Citation: WANG Si-hua, ZU Yun, QIN Yu-cai, ZHANG Xiao-tong, SONG Li-juan. Fabrication of effective desulfurization species active sites in the CeY zeolites and the adsorption desulfurization mechanisms[J]. Journal of Fuel Chemistry and Technology, ;2020, 48(1): 52-62. shu

Fabrication of effective desulfurization species active sites in the CeY zeolites and the adsorption desulfurization mechanisms

WANG Si-hua ¹ ,
ZU Yun ^1,2 ,
QIN Yu-cai ¹ ,
ZHANG Xiao-tong ¹ ,
SONG Li-juan ^1,2,,

1.
Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning Shihua University, Fushun 113001, China
2.
College of Chemistry and Chemical Engineering, China University of Petroleum(East China), Qingdao 266555, China

Corresponding author: SONG Li-juan, lsong56@263.net
Received Date: 19 August 2019
Revised Date: 28 October 2019

Fund Project: the National Natural Science Foundation of China 21376114the National Natural Science Foundation of China U1662135The project was supported by the National Natural Science Foundation of China (U1662135, 21376114)

Figures(11)

A series of CeY zeolites with different cerium loadings and calcined at different temperatures were prepared and used as the adsorbent for the desulfurization of thiophene containing model oil. The CeY zeolites were characterized by XRD, N₂ sorption, FT-IR spectroscopy and GC-SCD and GC-MSD techniques. The effects of aromatics and olefins on the adsorption desulfurization performance were investigated and the active species and reaction mechanism for the adsorption desulfurization on CeY zeolites were probed. The results indicate that the CeY zeolite calcined at 150 ℃ is provided with a large number of Brönsted acid sites and hydroxylated cerium species in the supercages, which can synergistically promote the thiophene oligomerization and then enhance the sulfur breakthrough adsorption capacity (18.45 mg (S)/g). However, a further increase in the calcination temperature and cerium loading may greatly reduce the number of active sites for the adsorption desulfurization and suppress the thiophene oligomerization reaction, leading to a significant decrease in the sulfur breakthrough adsorption capacity (4.03 mg (S)/g). For the thiophene model oils containing low concentration of 1-hexene (< 1.0%) or benzene (< 0.1%), the CeY-12.3-150 zeolite (with a cerium loading of 12.3% and calcined at 150 ℃) also exhibits a relatively high sulfur breakthrough adsorption capacity. However, a further increase in the content of 1-hexene or benzene in the feed may lead to a sharp decrease in the sulfur breakthrough adsorption capacity, due to the alkylation of thiophene and the adsorption mode of "S-H" bonding.
- CeY zeolites,
- effective active sites,
- Ce loadings,
- calcination temperatures,
- adsorption desulfurization
1. [1]
  YANG Yong-tan, YANG Hai-ying, ZONG Bao-ning, LU Wan-zhen. Determination and distribution of sulfur compounds in gasoline by gas chromatography-atomic emission detector[J]. Chin J Anal Chem, 2003,31(10):1153-1158. doi: 10.3321/j.issn:0253-3820.2003.10.001
2. [2]
  YANG Yong-tan, WANG Zheng. Determination and distribution of sulfur compounds in coked gasoline by gas chromatography-sulfur chemiluminescence detection[J]. Chin J Chromatogr, 2007,25(3):384-388. doi: 10.3321/j.issn:1000-8713.2007.03.021
3. [3]
  ZHU LI-jun, XIA Dao-hong, XIANG Yu-zhi, ZHOU Yu-lu. Composition analysis of sulfur compounds in hydrocoking gasoline[J]. Chem Eng Oil Gas, 2009,38(6):494-497. doi: 10.3969/j.issn.1007-3426.2009.06.009
4. [4]
  SONG C S. An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel[J]. Catal Today, 2003,86(1):211-263.
5. [5]
  DEHGHAN R, ANBIA M. Zeolites for adsorptive desulfurization from fuels:A review[J]. Fuel Process Technol, 2017,167:99-116. doi: 10.1016/j.fuproc.2017.06.015
6. [6]
  TAN P, JIANG Y, SUN L B, LIU X Q, ALBAHILY K, RAVON U, VINU A. Design and fabrication of nanoporous adsorbents for the removal of aromatic sulfur compounds[J]. J Mater Chem A, 2018,6(47):23978-24012. doi: 10.1039/C8TA09184F
7. [7]
  VELU S, MA X L, SONG C S. Selective adsorption for removing sulfur from jet fuel over zeolite-based adsorbents[J]. Ind Eng Chem Res, 2003,42(21):5293-5304. doi: 10.1021/ie020995p
8. [8]
  LIN L G, ZHANG Y Z, ZHANG H Y, LU F W. Adsorption and solvent desorption behavior of ion-exchanged modified Y zeolites for sulfur removal and for fuel cell applications[J]. J Colloid Interf Sci, 2011,360(2):753-759. doi: 10.1016/j.jcis.2011.04.075
9. [9]
  WANG H G, SONG L J, JIANG H, XU J, JIN L L, ZHANG X T, SUN Z L. Effects of olefin on adsorptive desulfurization of gasoline over Ce(Ⅳ)Y zeolites[J]. Fuel Process Technol, 2009,90(6):835-838. doi: 10.1016/j.fuproc.2009.03.004
10. [10]
  DUAN L H, GAO X H, MENG X H, ZHANG H T, WANG Q, QIN Y C, ZHANG X T, SONG L J. Adsorption, co-adsorption, and reactions of sulfur compounds, aromatics, olefins over Ce-exchanged Y zeolite[J]. J Phys Chem C, 2012,116(49):25748-25756. doi: 10.1021/jp303040m
11. [11]
  QIN Y C, MO Z S, YU W G, DONG S W, DUAN L H, GAO X H, SONG L J. Adsorption behaviors of thiophene, benzene, and cyclohexene on FAU zeolites:Comparison of CeY obtained by liquid-, and solid-state ion exchange[J]. Appl Surf Sci, 2014,292:5-15. doi: 10.1016/j.apsusc.2013.11.036
12. [12]
  ZU Y, ZHANG C, QIN Y C, ZHANG X T, ZHANG L, LIU H H, GAO X H, SONG L J. Ultra-deep adsorptive removal of thiophenic sulfur compounds from FCC gasoline over the specific active sites of CeHY zeolite[J]. J Energy Chem, 2019,39:256-267. doi: 10.1016/j.jechem.2019.04.010
13. [13]
  ZU Y, HUI Y, QIN Y C, ZHANG L, LIU H H, ZHANG X T, GUO Z S, SONG L J, GAO X H. Facile Fabrication of effective cerium (Ⅲ) hydroxylated species as adsorption active sites in CeY zeolite adsorbents towards ultra-deep desulfurization[J]. Chem Eng J, 2019,375122014. doi: 10.1016/j.cej.2019.122014
14. [14]
  SHI Y C, ZHANG W., ZHANG H X, TIAN F P, JIA C Y, CHEN Y Y. Effect of cyclohexene on thiophene adsorption over NaY and LaNaY zeolites[J]. Fuel Process Technol, 2013,110:24-32. doi: 10.1016/j.fuproc.2013.01.008
15. [15]
  SHI Y C, YANF X J, TIAN F P, JIA C Y, CHEN Y Y. Effects of toluene on thiophene adsorption over NaY and Ce(Ⅳ)Y zeolites[J]. J Nat Gas Chem, 2012,21(4):421-425. doi: 10.1016/S1003-9953(11)60385-X
16. [16]
  WANG Xiang-sheng, LUO Guo-hua. The removal of thiophene from coking benzene over HZSM-5 zeolite[J]. Chin J Catal, 1996,17(6):530-534.
17. [17]
  WANG J, XU F, XIE W J, MEI J Z, ZHANG Q Z, CAI J, CAI W M. The enhanced adsorption of dibenzothiophene onto cerium/nickel-exchanged zeolite Y[J]. J Hazard Mater, 2009,163(2/3):538-543.
18. [18]
  QIN Yu-cai, GAO Xiong-hou, DUAN Lin-hai, FAN Yue-chao, YU Wen-guang, ZHANG Hai-tao, SONG Li-juan. Effects on adsorption desulfurization of CeY zeolites:Acid catalysis and competitive adsorption[J]. Acta Phys-Chim Sin, 2014,30(3):544-550.
19. [19]
  LI J C, ZENG P H, ZHAO L, REN S Y, GUO Q X, ZHANG H J, WANG B J, LIU H H, PANG X M, GAO X H, SHEN B J. Tuning of acidity in CeY catalytic cracking catalysts by controlling the migration of Ce in the ion exchange step through valence changes[J]. J Catal, 2015,329:441-448. doi: 10.1016/j.jcat.2015.06.012
20. [20]
  LIAO J J, BAO W R, CHANG L P. An approach to study the desulfurization mechanism and the competitive behavior from aromatics:A case study on CeY zeolite[J]. Fuel Process Technol, 2015,140:104-112. doi: 10.1016/j.fuproc.2015.08.036
21. [21]
  LIAO J J, WANG Y, CHANG L P, BAO W R. A process for desulfurization of coking benzene by a two-step method with reuse of sorbent/thiophene and its key procedures[J]. Green Chem, 2015,17(5):3164-3175. doi: 10.1039/C4GC02505A
22. [22]
  DU X H, GAO X H, Zhang H T, LI X L, LIU P S. Effect of cation location on the hydrothermal stability of rare earth-exchanged Y zeolites[J]. Catal Commun, 2013,35:17-22. doi: 10.1016/j.catcom.2013.02.010
23. [23]
  KIM C W, KANG H C, HEO N H, SEFF K. Encapsulating photoluminescent materials in zeolites. Ⅱ. Crystal structure of fully dehydrated Ce₂₁H₄₆O₁₈-Y (Si/Al=1.69) containing Ce₄O₄⁴⁺, CeOH²⁺, Ce³⁺, and H⁺[J]. J Phys Chem C, 2015,119(43):24501-24511. doi: 10.1021/acs.jpcc.5b08373
24. [24]
  LEE E F T, REES L V C. Calcination of cerium (Ⅲ) exchanged Y zeolite[J]. Zeolites, 1987,7(5):446-450. doi: 10.1016/0144-2449(87)90013-3
25. [25]
  NERJ J G, MASCARENHAS Y P, BONAGAMBA T J, Mello N C, SOUZA-AGUIAR E F. Location of cerium and lanthanum cations in CeNaY and LaNaY after calcination[J]. Zeolites, 1997,18:44-49. doi: 10.1016/S0144-2449(96)00094-2
26. [26]
  BOLTON A P. The nature of rare-earth exchanged Y zeolites[J]. J Catal, 1971,22(1):9-15. doi: 10.1016/0021-9517(71)90259-4
27. [27]
  WANG N N, WANG Y, CHENG H F, FU M E, TAO Z, WU W Z. Relationship between two characteristic diffractions and the status of cationic lanthanum species in zeolite LaNaY[J]. J Porous Mater, 2013,20(5):1371-1378. doi: 10.1007/s10934-013-9723-1
28. [28]
  QIU L M, FU Y, ZHENG J Y, HUANG N G, LU L J, GAO X Z, XIN M D, LUO Y B, SHI Y Q, XU G T. Investigation on the cation location, structure and performances of rare earth-exchanged Y zeolite[J]. J Rare Earths, 2017,35(7):658-666. doi: 10.1016/S1002-0721(17)60960-8
29. [29]
  WANG M, JAEGERS N R, LEE M S, WAN C, HU J Z, SHI H, MEI D H, BURTON S D, CAMAIONI D M, GUTIERREZ O Y, GLEZAKOU V A, ROUSSEAU R, WANG Y, LERCHER J A. Genesis and stability of hydronium ions in zeolite channels[J]. J Am Chem Soc, 2019,141(8):3444-3455. doi: 10.1021/jacs.8b07969
30. [30]
  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]. J Fuel Chem Technol, 2015,43(7):862-869. doi: 10.3969/j.issn.0253-2409.2015.07.012
1. [1]
  Qin ZHU , Jiao MA , Zhihui QIAN , Yuxu LUO , Yujiao GUO , Mingwu XIANG , Xiaofang LIU , Ping NING , Junming GUO . Morphological evolution and electrochemical properties of cathode material LiAl_0.08Mn_1.92O₄ single crystal particles. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1549-1562. doi: 10.11862/CJIC.20240022
2. [2]
  Jiali CHEN , Guoxiang ZHAO , Yayu YAN , Wanting XIA , Qiaohong LI , Jian ZHANG . Machine learning exploring the adsorption of electronic gases on zeolite molecular sieves. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 155-164. doi: 10.11862/CJIC.20240408
3. [3]
  Ping LI , Geng TAN , Xin HUANG , Fuxing SUN , Jiangtao JIA , Guangshan ZHU , Jia LIU , Jiyang LI . Green synthesis of metal-organic frameworks with open metal sites for efficient ammonia capture. Chinese Journal of Inorganic Chemistry, 2025, 41(10): 2063-2068. doi: 10.11862/CJIC.20250020
4. [4]
  Yuhao SUN , Qingzhe DONG , Lei ZHAO , Xiaodan JIANG , Hailing GUO , Xianglong MENG , Yongmei GUO . Synthesis and antibacterial properties of silver-loaded sod-based zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 761-770. doi: 10.11862/CJIC.20230169
5. [5]
  Yiping HUANG , Liqin TANG , Yufan JI , Cheng CHEN , Shuangtao LI , Jingjing HUANG , Xuechao GAO , Xuehong GU . Hollow fiber NaA zeolite membrane for deep dehydration of ethanol solvent by vapor permeation. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 225-234. doi: 10.11862/CJIC.20240224
6. [6]
  Pei Li , Yuenan Zheng , Zhankai Liu , An-Hui Lu . Boron-Containing MFI Zeolite: Microstructure Control and Its Performance of Propane Oxidative Dehydrogenation. Acta Physico-Chimica Sinica, 2025, 41(4): 100034-0. doi: 10.3866/PKU.WHXB202406012
7. [7]
  Qinhui Guan , Yuhao Guo , Na Li , Jing Li , Tingjiang Yan . Molecular sieve-mediated indium oxide catalysts for enhancing photocatalytic CO₂ hydrogenation. Acta Physico-Chimica Sinica, 2025, 41(11): 100133-0. doi: 10.1016/j.actphy.2025.100133
8. [8]
  Yufang GAO , Nan HOU , Yaning LIANG , Ning LI , Yanting ZHANG , Zelong LI , Xiaofeng LI . Nano-thin layer MCM-22 zeolite: Synthesis and catalytic properties of trimethylbenzene isomerization reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1079-1087. doi: 10.11862/CJIC.20240036
9. [9]
  Shanghua Li , Malin Li , Xiwen Chi , Xin Yin , Zhaodi Luo , Jihong Yu . High-Stable Aqueous Zinc Metal Anodes Enabled by an Oriented ZnQ Zeolite Protective Layer with Facile Ion Migration Kinetics. Acta Physico-Chimica Sinica, 2025, 41(1): 100003-0. doi: 10.3866/PKU.WHXB202309003
10. [10]
  Yi RU , Tao MENG , Zhaoteng XUE , Dongsen MAO . Synergistic catalysis of Al distribution and pore structure in ZSM-5 zeolite for bioethanol-to-propylene. Chinese Journal of Inorganic Chemistry, 2026, 42(2): 247-262. doi: 10.11862/CJIC.20250255
11. [11]
  Weina Li , Hongbo Liu , Xuemei Tian . Reform of Blended Teaching in Inorganic Chemistry Courses Based on Effective Teaching. University Chemistry, 2026, 41(2): 36-44. doi: 10.12461/PKU.DXHX202502040
12. [12]
  Shunü Peng , Huamin Li , Zhaobin Chen , Yiru Wang . Simultaneous Application of Multiple Quantitative Analysis Methods in Gas Chromatography for the Determination of Active Ingredients in Traditional Chinese Medicine Preparations. University Chemistry, 2025, 40(10): 243-249. doi: 10.12461/PKU.DXHX202412043
13. [13]
  Geshan Zhang , Haodong Tang , Zongjian Liu , Feng Feng . Application of the BOPPPS Effective Teaching Model in Bilingual Physical Chemistry Instruction: A Case on Colligative Properties of Dilute Solutions. University Chemistry, 2025, 40(11): 376-381. doi: 10.12461/PKU.DXHX202412127
14. [14]
  Shiqian WEI , Xinyu TIAN , Hong LIU , Maoxia CHEN , Fan TANG , Qiang FAN , Weifeng FAN , Yu HU . Oxygen reduction reaction/oxygen evolution reaction catalytic performances of different active sites on nitrogen-doped graphene loaded with iron single atoms. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1776-1788. doi: 10.11862/CJIC.20250102
15. [15]
  Fei Xie , Chengcheng Yuan , Haiyan Tan , Alireza Z. Moshfegh , Bicheng Zhu , Jiaguo Yu . d-Band Center Regulated O₂ Adsorption on Transition Metal Single Atoms Loaded COF: A DFT Study. Acta Physico-Chimica Sinica, 2024, 40(11): 2407013-0. doi: 10.3866/PKU.WHXB202407013
16. [16]
  Xueqi Yang , Juntao Zhao , Jiawei Ye , Desen Zhou , Tingmin Di , Jun Zhang . 调节NNU-55(Fe)的d带中心以增强CO₂吸附和光催化活性. Acta Physico-Chimica Sinica, 2025, 41(7): 100074-0. doi: 10.1016/j.actphy.2025.100074
17. [17]
  Siyu ZU , Jianhui LUO , Qingfa SU , Jianchun WANG , Yizhen CHENG , Zhihang GUO , Jinhong BI . Preparation and degrading formaldehyde properties of TiO₂/flue gas desulfurization ash photocatalytic composites. Chinese Journal of Inorganic Chemistry, 2026, 42(7): 1437-1452. doi: 10.11862/CJIC.20260043
18. [18]
  Jilei LIANG , Mengmeng WU , Lü QI , Yunqi LIU , Chenguang LIU . In-situ preparation of mesoporous carbon-encapsulated NiMoS hydrodesulfurization catalyst. Chinese Journal of Inorganic Chemistry, 2026, 42(10): 2127-2137. doi: 10.11862/CJIC.20260127
19. [19]
  Youlin SI , Shuquan SUN , Junsong YANG , Zijun BIE , Yan CHEN , Li LUO . Synthesis and adsorption properties of Zn(Ⅱ) metal-organic framework based on 3, 3', 5, 5'-tetraimidazolyl biphenyl ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1755-1762. doi: 10.11862/CJIC.20240061
20. [20]
  Wenjuan SHI , Yuke LU , Xiuyuan LI , Lei HOU , Yaoyu WANG . Mg(Ⅱ) metal-organic frameworks based on biphenyltetracarboxylic acid: Synthesis and CO₂ adsorption and catalytic conversion performance. Chinese Journal of Inorganic Chemistry, 2025, 41(12): 2455-2463. doi: 10.11862/CJIC.20250220

Get Citation

PDF

XML

Metrics

PDF Downloads(9)
Abstract views(4151)
HTML views(652)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142