Preparation of WO3-TiO2/SBA-15 catalyst and its photocatalytic performance in oxidative desulfurization
-
摘要: 采用孔道内水解法制备了WO3-TiO2/SBA-15催化剂用于光催化氧化柴油脱硫, 利用XRD、SEM、EDS、N2吸附-脱附、FT-IR、TG-DTA和UV-vis等技术对该催化剂进行了表征, 考察了WO3和TiO2负载量、焙烧温度和焙烧时间对其光催化氧化脱硫性能的影响。结果表明, WO3和TiO2负载量分别为1.6%和15%, 焙烧温度500℃, 焙烧时间为3 h条件所制备的催化剂性能最佳; 在该条件下制备的WO3-TiO2/SBA-15催化剂仍保持SBA-15的六方介孔结构, 模拟柴油的脱硫率高达87.9%, 且具有良好的回收再生性能。
-
关键词:
- WO3-TiO2/SBA-15 /
- 光催化 /
- 氧化脱硫 /
- 柴油
Abstract: WO3-TiO2/SBA-15 catalyst was prepared by inner-pore hydrolysis method; it was characterized by XRD, SEM, EDS, N2 sorption, FT-IR, TG-DTA and UV-vis and used in the photocatalytic oxidative desulfurization of diesel oil. The effects of WO3 and TiO2 loading and calcination temperature and time on the performance of the WO3-TiO2/SBA-15 catalyst in its photocatalytic oxidative desulfurization were investigated. The results indicated that the optimum loadings of WO3 and TiO2 were 1.6% and 15%, respectively, and corresponding calcination temperature and time were 500℃ and 3h, respectively. Over the WO3-TiO2/SBA-15 catalyst prepared under the optimum conditions, in which the hexagonal mesoporous structure was well retained, the desulfurization rate of model diesel oil reached 87.9%. Moreover, the WO3-TiO2/SBA-15 catalyst also exhibited excellent reusability after regeneration.-
Key words:
- WO3-TiO2/SBA-15 /
- photocatalysis /
- oxidative desulfurization /
- diesel oil
-
表 1 SBA-15和1.6WO3-yTiO2/SBA-15样品的结构参数
Table 1 Textural parameters of SBA-15 and 1.6WO3-yTiO2/SBA-15 catalysts
Sample Surface
area
A/(m2·g-1)Pore
volume v/
(cm3·g-1)Pore
size
d /nmSBA-15 876.35 1.09 6.35 1.6WO3/SBA-15 849.42 0.99 6.32 1.6WO3-10TiO2/SBA-15 784.82 0.82 6.19 1.6WO3-15TiO2/SBA-15 763.65 0.76 6.25 1.6WO3-20TiO2/SBA-15 683.42 0.65 6.23 -
[1] ACHMANN S, HAGEN G, HÄMMERLE M, MALKOWSKY I M, KIENER C, MOOS R. Sulfur removal from low-sulfur gasoline and diesel fuel by metal-organic frameworks[J]. Chem Eng Technol, 2010, 33(2):275-280. doi: 10.1002/ceat.v33:2 [2] XIE D, HE Q H, SU YY, WANG T W, XU R F, HU B X. Oxidative desulfurization of dibenzothiophene catalyzed by peroxotungstate on functionalized MCM-41 materials using hydrogen peroxide as oxidant[J]. Chin J Catal, 2015, 36(8):1205-1213. doi: 10.1016/S1872-2067(15)60897-X [3] 张文岑, 万昆, 余国贤, 周晓龙, 李承烈.磷酸活化稻壳制备柴油脱硫吸附剂[J].石油学报:石油加工, 2010, 26(4):588-593. http://www.cnki.com.cn/Article/CJFDTOTAL-SXJG201004022.htmZHANG Wen-ling, WAN Kun, YU Guo-xian, ZHOU Xiao-long, LI Cheng-lie. Preparation of adsorbent for desulfurlzation of diesel fuel through activating rice hull by phosphoric acid[J]. Acta Pet Sin (Pet Proc Sect), 2010, 26(4):588-593. http://www.cnki.com.cn/Article/CJFDTOTAL-SXJG201004022.htm [4] FANG X A, GUO R A, YANG C M. The development and application of catalysts for ultra-deep hydrodesulfurization of diesel[J]. Chin J Catal, 2013, 34(1):130-139. doi: 10.1016/S1872-2067(11)60506-8 [5] WANG C, ZHU W S, XU Y H, XU H, ZHANG M, CHAO Y H, YIN S, LI H M, WANG J G. Preparation of TiO2/g-C3N4 composites and their application in photocatalytic oxidative desulfurization[J]. Ceram Int, 2014, 40(8):11627-11635. doi: 10.1016/j.ceramint.2014.03.156 [6] ZHANG J, ZHAO D S, WANG J L, YANG L Y. Photocatalytic oxidation of dibenzothiophene using TiO2/bamboo charcoal[J]. J Mater Sci, 2009, 44(12):3112-3117. doi: 10.1007/s10853-009-3413-z [7] KACHINA A, PREIS S, KALLAS J. Catalytic TiO2 oxidation of ethanethiol for environmentally begnin air pollution control of sulphur compounds[J]. Environ Chem Lett, 2006, 4(2):107-110. doi: 10.1007/s10311-006-0042-5 [8] TACHIKAWA T, FUJITSUKA M, MAJIMA T. Mechanistic insight into the TiO2 photocatalytic reactions:65 design of new photocatalysts[J]. J Phys Chem C, 2007, 111(14):5259-5275. doi: 10.1021/jp069005u [9] 冯翔, 史非, 刘敬肖, 董晓丽, 白麓楠, 王晓卡, 张秀芳. WO3-TiO2复合光催化材料的水热合成及其光催化性能[J].材料导报, 2013, 27(22):37-40.FENG Xiang, SHI Fei, LIU Jing-xiao, DONG Xiao-li, BAI Lu-nan, WANG Xiao-ka, ZHANG Xiu-fang. Hydrothermal synthesis and photocatalytic activity of WO3-TiO2 composite photocatalysts[J]. Mater Rev, 2013, 27(22):37-40. [10] 陆诚, 杨平, 杜玉扣, 华南平, 宋海燕.载体对负载型TiO2催化剂光催化性能的影响[J].催化学报, 2003, 24(4):248-252. http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA200304003.htmLU Cheng, YANG Ping, DU Yu-kou, HUA Nan-ping, SONG Hai-yan. Effects of supports on photocatalytic performance of supported TiO2 catalysts[J]. Chin J Catal, 2003, 24(4):248-252. http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA200304003.htm [11] 纪桂杰, 张耀兵, 付宁宁, 唐磊, 刘鹏, 沈健. Mn/Al-SBA-15的制备及吸附脱硫性能[J].燃料化学学报, 2015, 43(4):449-455. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18609.shtmlJI Gui-jie, ZHANG Yao-bing, FU Ning-ning, TANG Lei, LIU Peng, SHEN Jian. Preparation and adsorption desulfurization performance of Mn/Al-SBA-15[J].J Fuel Chem Technol, 2015, 43(4):449-455. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18609.shtml [12] 王喆, 纪桂杰, 沈健. TiO2/SBA-15光催化氧化汽油脱硫的研究[J].石油炼制与化工, 2015, 46(4):51-54. http://www.cnki.com.cn/Article/CJFDTOTAL-SYLH201504015.htmWANG Zhe, JI Gui-jie, SHEN Jian. Study of photocatalytic oxidative desulfurization of gasoline with TiO2/SBA-15[J]. Pet Process Petrochem, 2015, 46(4):51-54. http://www.cnki.com.cn/Article/CJFDTOTAL-SYLH201504015.htm [13] 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. doi: 10.1126/science.279.5350.548 [14] 马晶, 强亮生, 唐翔波, 唐冬雁. TiO2/SBA-15的快速合成法及其催化性能[J].无机化学学报, 2010, 26(6):963-969. http://www.cnki.com.cn/Article/CJFDTOTAL-WJHX201006006.htmMA Jing, QIANG Liang-sheng, TANG Xiang-bo, TANG Dong-yan. TiO2/SBA-15:Rapid synthesis and photocatalytic performance[J]. Chin J Inorg Chem, 2010, 26(6):963-969. http://www.cnki.com.cn/Article/CJFDTOTAL-WJHX201006006.htm [15] WANG X J, LI F T, LIU J X, KOU C G, ZHAO Y, HAO Y J, ZHAO D S. Preparation of TiO2 in ionic liquid via microwave radiation and in situ photocatalytic oxidative desulfurization of diesel oil[J]. Energy Fuels, 2012, 26(11):6777-6782. https://www.researchgate.net/publication/263990721_Preparation_of_TiO2_in_Ionic_Liquid_via_Microwave_Radiation_and_in_Situ_Photocatalytic_Oxidative_Desulfurization_of_Diesel_Oil [16] 刘阳, 王晟, 王驹, 许章炼, 陈文兴, 蒋杰, 韦坚红. WO3/TiO2纳米棒复合材料的制备及其光催化活性[J].催化学报, 2010, 31(4):485-489. http://cdmd.cnki.com.cn/Article/CDMD-10269-2009189270.htmLIU Yang, WANG Sheng, WANG Tao, XU Zhang-lian, CHEN Wen-xing, JIANG Jie, WEI Jian-hong. Preparation of WO3/TiO2nanorod composites and its photocatalytic activity[J]. Chin J Catal, 2010, 31(4):485-489. http://cdmd.cnki.com.cn/Article/CDMD-10269-2009189270.htm [17] 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. doi: 10.1016/S1872-2067(06)60004-1WU Shu-jie, HUANG Jia-hui, WU Tong-hao, SONG Ke, WANG Hong-su, XING Li-hong, XU Hai-yan, XU Ling, GUAN Jing-qi, KAN 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. doi: 10.1016/S1872-2067(06)60004-1 [18] BUSUIOC A M, MEYNEN V, BEYERS E, MERTENS M, COOL P, BILBA N, VANSANT E F. Structural features and photocatalytic behaviour of titania deposited within the pores of SBA-15[J]. Appl Catal A:Gen, 2006, 312(9):153-164. https://www.researchgate.net/publication/229341270_Structural_Features_and_Photocatalytic_Behaviour_of_Titania_Deposited_Within_the_Pores_of_SBA-15 [19] WANG Z H, CHEN B, QUAN G L, LI F, WU Q L, DIAN L H, DONG Y X, LI G, WU C B. Increasing the oral bioavailability of poorly water-soluble carbamazepine using immediate-release pellets supported on SBA-15 mesoporous silica[J]. Int J Nanomed, 2013, 7(11):5807-5818. https://www.researchgate.net/publication/233840484_Increasing_the_oral_bioavailability_of_poorly_water-soluble_carbamazepine_using_immediate-release_pellets_supported_on_SBA-15_mesoporous_silica [20] 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. http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA200505015.htmCHEN 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. http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA200505015.htm [21] PALCHEVA R, SPOJAKINA A, DIMITROV L, JIRATOVA K. 12-Tungstophosphoric heteropolyacid supported on modified SBA-15 as catalyst in HDS of thiophene[J]. Microporous Mesoporous Mater, 2009, 122(1/3):128-134. https://www.researchgate.net/publication/232412976_12-Tungstophosphoric_heteropolyacid_supported_on_modified_SBA-15_as_catalyst_in_HDS_of_thiophene [22] HUANG Y, LI K X, YAN L S, DAI Y H, HUANG Z M, XUE K P, GUO H Q, XIONG J J. Preparation of 2D hexagonal p6mm ordered mesoporous WO3-TiO2 composite materials and their visible-light photocatalytic activity[J]. Chin J Catal, 2012, 33(2):308-316. [23] VU T H T, NGUYEN T T T, NGUYEN P H T, DO M H, AU H T, NGUYEN T B, NGUYEN D L, PARK J S. Fabrication of photocatalytic composite of multi-walled carbon nanotubes/TiO2 and its application for desulfurization of diesel[J]. Mater Res Bull, 2012, 47(2):308-314. doi: 10.1016/j.materresbull.2011.11.016