was smaller than 14 nm,the BSA adsorption capacity of the sieve was only about 220 mg·g-1.The adsorption equilibrium data fits in the Langmuir model,where the coefficient of effective use of specific area of mesoporous molecular sieve was found to be 0.03,0.18,0.37 and 0.48,corresponding to the pore diameter of 10.1 nm,13.2 nm,15.4 nm and 21.4 nm,respectively.The equilibrium loading amount of LYS on SBA-15 materials with pore size of 15.4 nm could be up to 1000 mg·g-1.The coefficient of effective use of surface area of mesoporous molecular sieve with diameter of 3.9 nm,7.4 nm,10.1 nm,13.2 nm and 15.4 nm was 0.10,0.47,0.56,0.71 and 0.79,respectively.It is also noted that greater pore size of mesoporous molecular sieve would lead to a higher coefficient of effective use of surface area.     

四乙烯五胺功能化有序介孔氧化铝的合成及其CO2选择吸附性能研究

以九水硝酸铝为铝源,非表面活性剂柠檬酸为模板剂,稀氨水为沉淀剂合成有序介孔氧化铝（ OMA）。以四乙烯五胺（ TEPA）为活性组分,采用物理浸渍将其负载到OMA的内孔及比表面上,制备出氨基功能化的OMA用于CO2的选择吸附研究。采用XRD、BET和TEM对合成的吸附剂进行表征,通过自制的固定床反应器测量穿透曲线的方法研究其对CH4／CO2混合气的吸附分离性能。分别考察了负载量和吸附温度对吸附性能和分离因子的影响。结果表明,TEPA负载量为50％的吸附剂、吸附温度为70℃时对CO2吸附量最大,为2．598 mmol／g,TEPA／OMA经过10次吸附-脱附循环后,其吸附性能变化较小,仅下降了8．65％,具有较好的循环稳定性。     

CO2和N2吸附的研究札记

Experiments were made for the adsorption of CO2 and N2 on typical adsorbents to investigate the effects of porous structure and surface affinity of adsorbents as well as those of adsorption temperature and pressure that might cause the variation of adsorption mechanism. It is shown that polar surface tends to enlarge the adsorption difference between CO2 and N2, and the difference is more sensitive to temperature than the adsorbents with non-polar surface. The adsorbents with non-polar surface are not much sensitive to the effect of water vapor, though the water vapor interferes the separation remarkably. The separation coefficient linearly increases with the micropore volume per unit surface area of activated carbons, but no rule is shown on mesoporous silicon materials. The function of adsorption mechanism on the separation is not as much as expected.     

高稳定性介孔MgO-ZrO2纳米复合物对CO2吸附性能研究

用溶胶-凝胶法制备了介孔MgO-ZrO2纳米复合物,并通过XRD、氮吸附和CO2-TPD等手段表征了材料的结构特征和表面性质。XRD、氮吸附结果表明此纳米复合物具有典型的介孔结构,比表面积达183~212 m2/g,并且有较好的热稳定性,在700℃以下介孔孔道不会坍塌。另一方面,这种纳米复合物表面具有适中的碱性,其碱性位与基体结合牢固,稳定性好。由于其具有发达的孔隙和适中的碱性,二氧化碳在其表面的吸附量达1.6 mmol/g,且经数次循环后材料的吸附性能无明显下降。     

介孔SiO2吸附CO2的性能研究

以正硅酸乙酯（TEOS）为硅源,端氨基聚氧化丙烯醚（D2000）为模板剂,在水和乙醇的混合溶液中合成了蠕虫状介孔结构的介孔SiO₂（记为MSU-J）。采用物理浸渍的方法利用四乙烯五胺（TEPA）改性介孔MSU-J。采用红外、N₂吸附/脱附、元素分析表征改性介孔SiO₂。红外测试表明,经过物理浸渍可以将有机胺负载到介孔SiO₂上。N₂吸附/脱附试验表明,经过氨基修饰后,介孔SiO₂的介孔结构没有发生变化,但是介孔的孔容、孔径以及比表面积随着氨基浸渍量的增加而减小。在25℃和45℃,0.1 MPa下的纯CO₂吸附试验表明,氨基改性材料对CO₂吸附效果明显提高。当浸渍量为20%、吸附条件为25℃/0.1 MPa时,吸附量达到最大值138.6mg/g。当氨基含量继续增加时,吸附量反而降低。循环性试验表明,制备的吸附剂具有良好的循环性能,循环使用6次,材料的吸附量下降很少。     

氨基改性介孔二氧化硅对2-萘磺酸的吸附研究

用预水解法合成氨基改性介孔二氧化硅,考察了它对2-萘磺酸的吸附作用。实验表明,材料对2-萘磺酸吸附的最佳pH值为2.5,在25℃下的吸附等温线符合Langmuir模型,饱和吸附量可达142.4mg/g。吸附动力学符合准一级吸附动力学方程,相关系数R2为0.9952。共存无机离子SO2-4对2-萘磺酸有竞争吸附影响。用0.05mol/L的NaOH溶液再生后的材料,重复使用5次均能保持良好的吸附效果,可用于2-萘磺酸废水的吸附处理。     

分离乙烯-乙烷的Cu-MCM-48介孔络合吸附剂的合成、表征及吸附平衡研究

Copper incorporated MCM-48 molecular sieve adsorbents with different Cu content have been hydrothermally synthesized. The samples have been characterized by various physicochemical methods, including X-ray diffraction （XRD）, nitrogen adsorption （N2） and X-ray photoelectron spectroscopy （XPS）. The results reveal that Cu-MCM-48 with mass fraction of copper up to 10 % can still retain the uniform mesoporous framework of MCM-48. The copper in the framework of MCM-48 was easily auto-reduced to Cu（I） in N2 at high temperature, which did not alter the mesoporous structure of MCM-48. The adsorption equilibrium isotherms of ethylene and ethane on these molecular sieve adsorbents have been measured at 30℃. At 100 kPa, the adsorption capacities of ethylene on 5Cu-MCM-48 and 10Cu-MCM-48 are higher than those on MCM-48. The 10Cu-MCM-48 molecular sieve adsorbent has a higher selective adsorption ratio of ethylene to ethane, the separation factor is 3.8, and the amount of ethylene adsorbed is 11.1 ml·g ^-1.     

介孔碳材料的CO_2吸附性能研究进展

概述了温室气体的主要来源及目前的应对情况,并对比了非介孔碳材料和介孔碳材料对CO2的吸附性能。介孔碳材料因其较高的比表面积、较大孔容和均匀的孔径,具有较好的CO2吸附性能。同时指出了杂原子掺杂对于介孔碳材料的吸附性能的优化,并且对杂原子掺杂介孔碳CO2吸附剂的未来发展方向进行了展望。     

介孔二氧化硅合成及其吸附分离性能研究

以正硅酸乙酯为硅源,采用溶胶-凝胶法,通过调整合成体系pH与温度控制正硅酸乙酯的水解与缩聚过程,制备出4种不同孔径分布的介孔二氧化硅。以X射线衍射（XRD）、透射电镜（TEM）、N₂吸附-脱附、程序升温脱附（NH₃-TPD）、傅里叶红外光谱（FTIR）、热重（TG）等表征手段对二氧化硅物化性质进行表征,并考察4种介孔二氧化硅的烷/烯吸附分离性能。结果表明,介孔二氧化硅的硅羟基种类以自由羟基为主,随着合成终点pH增加,孔径增加,比表面积减少,硅羟基浓度降低,酸量减少,酸强度增加;孔径分布及酸性质对吸附分离性能影响明显,平均孔径为4.9 nm样品的酸强度适宜,分离度R_烷/烯>1,烯烃脱附速度快,吸/脱附速率比接近1,是较为理想的烷/烯分离吸附剂。     

胺功能化介孔二氧化硅捕集CO2的研究进展

胺功能化介孔二氧化硅因其高选择性、高吸附容量、快速的吸附动力学、良好的再生性能和循环稳定性受到广泛关注,在二氧化碳捕集技术中具有优良的应用前景。本文比较了胺改性的M41S、SBA-n、KIT-n、介孔二氧化硅泡沫、介孔二氧化硅纳米球和六方介孔二氧化硅的吸附性能,总结了MCM-41和SBA-15的结构特点。介绍了胺化合物的负载方式——湿法浸渍、化学接枝和原位聚合的胺负载原理。分析了硅源、载体内部性质、气体选择性和不同添加剂对胺功能化介孔二氧化硅材料吸附二氧化碳能力的影响。最后,点明了吸附剂未来的发展目标,对胺功能化介孔二氧化硅材料的研究方向进行了展望。指出未来可关注介孔二氧化硅微观结构和温度对胺与二氧化碳相互作用的影响,增强胺功能化介孔二氧化硅的稳定性,推进其在实际环境下的应用。     

CO2 adsorption using amine-functionalized mesoporous silica prepared via anionic surfactant-mediated synthesis

A series of directly amine-functionalized mesoporous silicas was prepared via an anionic surfactant-mediated synthesis method and applied to CO₂ adsorption at room temperature. The structurally robust amine functionality in the material accompanied by preferential positioning of amine groups normal to the surface of a silica support due to the S⁻N⁺  I⁻ mechanism proved to be beneficial for CO₂ adsorption. Rather than surface area or pore volume, amine content of the mesoporous material was found to be the governing factor to achieve high CO₂ adsorption capacity. Covalently bonded amine species in the mesoporous silica were robust enough to maintain steady adsorption performance during 10 repetitions of the adsorption–desorption cycle.     

Enhanced CO2 separation performance of mixed matrix membrane by incorporating amine-functionalized silica filler

Mixed matrix membranes (MMMs) owing to the tunable characteristics and functionalization ability can effectively substitute the highly intensive conventional membranes for industrial-scale CO₂ separation. Further, to strengthen the interfacial polymer-filler interaction, an interfacial design strategy incorporating active functional groups in the filler surface can be demonstrated. In this study, as-synthesized silica nanoparticles (SNPs) was surface functionalized by (3-aminopropyl) trimethoxysilane silica modifier (AFSNP). The CO₂ separation of poly (vinyl alcohol)/polyethylene glycol based MMM infused with surface-functionalized SNP (AFSNP) was conducted. The comparative study highlighted in-depth analysis of intrinsic physicochemical properties of as-synthesized membranes and nanoparticles. Detailed characterization such as advanced microscopic analysis, X-ray photoelectron spectroscopy (XPS) analysis and ninhydrin assay validated the successful grafting of amino groups onto the silica surface. The morphological inspection corroborated the consistent dispersion ability of the nanoparticles in the membrane matrix. The effect of the operating conditions on the membrane selectivity and CO₂ permeance were statistically analyzed by ANOVA. The CO₂ permeation result (CO₂ permeance and CO₂/N₂ selectivity) exhibited many fold increment with surface functionalization of SNPs compared to undoped silica MMM. The defect-free, performance-oriented CO₂-selective membrane thus opened up the possibility of this combination as a prospective contender for large-scale carbon capture studies.     

氨基改性有序介孔氧化铝吸附二氧化碳性能研究

采用硝酸铝为铝源,碳酸铵为沉淀剂,聚乙二醇（PEG1450）为模板剂,合成廉价的有序介孔氧化铝 （OMA）作为吸附剂载体。以2-氨基-2-甲基-1-丙醇（AMP）为氨基化表面修饰剂,对OMA采用过量浸渍法进行表面氨基化,制备一种高性能低成本的二氧化碳吸附剂OMA-AMP。通过BET法比表面积测定、X射线衍射（XRD）、透射电镜（TEM）、红外光谱（IR）等表征方法对改性前后吸附剂的比表面积、孔结构等特性进行表征,结果表明制备的 OMA-AMP具有比表面积大、孔径分布窄、孔结构有序等特点。利用模拟烟道气,从浸渍时间、吸附床层温度、气体流量以及AMP浓度4个变量考察吸附剂的性能。结果表明,OMA经过质量分数为50%的AMP浸渍12 h,在吸附温度为70 ℃、气体流量为40 mL/min条件下,OMA-AMP对二氧化碳的吸附量高达84.15 mg/g;吸附剂吸附性能较稳定,再生容易且效果良好;吸附剂制备成本低廉,吸附效率高。该吸附剂可以解决在二氧化碳捕集技术中成本居高不下的问题,在工业上具有实际应用价值。     

Amine‐functionalized mesoporous silica: A material capable of CO2 adsorption and fast regeneration by microwave heating

The surface of ordered mesoporous (MCM‐48) silica has been subjected to covalent grafting with silane molecules containing one to three amino groups. The dielectric properties of the materials were studied in detail, and the functionalized materials were used for CO₂ adsorption at room temperature, followed by regeneration under either conventional heating or microwave irradiation. It has been found that, as the intensity of functionalization with amino groups increases (from mono‐ to tri‐amino silanes) both the CO₂ load and the dielectric response at microwave frequencies increase. In particular, functionalization with a tri‐amino silane derivative gave the highest CO₂ adsorption and the fastest microwave heating, resulting in a fourfold acceleration of adsorbent regeneration. The grafted material was fully stable for at least 20 adsorption‐regeneration cycles, making it an ideal candidate for microwave‐swing adsorption (MWSA) processes. © 2015 American Institute of Chemical Engineers AIChE J, 62: 547–555, 2016     

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。     

Preparation of dendrimer polyol/mesoporous silica nanocomposite for reversible CO2 adsorption: Effect of pore size and polyol content

This paper focuses on the synthesis of polyol/MCM-48 nanocomposite materials with different percentages of polyalcohol dendrimer H20. The obtained materials were used for CO₂ adsorption. CO₂-TPD analysis showed that the samples containing 1 and 3 wt% of H20 dendrimer have low CO₂ adsorption capacity due to the occupation of active sites, The sample prepared with 0.5 wt% of H20 dendrimer exhibited higher adsorption capacity and thermal stability. The affinity toward CO₂ was found to be mainly due to the presence of organic moiety within the MCM-48 pores.     

氨基改性蠕虫型介孔SiO_2吸附CO_2性能的研究

采用D2000为模板剂,TEOS为硅源,在中性的条件下合成了具有较大孔径的蠕虫型介孔SiO2(MSU-J),并采用四乙烯五胺(TEPA)通过物理浸渍的方法制备不同质量分数的TEPA改性的MSU-J,得到具有高吸附量的CO2吸附剂。利用FT-IR,N2吸附/脱附及TG对所制备的样品进行表征。CO2的吸附试验是在不同氨基质量分数(20%,30%,50%,70%)以及不同温度下测试。吸附实验表明,浸渍TEPA后,吸附剂由单纯的物理吸附转变为以氨基为活性中心的化学吸附,且随着TEPA浸渍含量的增加吸附量先增加后降低,当TEPA负载量(质量分数)为50%时,吸附量可达到164.3 mg/g。温度对吸附剂的吸附性能也有一定的影响,最佳的吸附温度为25℃,这与吸附机理有关,随着温度的升高,反应向解吸附方向移动。循环性试验表明,所制备的吸附剂具有良好的循环性能,材料重复使用6次,对CO2吸附性能只有少量的下降,这可能是由于TEPA的挥发或者部分分解引起的。     

Removal of DDT from aqueous solutions using mesoporous silica materials

BACKGROUND: There are few reports about adsorbents for the effective removal of large‐molecule pesticides such as DDT (1,1,1‐trichloro‐2,2′ bis(p‐chlorophenyl)ethane). Some mesoporous silica materials and their modified derivatives might serve as good adsorbents for these large organic molecules because of their large pore diameter and special pore structures. In this work, the adsorption processes of DDT in aqueous solutions were investigated using different mesoporous silica materials, including HMS, MCM‐41, SBA‐15 and MCM‐48. RESULTS: All these materials exhibit efficient DDT removal, and the adsorption is a rapid process with over 50% of DDT removed within approximately 2 h. The efficiency of DDT removal is influenced by the adsorbent characteristics, such as pore volume, pore diameter, connectivity between pore channels and surface OH groups. The influences of water/acetone ratio and initial DDT concentration in solution were also explored. It was found that with enhancing DDT solubility, the addition of acetone in the reaction solution had no evident impact on DDT adsorption efficiency. Increasing the initial concentration of DDT resulted in a decrease of DDT adsorption efficiency. The adsorption kinetics of DDT on mesoporous silica material is shown to be pseudo‐second‐order. After thermal treatment at a relatively low temperature of 450 °C, the adsorbed DDT was completely decomposed and the adsorbents, except MCM‐41, were regenerated well. CONCLUSION: The results demonstrate the potential of a simple and efficient new approach for the removal of OCPs (organochlorine pesticides), especially large OCP molecules from surface water or groundwater. Copyright © 2008 Society of Chemical Industry