膜气体吸收法脱除电厂模拟烟气CO_2

介绍了化学吸收法、物理吸收法、吸附法、膜分离法、膜吸收法和低温蒸馏法等烟气减排技术,综述了近几年气体吸收膜法在减少电厂模拟烟气CO2排放中的研究进展及福建省膜研究开发情况,总结了气体吸收膜法发展与应用中存在的不足,指出膜气体吸收法的发展前景。     

熔融盐膜法脱除航天舱中CO2传质模型

基于电化学理论、膜分离与传质理论，采用非平衡态热力学，建立了熔融盐(43．5％ Li2CO2 25％K2CO3 31.5?Na2CO3)(mol.?膜法脱除C02数学模型。首先，根据熔盐体系离子的Hittorf迁移数、比电导、扩散系数等独立实验参数，计算得到体系的Onsager系数和模型参数，然后用计算机求得该模型的数值解。解的结果表明：影响CO2传质通量的因素主要有电流密度及C02在膜两侧的浓度差。在低电流密度下，浓差推动力起主导作用：在较高电流密度下，膜两侧浓差推动力对C02传质影响甚微，电流密度对C02的传质则起着决定性作用。为了进一步验证数学模型，在823K及常压条件下，模拟航天舱中的气体成分，进行了熔融盐膜法脱除CO2的实验研究。实验结果与模型理论解吻合较好。     

超临界CO2及超临界CO2/乙醇中磷脂酰胆碱的溶解度

利用动态法测定了磷脂酰胆碱(PC)在超临界CO2(SC-CO2)及超临界CO2/乙醇体系中的溶解度。在15~30 MPa压力(p)、313~343 K温度(T)条件下,PC在SC-CO2中的溶解度为x1(PC)=10-6~10-5,在SC-CO2/乙醇多元体系中,PC溶解度x2(PC)可提高至10-4。PC的溶解度与c(CO2)(d)、x(CH3CH2OH)(c)呈指数相关性。根据缔合反应规则,建立了质量作用模型x1(PC)=d3.89e(-2383.63/T-41.64)、x2(PC)=d3.17c0.36e(-1748.03/T-33.73),分别关联PC在SC-CO2、SC-CO2/乙醇中的溶解度,模型计算结果与溶解度实验数据较好吻合,关联误差(AARD)分别为4.31%、3.78%。     

CO2通过合成聚合物膜的促进传递

Two kinds of fixed carrier membrane materials containing secondary amine and carboxyl groups whichcan be used as carriers of CO2 were prepared. One was poly(N-vinyl-γ-sodium aminobutyrate)(PVSA), whichwas obtained through the hydrolysis of polyvinylpyrrolidone (PVP) synthesized with N-vinylpyrrolidone(NVP) byradical polymerization. The other was poly(N-vinyl-γ-sodium aminobutyrate-co-sodium acrylate)(VSA-SA), whichwas obtained through the hydrolysis of copolymer of N-vinylpyrrolidone and acrylamide(AAm) (NVP-AAm). Thecomposite membranes were developed with PVSA or VSA-SA as active layer and polysulfone (PS) as supportmembranes. The permeation rates of pure CO2 and CH4 gas as well as binary mixtures of CO2/CH4 throughthe composite membranes were measured. The results show that the composite membranes present better CO2permeation rates than other fixed carrier membranes do reported in literature. For example, at 26℃, 1330 Pa of CO2pressure, the PVSA/PS composite membrane displays a CO2 permeation rate of 5.95 × 10-7 cm3.cm-2.s-1.pa-1with CO2/CH4 ideal separation factor of 212.1. At 20℃, 6400Pa of CO2 pressure, the VSA-SA/PS compositemembrane displays a CO2 permeation rate of 4.24 × 10-8 cm3@cm-2.s-1.Pa-1 with CO2/CH4 ideal separationfactor of 429.7. The results with the gas mixtures are not as good as those obtained with pure gas because ofthe coupling effects between CO2 and CH4. The heat cross-linked membrane shows good separation factor due todensification of the polymer.     

富含二氧化碳的天然气分离及其利用

论述了国内外对富含二氧化碳的天然气分离技术的研究进展,包括：膜分离法、变压吸附（PSA）法、物理吸收法和化学吸收法等,并分析了天然气资源的深加工利用及其产品开发前景。     

二氧化碳气体综合利用研究进展

介绍了二氧化碳作为化工原料、生物原料和制冷剂方面的工业应用,指出利用核能和太阳能提供氢源,合成大宗化学原料,是解决CO2温室效应,实现能源循环利用的有效方法。     

二氧化碳选择性吸收方法的研究进展

综述了二氧化碳选择性吸收方法的研究进展,包括物理吸收法、化学吸收法、膜吸收法,并分析了各种方法的优缺点。     

Adsorption and Desorption of Carbon Dioxide and Nitrogen on Zeolite 5A

The adsorption equilibrium data of CO₂ and N₂ at (303, 333, 363, 393, 423) K ranging 0-1 bar on zeolite 5A is reported. The pressure and temperature range covers the operating pressure in adsorption units for CO₂ capture from power plants. Experimental data were fitted by the multi-site Langmuir model. The adsorbent is much more selective to CO₂: loading at 303 K and 100 kPa is 3.38 mol/kg while loading of N₂ at the same pressure is 0.22 mol/kg. The Clausius-Clapeyron equation was employed to calculate the isosteric enthalpy of adsorption. The fixed-bed adsorption and desorption of carbon dioxide and nitrogen on zeolite 5A pellets has been studied. A model based on the bi-LDF approximation for the mass transfer, taking into account the energy and momentum balances, had been used to describe the adsorption kinetics of carbon dioxide and nitrogen. The model predicted satisfactorily the breakthrough curves obtained with carbon dioxide–nitrogen mixtures. Desorption process (consisting of depressurization, blowdown, and purge) was also performed. Following the feasibility of concentration and capture of carbon dioxide from flue gases by Pressure Swing Adsorption (PSA) process was simulated. A CO₂ recovery of 91.0% with 53.9% purity was obtained using a five-step Skarstrom-type PSA cycle.     

气液两相流在炭膜微滤钛白悬浮液中的应用研究

采用平均孔径为1.0μm的管状多孔炭膜实验研究了炭膜微滤钛白悬浮液的过程中引入气体形成两相流的强化微滤过程.实验结果表明,在温度20℃、跨膜雎差0.04～0.16 MPa、料液流速0.85～1.56 m·s-1、气体流速0.29～2.02 m·S-1、悬浮液浓度0.1～1.0 g·L-1时,通入气体形成的气-液两相流可以大大强化微滤过程.两相流相对于单相流的最大稳定渗透通量可提高62%,而且达到稳定通量的时间也相应缩短.实验发现,在相同操作条件下膜组件竖直放置比水平放置时稳定渗透通量增加了12%;弹状流是有利的强化流型:两相流条件下随着跨膜压差的增加,稳定通量快速增加,在压力0.11 MPa 时通量达到最大值,然后随压力增加,渗透通量缓慢下降.     

CO_2/CH_4分离膜研究进展

介绍ＣＯ２／ＣＨ４分离膜的开发背景及发展历史;ＣＯ２／ＣＨ４分离膜材料及相应的成膜技术,并提出ＣＯ２／ＣＨ４分离膜的发展方向。     

城市垃圾污染监测用二氧化碳中甲烷气体标准物质的研制

城市垃圾填埋法由于会释放大量二氧化碳和甲烷温室气体而受到广泛关注。研制了城市垃圾污染监测用气体标准物质,该标准物质以垃圾场填埋气为背景气,避免了影响填埋场释放的甲烷及二氧化碳气体监测结果的基体效应。同时还可以模拟不同环境下的垃圾场填埋气,确保城市垃圾污染监测用气体分析仪器监测数据的准确性。采用称量法制备了一系列浓度为1%~65%(mol/mol)二氧化碳中甲烷气体标准物质,并对该气体标准物质的均匀性、稳定性及随压力变化的实验结果进行了分析与考察。结果表明,研制的气体标准物质量值准确,均匀性、稳定性好。该标准物质已获批为国家二级标准物质GBW(E)061757。     

渗透汽化分离DMF/水混合物的PVA-g-AAm膜的制备和表征

使用聚乙烯醇及丙烯酰胺这两种材料,合成了不同枝度的共聚物(PVA-g-AAm),并对两种渗透汽化复合膜(PVA-g-AAm)进行制备。黏均分子量是运用用黏度法测定的,而表征则分别由接触角,红外光谱(FT-IR)和热重(TGA)等方法进行测定。而DMF/水混合体系的渗透汽化分离主要是复合膜的运用,并对膜分离的影响因素进行分析。实验结果显示,分离性能最好的是接枝度为90%的PVA。而PVA的渗透量随着DMF质量分数的增加而减少,PVA的通量最小时是在0.25~0.65 kg/(m~2·h)之间,在0.2~而膜的分离因子达到最大时DMF质量分数为33%。而温度的增加可是渗透量增大,分离因子减小。     

Highly Perm-Selective Micro-Porous Hydrotalcite-Silica Membrane for Improved Carbon Dioxide-Methane Separation

A notable improvement of carbon dioxide (CO₂) adsorption in meso- and micro-porous membranes was observed when hydrotalcite (HT) was incorporated in the membranes. For carbon dioxide in carbon dioxide-methane (CH₄) mixture, HT-silica membrane successfully overcame the upper permeability/selectivity limitation for glassy and polymeric membranes, despite the absence of a solution-diffusion mechanism that is typically present in the glassy and polymeric membranes. The performance of HT-silica membrane was observed to exceed that of micro-porous silica and high performance zeolitic imidazolate framework (ZIF) membranes. Incorporating unnecessarily high HT content in silica membrane, however, caused the membrane to lose its molecular sieving capacity and resulted in reduced selectivity of the gas.     

Ionic Liquids‐Based Membranes for Carbon Dioxide Separation

Ionic liquids (ILs) have gained wide‐spread focus owing to its negligible vapor pressure, low heat capacity, high thermal stability, and structural diversity. The solubility and selectivity toward carbon dioxide has made ILs a unique platform that possess the potential in gas separations. In particularly, combining functional ILs with membranes and porous supports is an efficient way to design task‐specific materials for CO₂ separations. This minireview summarizes the developments and advances of ionic liquids‐based membranes for CO₂ separations in recent three years, with an emphasis on the strategy of incorporating ionic liquids and CO₂ separation performance.     

温和条件下CoPc/TiO2光催化还原CO2

采用浸渍法制备的TiO2负载钴酞菁(CoPc/TiO2)为光催化剂,在碱性水溶液中、可见光照下,CO2可被光催化还原为产物HCOOH、CO、CH4。对催化剂的制备条件进行了考察,在m(CoPc)∶m(TiO2)=1∶100、催化剂浸渍时间12 h、浸渍溶剂为甲苯、催化剂焙烧温度200℃的条件下,还原总产物量最高可达1 075.38μmol/g-cat,其中甲酸为主产物,最高可达708.54μmol/g-cat。对催化剂进行了XRD、DRS表征,证实了CoPc在TiO2表面的负载。结果表明:用该催化剂在可见光照及常温常压下,于水溶液中就可将CO2还原。其次,实验还发现光照下可产生电子转移,实现了电荷的重新分配,以降低电子-空穴的重新结合;TiO2表面应有一定的空隙率,有利于CO2在其表面获得电子被还原。     

CO2加氢合成二甲醚催化剂的研究

考察了复合方法对二氧化碳加氢合成二甲醚催化剂CuO-ZnO-Al2O3/HZSM-5的影响。研究结果表明,在分装法、混装法、干混法、湿混法、共沉淀沉积法和共沉淀浸渍法等方法中,以干混法制备的复合催化剂对于二氧化碳加氢直接合成二甲醚的催化反应性能最适宜。在制备复合催化剂时,应尽量使催化剂中两种活性中心接触紧密,发挥其协同效应,但是不能使两种活性中心相互覆盖,以致生成非活性物种。     

木质素酚醛树脂炭膜的CP/MAS 13C NMR表征

采用固体核磁共振技术CP/MAS 13C NMR分析了木质素酚醛树脂炭膜。结果显示木质素含量的变化影响到炭膜的结构,如:炭膜中侧链烷基碳、非酚型紫丁香基和羟甲基碳结构。     

充气膜技术在处理叠氮化物废水中的应用

简要介绍了充气膜技术的基本原理，讨论了应用该技术分离和回收起爆药废水中叠氮化物的影响因素。实验结果表明：叠氮化物的传质速率与吸收液的浓度和流量无关；化学吸收比真空抽吹和压缩空气吹扫对叠氮化物具有更高的去除率；叠氮化物的传质速率与膜性能有关；随着废水中其它挥发组分的增加，叠氮化物的传质速率相应降低。     

一种测量超临界CO2在聚合物中溶解行为的新装置

设计了一种测量超临界CO2（ScCO2）在聚合物中溶解行为的装置,并通过测量温度在443.15~463.15 K,压力在7.5~9.5 MPa范围内ScCO2在聚苯乙烯（PS）中的溶解度及溶解速度验证装置的可行性。结果表明,溶解度实验值与计算值的相对误差低于20 %,而依据实验值计算的扩散系数与文献值表现出相同数量级,由此说明新装置能够进行ScCO2在聚合物中溶解行为的测量。     

介孔材料TiO2/SBA-15制备及光催化性能研究

以三嵌段共聚物P123为结构导向剂、甘油作为助溶剂合成了孔道长度可控的六方介孔硅基材料SBA-15,随后在绿色溶媒超临界二氧化碳中合成介孔材料TiO2/SBA-15,利用XRD、N2吸附-脱附、SEM、TEM和EDX等技术对其结构进行分析表征。结果表明甘油的加入可以有效调控SBA-15的孔道长度,TiO2纳米颗粒负载之后,SBA-15六方介孔结构可以得到保持。以染料亚甲基蓝作为模拟污染物对其进行光催化降解测试,合成的负载材料TiO2/SBA-15的降解效果要远远超过纳米TiO2颗粒,同时SBA-15孔道长度越短,其降解效果越好。