Study on the preparation of Mn/Al-SBA-15 and its adsorption desulfurization performance
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摘要: 以嫁接法制备的Al-SBA-15为载体,醋酸锰为活性组分前驱体,通过浸渍法制备Mn/Al-SBA-15吸附剂。利用X射线衍射(XRD)、N2吸附-脱附、NH3程序升温脱附(NH3-TPD)、吡啶-原位傅里叶变换红外(Py-FTIR)和X射线光电子能谱(XPS)等表征手段对吸附剂进行分析,以模拟汽油中噻吩的脱除反应为模型反应考察了吸附剂的吸附性能,确定了吸附剂的最佳Al/Si物质的量比,并结合表征结果对吸附剂脱硫过程进行机理探讨,最后研究了吸附剂的再生性能。实验结果表明,当Al/Si(mol ratio)为1:45时,吸附剂脱硫性能最高;吸附剂主要通过酸碱作用吸附噻吩分子;Al的引入提高了吸附剂的结构稳定性,从而提高了吸附剂的再生性能。Abstract: Mn/Al-SBA-15 absorbent was synthesized by impregnation using Al-SBA-15 prepared by grafting method as support, manganese acetate as precursor of active component. The samples were characterized by means of XRD, N2 adsorption-desorption, NH3-TPD, Py-FTIR and XPS. The adsorbent was used for adsorption desulfurization of simulated gasoline. The optimum molar ratio of Al/Si was determined through combining characterization of samples and their desulfurization performance. The mechanism of adsorption desulfurization was proposed. The regeneration properties were also studied. The results showed that when the molar ratio of Al/Si was 1:45, the performance of adsorbent was the best. The thiophene was adsorbed through acid-base reaction. The introduction of Al improved the stability and the regeneration of the adsorbent.
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Key words:
- thiophene /
- adsorption /
- SBA-15 /
- acidity /
- regeneration
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王军民, 袁铁. 超低硫清洁汽油的生产技术进展[J]. 天然气与石油, 2001, 19(4):14-17. (WANG Jun-min, YUAN Tie. The progress of ultra-low sulfur clean gasoline production technology[J]. Nat Gas Oil, 2001, 19(4):14-17.) 赵乐平, 关明华, 庞宏, 尤百玲. 无硫汽油技术方案的选择[C]//第十届全国工业催化技术及应用年会论文集. 西安:工业催化杂志社, 2013:303-305. (ZHAO Le-ping, GUAN Ming-hua, PANG Hong, YOU Bai-ling. No sulfur-content gasoline technology scheme[C]//The Essays of the Tenth National Industrial Catalysis Technology and Application. Xi'an:Industrial Catalysis Press, 2013:303-305.) WANG W B, WANG S J, LIU H Y, WANG Z X. Desulfurization of gasoline by a new method of electrochemical catalytic oxidation[J]. Fuel, 2007, 86(17):2747-2753. 朱全力, 赵旭涛, 赵振兴, 马洪江, 邓友全. 加氢脱硫催化剂与反应机理的研究进展[J]. 分子催化, 2006, 20(4):372-383. (ZHU Quan-li, ZHAO Xu-tao, ZHAO Zhen-xing, MA Hong-jiang, DONG You-quan. The research progress of hydrodesulfurization catalyst and reaction mechanism[J]. J Mol Catal (China), 2006, 20(4):372-383.) SENTORUN-SHALABY C, SAHA S K, MA X L, SONG C S. Mesoporous-molecular-sieve-supported nickel sorbents for adsorptive desulfurization of commercial ultra-low-sulfur diesel fuel[J]. Appl Catal B:Environ, 2011, 101(3):718-726. CHEN H, WANG Y H, YANG F H, YANG R T. Desulfurization of high-sulfur jet fuel by mesoporous π-complexation adsorbents[J]. Chem Eng Sci, 2009, 64(24):5240-5246. KO C H, PARK J G, PARK J C, SONG H, HAN S, KIM J. Surface status and size influences of nickel nanoparticles on sulfur compound adsorption[J]. Appl Surf Sci, 2007, 253(13):5864-5867. ALHAMED Y A, BAMUFLEH H S. Sulfur removal from model diesel fuel using granular activated carbon from dates' stones activated by ZnCl2[J]. Fuel, 2009, 88(1):87-94. TANG K, SONG L J, DUAN L H, LI X Q, GUI J Z, SUN Z L. Deep desulfurization by selective adsorption on a heteroatoms zeolite prepared by secondary synthesis[J]. Fuel Process Technol, 2008, 89(1):1-6. KE T, XIN H. Deep desulfurization of model gasoline by adsorption on mesoporous CeMCM-41[J]. Pet Sci Technol, 2010, 28(6):573-581. TIAN F P, SHEN Q C, FU Z K, WU Y H, JIA C Y. Enhanced adsorption desulfurization performance over hierarchically structured zeolite Y[J]. Fuel Process Technol, 2014, 128:176-182. NIE Y, DONG Y X, BAI L, DONG H F, ZHANG X P. Fast oxidative desulfurization of fuel oil using dialkylpyridinium tetrachloroferrates ionic liquids[J]. Fuel, 2013, 103:997-1002. GAO H S, LUO M F, XING J M, WU Y, LI W L, LIU Q F, LIU H Z. Desulfurization of fuel by extraction with pyridinium-based ionic liquids[J]. Ind Eng Chem Res, 2008, 47(21):8384-8388. CHEN J, LI J D, QI R B, YE H, CHEN C X. Pervaporation separation of thiophene-heptane mixtures with polydimethylsiloxane (PDMS) membrane for desulfurization[J]. Appl Biochem Biotechnol, 2010, 160(2):486-497. ITO E, VAN VEEN J A. On novel processes for removing sulphur from refinery streams[J]. Catal Today, 2006, 116(4):446-460. 张景成, 柳云骐, 安高军, 柴永明, 付庆涛, 刘晨光. 吸附脱硫技术生产清洁油品[J]. 化学进展, 2008, 20(11):1834-1845. (ZHANG Jing-cheng, LIU Yun-qi, AN Gao-jun, CHAI Yong-ming, FU Qing-tao, LIU Chen-guang. The adsorptive desulfurization technologies for ultra-clean oil production[J]. Prog Chem, 2008, 20(11):1834-1845.) 唐晓东, 李林, 曾雪玲, 赖先熔. 汽油活性炭基脱硫吸附剂的制备与评价[J]. 燃料化学学报, 2009, 37(5):629-634. (TANG Xiao-dong, LI Lin, ZENG Xue-ling, LAI Xian-rong. Preparation and evaluation of gasoline activated carbon-based desulfurization adsorbent[J]. J Fuel Chem Technol, 2009, 37(5):629-634.) 岳军, 刘晓勤, 姚虎卿. CuCl负载型吸附剂的深度脱硫性能研究[J]. 高校化学工程学报, 2007, 20(6):1001-1004. (YUE Jun, LIU Xiao-qin, YAO Hu-qing. Deep desulfurization performance of CuCl supported adsorbents[J]. J Chem Eng Chin Univ, 2007, 20(6):1001-1004.) WANG Y H, YANG R T, HEINZEL J M. Desulfurization of jet fuel by π-complexation adsorption with metal halides supported on MCM-41 and SBA-15 mesoporous materials[J]. Chem Eng Sci, 2008, 63(2):356-365. MENG X R, QIU G H, WANG G, CAI Q H, WANG Y H. Durable and regenerable mesoporous adsorbent for deep desulfurization of model jet fuel[J]. Fuel Process Technol, 2013, 111:78-85. ZHAO D Y, FENG J L, HUO Q S, MELOSH N, FREDRICKSON G H, CHMELKA B F, STUCKY G D. Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores[J]. Science, 1998, 279(5350):548-552. KRUK M, JARONIEC M, KO C H, RYOO R. Characterization of the porous structure of SBA-15[J]. Chem Mater, 2000, 12(7):1961-1968. 吴淑杰, 黄家辉, 吴通好, 宋科, 王虹苏, 邢丽红, 徐海燕, 徐玲, 管景奇, 阚秋斌. Al-SBA-15 介孔分子筛的合成、表征及其在苯酚叔丁基化反应中的催化性能[J]. 催化学报, 2006, 27(1):9-14. (WU Shu-jie, HUANG Jia-hui, WU Tong-hao, SONG Ke, WANG Hong-su, XING Li-hong, XU Hai-yan, XU Ling, GUAN Jing-qi, HAN Qiu-bin. Synthesis, characterization, and catalytic performance of mesoporous Al-SBA-15 for Tert-butylation of phenol[J]. Chin J Catal, 2006, 27(1):9-14.) 郭卓, 朱广山, 辛明红, 刘成站, 裘式纶. C60/SBA-15介孔复合材料的合成及其荧光性质的研究[J]. 高等学校化学学报, 2005, 26(10):1917-1920. (GUO Zhuo, ZHU Guang-shan, XIN Ming-hong, LIU Cheng-zhan, QIU Shi-lun.Synthesis and fluorescence properties of fulleride encapsulated in mesoporous SBA-15 host[J]. Chem J Chin Univ, 2005, 26(10):1917-1920.) 陈杨英, 韩秀文, 包信和. W-SBA-15介孔分子筛的直接合成及其对环己烯环氧化反应的催化性能[J]. 催化学报, 2005, 26(5):412-416. (CHEN Yang-ying, HAN Xiu-wen, BAO Xin-he. Direct synthesis of W-SBA-15 mesoporous molecular sieves and their catalytic performance for epoxidation of cyclohexene[J]. Chin J Catal, 2005, 26(5):412-416.) HUANG P, PAN S W, HUANG B C, CHENG H, YE D Q, WU L J, FU M L, LU S L. Structural properties of MnOx/Al-SBA-15 in low-temperature selective catalytic reduction of NOx with NH3[J]. Acta Phys-Chim Sin, 2013, 29(1):176-182. PUTZ M V, RUSSO N, SICILIA E. On the applicability of the HSAB principle through the use of improved computational schemes for chemical hardness evaluation[J]. J Comput Chem, 2004, 25(7):994-1003. PEARSON R G. Hard and soft acids and bases[J]. J Am Chem Soc, 1963, 85(22):3533-3539.
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