【作者】 赵丹丹；

【导师】 张兵；

【作者基本信息】 沈阳工业大学 ， 化学工程， 2015， 硕士

【摘要】 炭膜（通常全称为炭分子筛膜）是通过炭化有机聚合物膜而成，通过分子筛分机理对气体进行高效分离。因炭膜具有高效、节能、环保、过程易于控制、操作方便、易于放大等优点，在气体分离、液体分离、生物提纯、膜反应器及燃料电池等许多生产和生活领域显示出卓越的应用前景，近三十年来吸引了越来越多研究者的关注。但是，由于质地脆、造价高等问题严重地制约了炭膜的发展，而一直未能真正大规模工业化。鉴于此，本文通过将炭膜复合在高强度支撑体表面制备具有高强度机械性能的气体分离炭膜，并开发其在高附加值化学反应过程中的应用，从而为解决炭膜所面临的发展难题，为促进商业化应用奠定基础和提供依据。首先，以廉价的酚醛树脂为支撑体，考察了成型压力及ZSM-5沸石分子筛加入量对孔径分布及孔隙率的影响；以1,4-双(4-氨基-2-三氟甲基-苯氧基)苯-1,2,3,4-环丁烷四甲酸二酐基聚酰亚胺（6FAPB-CBDA）为前驱体，ZSM-5沸石分子筛为改性剂，分别采用滴加和旋涂两种成膜方法制备了复合炭膜。通过热重分析，红外光谱、X射线衍射、扫描电镜、氮吸附以及渗透法等手段对样品的热稳定性、官能团演变、碳结构、炭膜微观形貌、孔隙结构与气体分离性能进行了分析。考察了成膜方法、ZSM-5含量、渗透温度、渗透压力、炭化温度对炭膜的气体分离性能的影响。最后，将分离性能优异的炭膜耦合在反应器内，用于强化甲醇水蒸气重整制氢反应，考察了反应温度、炭化温度、反应器构型对甲醇转化率及氢气收率的影响。结果表明：（1）经900℃炭化的支撑体其孔半径随制备压力的增大而降低，最佳的制备压力为2MPa，此时孔半径主要分布在0.4-0.6μm，孔隙率为53.25%；支撑体经ZSM-5杂化改性后有利于提高机械强度，但同时孔隙率降低不适宜用作制备复合炭膜的支撑体。（2）炭膜的最佳炭化温度为650°C，其中滴加法制备的复合炭膜的最佳滴数为20滴，对H2/N2，CO2/N2，O2/N2的选择性分别为132.52，18.47及8.27，对压缩空气中氧氮的选择性为5.3。（3）旋涂法制备的炭膜最佳旋涂次数为6次，对H2/N2，CO2/N2，O2/N2的最佳选择性分别为490.2，67.66及34.84。采用旋涂法及6次涂膜-干燥条件，经ZSM-5杂化改性后，炭膜渗透性及选择性均降低。随着掺杂量从0.1%增大到0.5%，炭膜的分离性能逐渐下降。（4）当将上述最佳旋涂法所制备的炭膜用于强化反应时，在最佳反应温度为260°C时取得最大的氢气收率为51.5%，甲醇转化率为75%，分别是传统固定床反应器的1.21倍及1.24倍。更多还原

【Abstract】 Carbon membranes (carbon molecular sieve membranes for full name) are usuallyfabricated by the pyrolysis of organic membranes, which can effectively separate gas mixturedepending on molecular sieving mechanism. Over the past30years, carbon membranes havegained much attention because of its advantages, such as high efficiency, energy saving,environmental protection, convenient operation, easy control, easy scaleup and easy operation.Carbon membranes show a good appilication prospect in gases or liquid separation, biomasspurification, membrane reactor, fuel cell and so on. However, the industrial development ofcarbon membranes is still limited by the vital restriction of high-cost and brittlement. To solvethese problems the following solutions were proposed in this thesis: first, carbon membraneswere preparaed by compositing a separation layer on the support to improve the mechanicalperformance. Second, the as-prepared carbon membranes were applied for the intensificationof chemical reaction process with high added value. It is believed that the present work isfavorable for resolving the issues confronted by carbon membranes and consequentlypromotes the commercial application by building the academic and practical foundation.First, the support was fabricated with inexpensive phenolic resin. The effect of mouldingpressure and the dosage of ZSM-5on the pore size distribution and porosity were investigated.Composite carbon membranes were prepared by adopting6FAPB-CBDA type polymide asprecursor material and ZSM-5as modifier by two membrane-forming methods of drop-coatingand spin-coating methord, respectively. Thermogravimetry, Fourier transformed infraredspectroscopy, scanning electron microscopy, transmission electron microscopy, x-raydiffraction, nitrogen adsorption and permeation, etc., were utilized to analysis the thermalstability of precursor, evolution of functional groups, morphology, pore structure, carbonstructure and gas separation performance of the samples. The influence factors, such asmembrane-forming method, the dosage of ZSM-5, permeating-temperature and pressure, andcarbonization temperature, on the separation performance of carbon membranes wereinvestigated. Finally, the carbon membranes with excellent separation performance werecouplied in the reactor and used to intensify the reaction of hydrogen product from methanolsteam reforming. The effect of reaction temperature, the carbonization temperature of carbonmembranes and the type of reactor on the methanol conversion and hydrogen yield wasstudied.Results have shown that:(1) The pore radius size of support carbonized at900°Cdecreases with the increase of moulding pressure. The optimum moulding pressure is2MPa, from which the pore radius size of as-sythesized support is mainly distributed in0.4-0.6μmalong with the porosity of53.25%. The modified support with ZSM-5is beneficial to theenhancement of mechanical strength. Nevertheless, it is not suitable for the usage of supportdue to the silmutanuous reduction of porosity.(2) For drop-coating, the optimum separationperformance is achived at the selectivities of132.52(H2/N2),18.47(CO2/N2),8.27(O2/N2)and5.3(compressed air) when the preparation condition is carbonization temperature at650°C and20droplets.(3) For spin–coating, the optimum separation performance is achived atthe selectivities of490.2(H2/N2),67.66(CO2/N2) and34.84(O2/N2) when the preparationcondition is coating-drying cycles6times and carbonization at650°C. In comparison, theincorporation of ZSM-5into membranes results into the reduction of permeability andselectivity of carbon membranes prepared by spin-coating and coating-drying of6cycles.(4)When the abovementioned optimum carbon membranes from spin-coating method wereapplied to intensify the reaction, the optimum results is reached to51.5%(hydrogen yield)and75%(conversion) at the conditions of reaction temperature of260°C. Those two valuesare correspondingly1.21time and1.24times in magnitude in contrast with traditional fixedbed reactor.更多还原