Mechanisms of thiophene conversion over the modified Y zeolites under catalytic cracking conditions

ZU Yun; QIN Yu-cai; GAO Xiong-hou; MO Zhou-sheng; ZHANG Lei; ZHANG Xiao-tong; SONG Li-juan

Volume 43 Issue 07

Jul. 2015

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Article Navigation > Journal of Fuel Chemistry and Technology > 2015 > 43(07): 862-869

ZU Yun, QIN Yu-cai, GAO Xiong-hou, MO Zhou-sheng, ZHANG Lei, ZHANG Xiao-tong, SONG Li-juan. Mechanisms of thiophene conversion over the modified Y zeolites under catalytic cracking conditions[J]. Journal of Fuel Chemistry and Technology, 2015, 43(07): 862-869.

Citation:

ZU Yun, QIN Yu-cai, GAO Xiong-hou, MO Zhou-sheng, ZHANG Lei, ZHANG Xiao-tong, SONG Li-juan. Mechanisms of thiophene conversion over the modified Y zeolites under catalytic cracking conditions[J]. Journal of Fuel Chemistry and Technology, 2015, 43(07): 862-869.

Citation:

ZU Yun, QIN Yu-cai, GAO Xiong-hou, MO Zhou-sheng, ZHANG Lei, ZHANG Xiao-tong, SONG Li-juan. Mechanisms of thiophene conversion over the modified Y zeolites under catalytic cracking conditions[J]. Journal of Fuel Chemistry and Technology, 2015, 43(07): 862-869.

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Mechanisms of thiophene conversion over the modified Y zeolites under catalytic cracking conditions

1.
Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning Province, Liaoning Shihua University, Fushun 113001, China;
2.
Lanzhou Petrochemical Research Center, Petrochemical Research Institute, Petro China Company Limited, Lanzhou 730060, China;
3.
College of Chemistry & Chemical Engineering, China University of Petroleum (East China), Qingdao 266555, China

Received Date: 2015-05-30
Rev Recd Date: 2015-06-30
Publish Date: 2015-07-30

Abstract

Abstract

The mechanisms of thiophene conversion over various Y zeolites, viz., HY, Ni-modified NiY and rare earths metal-modified REY, were investigated under catalytic cracking conditions in a fix-bed reactor. The final products of thiophene conversion were analyzed by using a gas chromatography with flame ionization detector (GC-FID), a gas chromatography with sulfur chemiluminescence detector (GC-SCD) and an in situ infrared spectrometer. The results were then correlated with the acidic properties of the zeolites, which indicated that the mechanisms of thiophene interacting with these Y zeolites are dependent on the state and occurrence mode of the modified metallic cation and/or the extraframework aluminum species, which can modulate the Brnsted and Lewis acidities in the zeolites. For the NiY zeolites, the thiophene molecules are mainly adsorbed on the Lewis acidic sites associated with the NiOH⁺ species; the species of Ni₄AlO₄³⁺ and those generated from the Ni²⁺ and the extraframework aluminum can weaken the Brnsted acidity and then reduce the cracking activity of the zeolite. Polymerization and cracking reactions are observed for the conversion of thiophene over the HY and REY zeolites. For the HY zeolites, 2,2',5',2''-terthiophene can be found, which is ascribed to the Brnsted acid sites adjacent to extraframework aluminum species (AlO⁺ or so on); some subsequent reactions of hydrogen transfer and cracking can also be detected. Over the REY zeolite, hydrogen transfer and cracking reactions of thiophene oligomer species derived on the Brnsted acid sites adjacent to extraframework aluminum species (Al(OH)₂⁺, Al(OH)²⁺ and so on) can be promoted by the Lewis acid center related to the RE species.
- thiophene,
- modified Y zeolite,
- catalytic cracking,
- acidity,
- reaction mechanism

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References(25)

References

殷长龙, 夏道宏. 催化裂化汽油中类型硫含量分布[J]. 燃料化学学报, 2001, 29(3): 256-258. (YIN Chang-long, XIA Dao-hong. Distribution of sulfur compounds in the full-range FCC and RFCC gasoline[J]. J Fuel Chem Technol, 2001, 29(3): 256-258.)

WHITING G T, MEIRER F, VALENCIA D, WECKHUYSEN BERT M. Selective staining of Brönsted acidity in zeolite ZSM-5-based catalyst extrudates using thiophene as a probe[J]. Phys Chem Chem Phys, 2014, 16(39): 21531-21542.

JAIMES L, DE LASA H. Catalytic conversion of thiophene under mild conditions over a ZSM-5 catalyst. A kinetic model[J]. Ind Eng Chem Res, 2009, 48(16): 7505-7516.

Yu S Y, WAKU T, IGLESIA E. Catalytic desulfurization of thiophene on H-ZSM5 using alkanes as co-reactants[J]. Appl Catal A: Gen, 2003, 242(1): 111-121.

POTAPENKO O V, DORONIN V P, SOROKINA T P. Transformations of thiophene compounds under catalytic cracking conditions[J]. Appl Catal B: Environ, 2012, 117: 177-184.

山红红, 李春义, 赵辉, 杨朝合, 张建芳. 噻吩在USY沸石上的裂化脱硫反应机理探索[J]. 燃烧化学报, 2001, 29(6): 481-485. (SHAN Hong-hong, LI Chun-yi, ZHAO Hui, YANG Chao-he, ZHANG Jian-fang. Discussions on the mechanism of thiophene cracking over a USY zeolite[J]. J Fuel Chem Technol, 2001, 29(6): 481-485.)

LI B, GUO W, YUAN S, HU J, WANG J, JIAO H. A theoretical investigation into the thiophene-cracking mechanism over pure Brönsted acidic zeolites[J]. J Catal, 2008, 253(1): 212-220.

PANG X, ZHANG L, SUN S, LIU T, GAO X. Effects of metal modifications of Y zeolites on sulfur reduction performance in fluid catalytic cracking process[J]. Catal Today, 2007, 125(3): 173-177.

秦玉才, 高雄厚, 裴婷婷, 郑兰歌, 王琳, 莫周胜, 宋丽娟. 噻吩在稀土离子改性 Y 型分子筛上吸附与催化转化研究[J]. 燃料化学学报, 2013, 41(7): 889-896. (QIN Yu-cai, GAO Xiong-hou, PEI Ting-ting, ZHENG Lan-ge, WANG Lin, MO Zhou-sheng, SONG Li-juan. Adsorption and catalytic conversion of thiophene on Y-type zeolites modified with rare-earth metal ions[J]. J Fuel Chem Technol, 2013, 41(7): 889-896.)

张畅, 秦玉才, 高雄厚, 张海涛, 莫周胜, 初春雨, 张晓彤, 宋丽娟. Ce 改性对 Y 型分子筛酸性及其催化转化性能的调变机制[J]. 物理化学学报, 2015, 31(2): 344-352. (ZHANG Chang, QIN Yu-cai, GAO Xiong-hou, ZHANG Hai-tao, MO Zhou-sheng, CHU Chun-yu, ZHANG Xiao-tong, SONG Li-juan. Modulation mechanisms of the acidity and catalytic properties of Y zeolites modified by cerium cations[J]. Acta Phys Chim Sin, 2015, 31(2): 344-352.)

NIWA M, SUZUKI K, ISAMOTO K. Identification and measurements of strong brφnsted acid site in ultrastable Y (USY) zeolite[J]. J Phys Chem B, 2006, 110(1): 264-269.

DATKA J, GIL B, BARAN P. IR study of heterogeneity of OH groups in zeolite HY-splitting of OH and OD bands[J]. J Mol Struct, 2003, 645(1): 45-49.

ALMUTAIRI S M T, MEZARI B, FILONENKO G A. Influence of extraframework aluminum on the Brφnsted acidity and catalytic reactivity of faujasite zeolite[J]. Chem Cat Chem, 2013, 5(2): 452-466.

LI S, ZHENG A, SU Y, ZHANG H, CHEN L, YANG J, YE C, DENG F. Brφnsted/Lewis acid synergy in dealuminated HY zeolite: A combined solid-state NMR and theoretical calculation study[J]. J Am Chem Soc, 2007, 129(36): 11161-11171.

LI S, ZHENG A, SU Y, FANG H, SHEN W, YU Z, CHEN L, DENG F. Extra-framework aluminium species in hydrated faujasite zeolite as investigated by two-dimensional solid-state NMR spectroscopy and theoretical calculations[J]. Phys Chem Chem Phys, 2010, 12(15): 3895-3903.

WARD J W. Spectroscopic study of the surface of zeolite Y. II. Infrared spectra of structural hydroxyl groups and adsorbed water on alkali, alkaline earth, and rare earth ion-exchanged zeolites[J]. J Phys Chem, 1968, 72(12): 4211-4223.

WARD J W. Spectroscopic study of the surface of zeolite Y. Part 4.—Infrared studies of structural hydroxyl groups and adsorbed water on some transition metal ion-exchanged zeolites[J]. Trans Faraday Soc, 1971, 67: 1489-1499.

宋丽娟, 潘明雪, 秦玉才, 鞠秀芳, 段林海, 陈晓陆. NiY 分子筛选择性吸附脱硫性能及作用机理[J]. 高等学校化学学报, 2011, 32(3): 787-792. (SONG Li-juan, PAN Ming-xue, QIN Yu-cai, JU Xiu-fang, DUAN Lin-hai, CHEN Xiao-lu. Selective adsorption desulfurization performance and adsorptive mechanisms of NiY zeolites[J]. Chem J Chin Univ, 2011, 32(3): 787-792.)

董世伟, 秦玉才, 阮艳军, 王源, 于文广, 张磊, 范跃超, 宋丽娟. 改性 Y 型分子筛对 FCC 汽油脱硫性能的研究[J]. 燃料化学学报, 2013, 41(3): 341-346. (DONG Shi-wei, QIN Yu-cai, RUAN Yan-jun, WANG Yuan, YU Wen-guang, ZHANG Lei, FAN Yue-chao, SONG Li-juan. Performance of adsorptive desulfurization for FCC gasoline over modified Y zeolites[J]. J Fuel Chem Technol, 2013, 41(3): 341-346.)

MIGDAL M A, MIKULI E, DZIEMBAJ R, MAJDA D, HETMANCZYK L. Thermal decomposition of (NO₃)₂, (NO₃)₂ and (NO₃)₂[J]. Thermochim Acta, 2004, 419(1): 223-229.

李宣文, 佘励勤, 刘兴云. LaHY 表面与NaOH 的作用及酸性表面性质研究[J].催化学报, 1983, 4(1): 43-50. (LI Xuan-wen, SHE Li-qin, LIU Xing-yun. Studies on the interaction between NaOH and acidic sites on LaHY surface and the nature of acidic surface of LaHY[J]. Chin J Catal, 1983, 4(1): 43-50.)

SEO S M, PARK M, CHUNG D Y, LIM W T. Preparation of excessively Ni²⁺-exchanged zeolite Y (FAU, Si/Al=1.70) and its single-crystal structure[J]. J Porous Mater, 2014, 21(5): 521-530.

NIWA M, SUZUKI K, ISAMOTO K, KATADA N. Identification and measurements of strong brφnsted acid site in ultrastable Y (USY) zeolite[J]. J Phys Chem B, 2006, 110(1): 264-269.

EISENBACH D, GALLEI E. Infrared spectroscopic investigations relating to coke formation on zeolites: I. Adsorption of hexene-1 and n-hexane on zeolites of type Y[J]. J Catal, 1979, 56(3): 377-389.

SHI Y, ZHANG W, ZHANG H, TIAN F, JIA C, CHEN Y. Effect of cyclohexene on thiophene adsorption over NaY and LaNaY zeolites[J]. Fuel Process Technol, 2013, 110: 24-32.

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