B2O3对Ag/TiO2-Al2O3吸附剂的柴油吸附脱硫性能影响

李莉达; 许承志; 郑美琴; 陈晓晖

B₂O₃对Ag/TiO₂-Al₂O₃吸附剂的柴油吸附脱硫性能影响

李莉达^1,2,
许承志^1,2,
郑美琴^1,2,
陈晓晖^1,2,

1.
福州大学化肥催化剂国家工程研究中心, 福建福州 350002;
2.
福州大学石油化工学院, 福建福州 350116

基金项目: The project was supported by the National Natural Science Foundation of China

详细信息

通讯作者:
陈晓晖,E-mail:chenxhfzu@fzu.edu.cn.

中图分类号: O643
计量
- 文章访问数: 378
- HTML全文浏览量: 25
- PDF下载量: 399
- 被引次数: 0
出版历程
- 收稿日期: 2015-04-16
- 修回日期: 2015-06-25
- 刊出日期: 2015-08-30

Effect of B₂O₃ modified Ag/TiO₂-Al₂O₃ adsorbents on the adsorption desulfurization of diesel

1.
National Engineering Research Center of Chemical Fertilizer Catalysts, Fuzhou 350002, China;
2.
School of Chemical Engineering, Fuzhou University, Fuzhou 350116, China

Funds: The project was supported by the National Natural Science Foundation of China

摘要

摘要: 采用浸渍法制备了不同B₂O₃负载量(e.g. 5%~20% (w))的Ag/TiO₂-B₂O₃-Al₂O₃吸附剂。以含硫量为245.36mg(S)/L 的商业柴油作为考察对象,常温常压下采用静态评价进行吸附脱硫性能研究。结果表明,B₂O₃改性后的Ag/TiO₂-Al₂O₃吸附剂的柴油吸附脱硫活性有了较大提高,当B₂O₃的负载量为15%时,吸附剂的吸附脱硫活性最高,2%Ag/4%TiO₂-15%B₂O₃-Al₂O₃ (w)的饱和吸附硫容达到2.36mg(S)/g 吸附剂。这对于未经预处理的商业柴油而言,吸附脱硫活性已经达到较高水平。采用N₂物理吸附、O₂化学吸附、X射线衍射(XRD)、NH₃程序升温脱附(NH₃-TPD)、傅里叶红外光谱(FT-IR spectra)、¹¹B核磁共振(¹¹B-NMR)等表征手段对不同负载量B₂O₃改性Ag/TiO₂-Al₂O₃吸附剂的织构性质、晶相结构和表面酸性的影响进行研究。关联活性测试和表征结果发现,吸附剂的吸附脱硫活性主要与吸附剂的表面弱酸性有关,而B₂O₃改性在吸附剂表面引入了较多的四配位的BO₄物种,能显著增加吸附剂表面弱酸性位点数量,提高吸附剂的吸附脱硫活性。
- Ag基吸附剂 /
- 柴油 /
- 吸附脱硫 /
- 弱酸性位点
Abstract: Ag/TiO₂-B₂O₃-Al₂O₃ adsorbents with different B₂O₃ loadings (e.g. 5%~20% (w)) were prepared by impregnation. Static adsorption tests were carried out by contacting the adsorbents with commercial diesel containing 245.36mg(S)/L sulfur at ambient conditions to investigate the adsorption desulfurization activity. The results show that Ag/TiO₂-Al₂O₃ modified by B₂O₃ exhibits a great enhancement for the adsorption desulfurization activity. When B₂O₃ (15%) was loaded, 2%Ag/4%TiO₂-15%B₂O₃-Al₂O₃ (w) could achieve the best desulfurization activity with a saturation capacity of 2.36mg(S)/g adsorbent. This is a significant achievement regarding the desulfurization efficiency, especially for commercial diesel without pretreatment. The effects of B₂O₃ on the textural properties, crystal structure and surface acidity properties of the adsorbent were studied by N₂-physisorption, O₂-chemisorption, X-ray diffraction (XRD), temperature-programmed desorption of ammonia (NH₃-TPD), Fourier transform infrared spectrometer (FT-IR spectra) and ¹¹B nuclear magnetic resonance (¹¹B-NMR) techniques. Correlating the characterizations with the desulfurization activity, it is found that the adsorption desulfurization activity is well related with the amounts of weak acid sites on the adsorbents. B₂O₃ modification induces larger amounts of BO₄ species and improves the surface weak acidity, resulting in a higher adsorption desulfurization activity.
- B₂O₃ /
- silver-based adsorbent /
- diesel /
- adsorption desulfurization

HTML全文

参考文献(36)

PARK J G, KO C H, YI K B, PARK J H, HAN S S, CHO S H, KIM J N. Reactive adsorption of sulfur compounds in diesel on nickel supported on mesoporous silica[J]. Appl Catal B: Environ, 2008, 81(3): 244-250.

XIAO J, WANG X, FUJII M, YANG Q, SONG C. A novel approach for ultra-deep adsorptive desulfurization of diesel fuel over TiO₂-CeO₂/MCM-48 under ambient conditions[J]. AIChE J, 2013, 59(5): 1441-1445.

SAMOKHVALOV A, TATARCHUK B J. Review of experimental characterization of active sites and determination of molecular mechanisms of adsorption, desorption and regeneration of the deep and ultradeep desulfurization sorbents for liquid fuels[J]. Catal Rev, 2010, 52(3): 381-410.

XIAO J, WU L, WU Y, LIU B, DAI L, LI Z, XIA Q, XI H. Effect of gasoline composition on oxidative desulfurization using a phosphotungstic acid/activated carbon catalyst with hydrogen peroxide[J]. Appl Energy, 2014, 113: 78-85.

KIM J H, MA X, ZHOU A, SONG C. Ultra-deep desulfurization and denitrogenation of diesel fuel by selective adsorption over three different adsorbents: a study on adsorptive selectivity and mechanism[J]. Catal Today, 2006, 111(1): 74-83.

VELU S, SONG C, ENGELHARD M H, CHIN Y H. Adsorptive removal of organic sulfur compounds from jet fuel over K-exchanged NiY zeolites prepared by impregnation and ion exchange[J]. Ind Eng Chem Res, 2005, 44(15): 5740-5749.

孟璇, SALISSOU ZAKATY M N, 翁惠新, 施力. 不同载体的镍基氧化锌对噻吩的吸附脱除性能[J]. 燃料化学学报, 2012, 40(3): 364-369.(MENG Xuan, SALISSOU ZAKATY M N, WENG Hui-xin, SHI Li. Adsorptive removal of thiophene over nickel-based ZnO with different supports[J]. J Fuel Chem Technol, 2012, 40(3): 364-369.)

XU X, ZHANG S, LI P, SHEN Y. Desulfurization of Jet-A fuel in a fixed-bed reactor at room temperature and ambient pressure using a novel selective adsorbent[J]. Fuel, 2014, 117: 499-508.

VELU S, MA X, SONG C. Selective Adsorption for removing sulfur from jet fuel over zeolite-based adsorbents[J]. Ind Eng Chem Res, 2003, 42(21): 5293-5304.

WATANABE S, MA X, SONG C. Characterization of structural and surface properties of nanocrystalline TiO₂-CeO₂ mixed oxides by XRD, XPS, TPR, and TPD[J]. J Phys Chem C, 2009, 113(32): 14249-14257.

孙霞, 王学松, 李健生. 原位水热合成Ce(Ⅳ)-X分子筛及对噻吩的吸附性能[J]. 燃料化学学报, 2012, 40(12): 1480-1486.(SUN Xia,WANG Xue-song,LI Jian-sheng. In situ hydrothermal synthesis of cerium-incorporated X zeolites and their performance in thiophene adsorption[J]. J Fuel Chem Technol, 2012, 40(12): 1480-1486.)

HERNáNDEZ-MALDONADO A J, YANG R T, CANNELLA W. Desulfurization of commercial jet fuels by adsorption via π-Complexation with vapor phase ion exchanged Cu(I)-Y zeolites[J]. Ind Eng Chem Res, 2004, 43(19): 6142-6149.

YANG X, ERICKSON L E, HOHN K L. Sol-Gel Cu-Al₂O₃ Adsorbents for selective adsorption of thiophene out of hydrocarbon[J]. Ind Eng Chem Res, 2006, 45(18): 6169-6174.

SHAO X C, DUAN L H, WU Y Y, QIN Y C, YU W G, WANG Y, LI H L, SUN Z L, SONG L J. Effect of surface acidity of CuO-SBA-15 on adsorptive desulfurization of fuel oils[J]. Acta Phys-Chim Sin, 2012, 28(6): 1467-1473.

李文秀, 崔安磊, 范俊刚, 孙向乐, 张志刚. 载铜球形活性炭的制备及其吸附脱硫性能的研究[J]. 燃料化学学报, 2013, 41(5): 613-618.(LI Wen-xiu, CUI An-lei, FAN Jun-gang, SUN Xiang-le, ZHANG Zhi-gang. Synthesis of spherical activated carbon supported copper catalyst and its performance for adsorptive desulfudzation[J]. J Fuel Chem Technol, 2013, 41(5): 613-618.)

HERNÁNDEZ-MALDONADO A J, YANG R T. Desulfurization of liquid fuels by adsorption via π complexation with Cu(I)-Y and Ag-Y zeolites[J]. Ind Eng Chem Res, 2002, 42(1): 123-129.

CHEN H, WANG Y, 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.

NAIR S, TATARCHUK B J. Supported silver adsorbents for selective removal of sulfur species from hydrocarbon fuels[J]. Fuel, 2010, 89(11): 3218-3225.

HUSSAIN S A H M, TATARCHUK B J. Adsorptive desulfurization of jet and diesel fuels using Ag/TiO_x-Al₂O₃ and Ag/TiO_x-SiO₂ adsorbents[J]. Fuel, 2013, 107: 465-473.

WANG Y, YANG R T, HEINZEL J M. Desulfurization of jet fuel by -complexation adsorption with metal halides supported on MCM-41 and SBA-15 mesoporous materials[J]. Chem Eng Sci, 2008, 63(2): 356-365.

XIAO J, SONG C, MA X, LI Z. Effects of aromatics, diesel additives, nitrogen compounds, and moisture on adsorptive desulfurization of diesel fuel over activated carbon[J]. Ind Eng Chem Res, 2012, 51(8): 3436-3443.

HUSSAIN S A H M, TATARCHUK B J. Mechanism of hydrocarbon fuel desulfurization using Ag/TiO₂-Al₂O₃ adsorbent[J]. Fuel Process Technol, 2014, 126: 233-242.

SHEN Y, XU X, LI P. A novel potential adsorbent for ultra deep desulfurization of jet fuels at room temperature[J]. RSC Adv, 2012, 2(15): 6155.

PARK S J, KIM S M, WOO M H, BAE J W, JUN K W, HA K S. Effects of titanium impurity on alumina surface for the activity of Co/Ti-Al₂O₃ Fischer-Tropsch catalyst[J]. Appl Catal A: Gen, 2012, 419-420: 148-155.

DE RESENDE N S, EON J G, SCHMAL M. Pt-TiO₂-γAl₂O₃ catalyst: I. Dispersion of platinum on alumina-grafted titanium oxide[J]. J Catal, 1999, 183(1): 6-13.

李文生, 尹双凤, 代威力, 徐柏庆, 周小平. 经高温活化焙烧的B₂O₃/ZrO₂催化剂的织构/结构和表面酸性[J]. 分子催化, 2007, 21(4): 308-314.(LI Wen-sheng, YIN Shuang-feng, DAI Wei-li, XU Bo-qing, ZHOU Xiao-ping. The texture, structure and surface acidity of B₂O₃/ZrO₂ solid acid catalyst calcined at 700℃[J]. J Mol Catal (China), 2007, 21(4): 308-314.)

于琴琴, 刘彤, 王卉, 肖丽萍, 陈敏, 蒋晓原, 郑小明. 低温等离子体协助B₂O₃/γ-Al₂O₃选择催化还原NO[J]. 催化学报, 2012, 33(5): 783-789.(YU Qin-qin, LIU Tong, WANG Hui, XIAO Li-ping, CHEN Min, JIANG Xiao-yuan, ZHENG Xiao-ming. Cold plasma-assisted selective catalytic reduction of NO over B₂O₃/γ-Al₂O₃[J]. Chin J Catal, 2012, 33(5): 783-789.)

PÉREZ-MARTÍNEZ D J, ELOY P, GAIGNEAUX E M, GIRALDO S A, CENTENO A. Study of the selectivity in FCC naphtha hydrotreating by modifying the acid-base balance of CoMo/γ- Al₂O₃ catalysts[J]. Appl Catal A: Gen, 2010, 390(1/2): 59-70.

SING K S W, EVERETT D H, HAUL R A W, MOSCOU L, PIEROTTI R A, ROUQUEROL J, SIEMIENIEWSKA T. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984)[J]. Pure Appl Chem, 1985, 57(4): 603-619.

USMAN, KUBOTA T, ARAKI Y, ISHIDA K, OKAMOTO Y. The effect of boron addition on the hydrodesulfurization activity of MoS₂/Al₂O₃ and Co-MoS₂/Al₂O₃ catalysts[J]. J Catal, 2004, 227(2): 523-529.

BAUTISTA F M, CAMPELO J M, GARCIA A, LUNA D, MARINAS J M, MORENO M C, ROMERO A A. Acidity and catalytic activity of AlPO₄-B₂O₃ and Al₂O₃-B₂O₃ (5~30% B₂O₃) systems prepared by impregnation[J]. Appl Catal A: Gen, 1998, 170(1): 159-168.

BAUTISTA F M, CAMPELO J M, GARCIA A, LUNA D, MARINAS J M., MORENO M C, ROMERO A A, NAVIO J A, MACIAS M. Structural and textural characterization of AlPO₄-B₂O₃ and Al₂O₃-B₂O₃ (5~30% B₂O₃) systems obtained by boric acid impregnation[J]. J Catal, 1998, 173(2): 333-344.

SAIH Y, SEGAWA K. Catalytic activity of CoMo catalysts supported on boron-modified alumina for the hydrodesulphurization of dibenzothiophene and 4,6-dimethyldibenzothiophene[J]. Appl Catal A: Gen, 2009, 353(2): 258-265.

SATO S, KUROKI M, SODESAWA T, NOZAKT F, MACIEL G E. Surface structure and acidity of alumina-boria catalysts[J]. J Mol Catal A: Chem, 1995, 104(2): 171-177.

PEIL K P, GALYA L G, MARCELIN G. Acid and catalytic properties of nonstoichiometric aluminum borates[J]. J Catal, 1989, 115(2): 441-451.

EFFENBERGER H, LENGAUER C L, PARTHÉE. Trigonal B₂O₃ with higher space-group symmetry: Results of a reevaluation[J]. Monatshefte für Chemie, 2001, 132(12): 1515-1517.

施引文献

资源附件(0)

访问统计