CAJ | 학술논문

沼气的主要成分是CH4和CO2，有效地去除沼气中的CO2是确保沼气成为优质燃气的必要条件。吸附法是去除沼气中CO2的有效方法，研制性能优良的吸附剂是吸附法研究的核心问题。该文以FNG-II型硅胶为载体，乙醇胺（ ethanolamine ， MEA ）为改性剂，制备了 MEA 改性硅胶吸附剂，表示为 FS-MEA （ FNG-II Silica-ethanolamine）。用X射线衍射、N2物理吸附脱附法、热重-差热、红外光谱等手段对吸附材料的结构、比表面积、孔结构、改性后结构变化等进行了分析。通过动态吸附分离试验，考察了FS-MEA对CH4/CO2的分离性能。结果表明：改性方法可将MEA附着在载体内孔表面，制得的FS-MEA可有效地分离CH4/CO2，但经过2次使用再生后，FS-MEA对CH4/CO2的分离性能有所下降，因此必须提高乙醇胺改性硅胶吸附剂的再生性能，才有可能使其应用于沼气提纯。
소기적주요성분시CH4화CO2，유효지거제소기중적CO2시학보소기성위우질연기적필요조건。흡부법시거제소기중CO2적유효방법，연제성능우량적흡부제시흡부법연구적핵심문제。해문이FNG-II형규효위재체，을순알（ ethanolamine ， MEA ）위개성제，제비료 MEA 개성규효흡부제，표시위 FS-MEA （ FNG-II Silica-ethanolamine）。용X사선연사、N2물리흡부탈부법、열중-차열、홍외광보등수단대흡부재료적결구、비표면적、공결구、개성후결구변화등진행료분석。통과동태흡부분리시험，고찰료FS-MEA대CH4/CO2적분리성능。결과표명：개성방법가장MEA부착재재체내공표면，제득적FS-MEA가유효지분리CH4/CO2，단경과2차사용재생후，FS-MEA대CH4/CO2적분리성능유소하강，인차필수제고을순알개성규효흡부제적재생성능，재유가능사기응용우소기제순。
The major components of biogas by anaerobic digestion are CH4 and CO2, so it is necessary to selectively separate CO2 from CH4 in order to improve heating value of biogas. Adsorption technology has been considered a competitive method for separating gases because of its relatively simple equipment and low energy consumption. It is well known that developing an excellent adsorbent is the key issue for adsorption separation. In the present work, MEA-modified FNG-II silica adsorbent was prepared by a conventional wet impregnation technique and the new adsorbent was named as FS-MEA. Silica was selected as the substrate and monoethanolamine (MEA) was modified at the outer surface of substrate. In order to coat the silica surface with MEA uniformly, MEA was dissolved in methanol in advance. The new adsorbent was characterized by powder X-ray diffraction (XRD), nitrogen adsorption/desorption, thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR) to determine pore pacing, pore volume, pore diameter, the organic loading on the substrate and amines. The results of XRD and nitrogen adsorption/desorption for the adsorbents showed that FNG-II silica contains a large amount of disordered mesopores. After 30 wt.%MEA loading, the mesoporous structures were preserved, but the specific surface area and pore volume decreased, which provided strong evidence that MEA could be attached to the inner pore surfaces of the silica. This result is in agreement with FTIR analysis. The TGA curves showed a unique significant mass loss on FNG-II silica under atmospheric pressure from 29℃to 870℃and the weight loss was derived from desorption of moisture. However for cases of FS-MEA, two major mass loss steps were observed in the same conditions. The first step in the range of 29℃to 170℃was attributed to desorption of moisture and CO2 that absorbed in MEA modified on the substrate. The second mass loss step occurred when the temperature was higher than 210℃, which were ascribed to the volatilization and/or decomposition of MEA. The TGA/DTA results provided further evidence that MEA was successfully modified on the substrate, and the new adsorbent can not be used higher than 210℃. The dynamic adsorption experiments were carried out to investigate the adsorbent’s separation capacity. The mixture of CH4 (65.6%) and CO2 (34.4%) was used for measuring breakthrough curves, from which the separation coefficient between the two gases was evaluated. The adsorbent was packed in a steel column of length 250 mm and inner diameter 11 mm, and the gas mixture flowed through the column with 200 cm3/min flow rate. The adsorption experiments were carried out at 298 K and 0.2 MPa. The results indicated that FS-MEA efficiently separated CH4 from CO2. The separation coefficient calculated is 4.53, which is better than that of some conventional adsorbents. Compared to the TGA/DTA results, the regeneration temperature of FS-MEA was identified as 110℃, because moisture and CO2 desorbed from 45℃ to 170℃, and the desorption rate was greatest at 106℃. After regeneration, the separation performance of FS-MEA for CH4 and CO2 decreased after its third use.