Abstract
This study offers an investigation of the catalytic activity of TiO2/SiO2 during oxidative desulfurization (ODS) of a model fuel that includes dibenzothiophene (DBT), using hydrogen peroxide (H2O2) as a green oxidant in the absence of UV irradiation. For the first time, though a novel and simple protocol, TiO2/SiO2 nanohybrid was synthesized using ascorbic acid and glycerol as green complexing and polymerizing agents, respectively. The TiO2/SiO2 catalyst was thoroughly characterized by XRD, FT-IR, nitrogen adsorption-desorption measurements, TEM, FESEM, and TGA. Results revealed a high catalytic oxidative activity for the catalyst in the removal of DBT regarding sulfur removal up to 99.4% within 20 min under optimum reaction conditions. The main factors affecting the ODS process, including catalyst dosage, temperature, O/S molar ratio, and different oxidizing agents, were evaluated to identify optimum conditions. The desulfurization efficiency of the recoverable catalysts showed no loss in activity after four times. The present article suggests a new and green method for the synthesis and characterization of an efficient catalyst (TiO2/SiO2) in deep oxidative desulfurization at 25 °C and removal of refractory organosulfur compounds that yield ultra-low sulfur fuels. Also, it proved to have a much higher catalytic oxidation capacity when compared to pure TiO2.
Similar content being viewed by others
References
Abdelrahman AA, Betiha MA, Rabie AM, Ahmed HS, Elshahat MF (2018) Removal of refractory Organo-sulfur compounds using an efficient and recyclable {Mo132}nanoball supported graphene oxide. J Mol Liq 252:121–132. https://doi.org/10.1016/j.molliq.2017.12.124
Abro R, Gao S, Chen X, Yu G, Abdeltawab AA, Al-Deyab SS (2016) Oxidative desulfurization of gasoline by ionic liquids coupled with extraction by organic solvents. J Braz Chem Soc 27:998–1006. https://doi.org/10.5935/0103-5053.20150355
Alhadhami A, Al-Ghamry MA, Atta AH, El-Shenawy AI, Refat MS, Al Omar MA, Naglah AM (2017) Physicochemical studies on the desulfurization process of organosulfur compounds occur in crude oil by metallo-complexation method. J Mol Liq 231:94–97. https://doi.org/10.1016/j.molliq.2017.01.095
Ahmadpour J, Ahmadi M, Javdani A (2019) Hydrodesulfurization unit for natural gas condensate. J Therm Anal Calorim 135:1943–1949. https://doi.org/10.1007/s10973-018-7512-4
Bascom R, Bromberg PA, Costa DL, Devlin R, Dockery DW, Frampton MW, Lambert W, Samet JM, Speizer FE, Utell M (1996) Health effects of outdoor air pollution. Am J Respir Crit Care Med 153:477–498. https://doi.org/10.1164/ajrccm.153.2.8564086
Bhadra BN, Song JY, Khan NA, Jhung SH (2017) TiO2-containing carbon derived from a metal–organic framework composite: a highly active catalyst for oxidative desulfurization. ACS Appl Mater Interfaces 9:31192–31202. https://doi.org/10.1021/acsami.7b10336
Bhasarkar JB, Dikshit PK, Moholkar VS (2015b) Ultrasound assisted biodesulfurization of liquid fuel using free and immobilized cells of Rhodococcus rhodochrous MTCC 3552: A mechanistic investigation. Bioresour Technol 187:369–378. https://doi.org/10.1016/j.biortech.2015.03.102
Bhasarkar JB, Chakma S, Moholkar VS (2015a) Investigations in physical mechanism of the oxidative desulfurization process assisted simultaneously by phase transfer agent and ultrasound. Ultrason Sonochem 24:98–106. https://doi.org/10.1016/j.ultsonch.0.2014.11.008
Davoodi-Dehaghani F, Vosoughi M, Ziaee AA (2010) Biodesulfurization of dibenzothiophene by a newly isolated Rhodococcus erythropolis strain. Bioresour Technol 101:1102–1105. https://doi.org/10.1016/j.biortech.2009.08.058
Do Duong D (1998) Adsorption Analysis: Equilibria And Kinetics (With CD Containing Computer Matlab Programs). https://doi.org/10.1142/p111.
Gao G, Cheng S, An Y, Si X, Fu X, Liu Y, Zhang H, Wu P, He MY (2010) Oxidative desulfurization of aromatic sulfur compounds over titanosilicates. ChemCatChem 2:459–466. https://doi.org/10.1002/cctc.200900073
Guo X, Bao L, Chang L, Bao W, Liao J (2019) Influence of modifications on the deep desulfurization behavior of NaY and Na13X zeolites in gasoline. Environ Sci Pollut Res 26:1–9. https://doi.org/10.1007/s11356-019-04824-9
Hernández-Maldonado AJ, Yang FH, Qi G, Yang RT (2005) Desulfurization of transportation fuels by π-complexation sorbents: Cu (I)-, Ni (II)-, and Zn (II)-zeolites. Appl Catal B Environ 56:111–126. https://doi.org/10.1016/j.apcatb.2004.06.023
Hou Y, Liu M, Huang Y, Zhao L, Wang J, Cheng Q, Niu Q (2017) Gasoline desulfurization by a TiO2-filled ethyl cellulose pervaporation membrane. J Appl Polym Sci 134. 43409https://doi.org/10.1002/app.43409
Javadli R, De Klerk A (2012) Desulfurization of heavy oil. Appl Petrochem Res 1:3–19. https://doi.org/10.1007/s13203-012-0006-6
Jafarpour M, Rezaeifard A, Ghahramaninezhad M, Feizpour F (2015) Dioxomolybdenum (vi) complex immobilized on ascorbic acid coated TiO2 nanoparticles catalyzed heterogeneous oxidation of olefins and sulfides. Green Chem 17:442–452. https://doi.org/10.1039/C4GC01398K
Jiang X, Li H, Zhu W, He L, Shu H, Lu J (2009) Deep desulfurization of fuels catalyzed by surfactant-type decatungstates using H2O2 as oxidant. Fuel 88:431–436. https://doi.org/10.1016/j.fuel.2008.11.010
Kabala SJ (1989) The economic effects of sulfur dioxide pollution in Poland. Ambio 18:250–251
Kannaiyan D, Kochuveedu ST, Jang YH, Jang YJ, Lee JY, Lee J, Lee J, Kim J, Kim DH (2010) Enhanced photophysical properties of nanopatterned titania nanodots/nanowires upon hybridization with silica via block copolymer templated sol-gel process. Polymers 2:490–504. https://doi.org/10.3390/polym2040490
Kim TW, Kim MJ, Kleitz F, Nair MM, Guillet-Nicolas R, Jeong KE, Chae HJ, Kim CU, Jeong SY (2012) Tailor-made mesoporous Ti-SBA-15 catalysts for oxidative desulfurization of refractory aromatic sulfur compounds in transport fuel. ChemCatChem 4:687–697. https://doi.org/10.1002/cctc.201100417
Kulkarni PS, Afonso CA (2010) Deep desulfurization of diesel fuel using ionic liquids: current status and future challenges. Green Chem 12:1139–1149. https://doi.org/10.1039/C002113J
Li C, Zhang J, Li Z, Yin J, Cui Y, Liu Y, Yang G (2016c) Extraction desulfurization of fuels with ‘metal ions’ based deep eutectic solvents (MDESs). Green Chem 18:3789–3795. https://doi.org/10.1039/C6GC00366D
Li S, Mominou N, Wang Z, Liu L, Wang L (2016b) Ultra-deep desulfurization of gasoline with cuw/tio2–go through photocatalytic oxidation. Energy Fuel 30:962–967. https://doi.org/10.1021/acs.energyfuels.5b02790
Li X, Xu Y, Zhang C, Wang H, Song Y, Zhang W, Li C (2018) H2O2-assisted hydrothermal synthesis of TiO2-SiO2 and its enhanced photocatalytic-adsorptive desulfurization performance for model fuel. Fuel 226:527–535. https://doi.org/10.1016/j.fuel.2018.04.046
Lorençon E, Alves DC, Krambrock K, Ávila ES, Resende RR, Ferlauto AS, Lago RM (2014) Oxidative desulfurization of dibenzothiophene over titanate nanotubes. Fuel 132:53–61. https://doi.org/10.1016/j.fuel.2014.04.020
Miao G, Ye F, Wu L, Ren X, Xiao J, Li Z, Wang H (2015) Selective adsorption of thiophenic compounds from fuel over TiO2/SiO2 under UV-irradiation. J Hazard Mater 300:426–432. https://doi.org/10.1016/j.jhazmat.2015.07.027
Mojaverian Kermani A, Ahmadpour A, Rohani Bastami T, Ghahramaninezhad M (2018) {Mo132} nanoball supported on activated carbon as efficient catalyst for deep oxidative desulfurization of fuels at room temperature. N J Chem 42:12188–12197. https://doi.org/10.1039/c8nj01735b
Mokhtar WNAW, Bakar WAWA, Ali R, Kadir AAA (2015) Catalytic oxidative desulfurization of diesel oil by Co/Mn/Al2O3 catalysts—tert-butyl hydroperoxide (TBHP) system: preparation, characterization, reaction, and mechanism. Clean Techn Environ Policy 17:1487–1497. https://doi.org/10.1007/s10098-014-0797-5
Nilchi A, Janitabar-Darzi S, Rasouli-Garmarodi S (2011) Sol-gel preparation of nanoscale TiO2/SiO2 composite for eliminating of Con Red azo dye. Mater Sci Appl 2:476–480. https://doi.org/10.4236/msa.2011.25064
Pakdel E, Daoud WA, Wang X (2013) Self-cleaning and superhydrophilic wool by TiO2/SiO2 nanocomposite. Appl Surf Sci 275:397–402. https://doi.org/10.1016/j.apsusc.2012.10.141
Pawelec B, Navarro RM, Campos-Martin JM, Fierro JLG (2011) Retracted article: towards near zero-sulfur liquid fuels: a perspective review. Catal Sci Technol 1:23–42. https://doi.org/10.1039/C0CY00049C
Peng H, Wang X, Li G, Pang H, Chen X (2010) Facile synthesis of rice-like anatase TiO2 nanocrystals. Mater Lett 64:1898–1901. https://doi.org/10.1016/j.matlet.2010.05.053
Piscopo CG, Tochtermann J, Schwarzer M, Boskovic D, Maggi R, Maestri G, Loebbecke S (2018) Titania supported on silica as an efficient catalyst for deep oxidative desulfurization of a model fuel with exceptionally diluted H2O2. React Chem Eng 3:13–16. https://doi.org/10.1002/cctc.200900073
Qin B, Shen Y, Xu B, Zhu S, Li P, Liu Y (2018) Mesoporous TiO2–SiO2 adsorbent for ultra-deep desulfurization of organic-S at room temperature and atmospheric pressure. RSC Adv 8:7579–7587. https://doi.org/10.1039/C8RA00112J
Röthlisberger A, Prins R (2005) Intermediates in the hydrodesulfurization of 4, 6-dimethyl-dibenzothiophene over Pd/γ-Al2O3. J Catal 235:229–240. https://doi.org/10.1016/j.jcat.2005.08.007
Shen C, Wang YJ, Xu JH, Luo GS (2016) Oxidative desulfurization of DBT with H2O2 catalysed by TiO2/porous glass. Green Chem 18:771–781. https://doi.org/10.1039/C5GC01653C
Stanislaus A, Marafi A, Rana MS (2010) Recent advances in the science and technology of ultra low sulfur diesel (ULSD) production. Catal Today 153:1–68. https://doi.org/10.1016/j.cattod.2010.05.011
Thornburg NE, Notestein JM (2017) Rate and Selectivity Control in Thioether and Alkene Oxidation with H2O2 over Phosphonate-Modified Niobium (V)–Silica Catalysts. ChemCatChem 9:3714–3724. https://doi.org/10.1002/cctc.201700526
Tian F, Shen Q, Fu Z, Wu Y, Jia C (2014) Enhanced adsorption desulfurization performance over hierarchically structured zeolite Y. Fuel Process Technol 128:176–182. https://doi.org/10.1016/j.fuproc.2014.07.018
Wang C, Zhu W, Xu Y, Xu H, Zhang M, Chao Y, Yin S, Li H, Wang J (2014) Preparation of TiO2/g-C3N4 composites and their application in photocatalytic oxidative desulfurization. Ceram Int 40:11627–11635. https://doi.org/10.1016/j.ceramint.2014.03.156
Wang R, Yu F, Zhang G, Zhao H (2010a) Performance evaluation of the carbon nanotubes supported Cs2.5H0.5PW12O40 as efficient and recoverable catalyst for the oxidative removal of dibenzothiophene. Catal Today 150:37–41. https://doi.org/10.1016/j.cattod.2009.10.001
Wang R, Zhang G, Zhao H (2010b) Polyoxometalate as effective catalyst for the deep desulfurization of diesel oil. Catal Today 149:117–121. https://doi.org/10.1016/j.cattod.2009.03.011
Wang XJ, Li FT, Liu JX, Kou CG, Zhao Y, Hao YJ, Zhao D (2012) Preparation of TiO2 in ionic liquid via microwave radiation and in situ photocatalytic oxidative desulfurization of diesel oil. Energy Fuel 26:6777–6782. https://doi.org/10.1021/ef301337y
Wang XS, Li L, Liang J, Huang YB, Cao R (2017) Boosting oxidative desulfurization of model and real gasoline over phosphotungstic acid encapsulated in metal–organic frameworks: the window size matters. ChemCatChem 9:971–979. https://doi.org/10.1002/cctc.201601450
Wang Y, Yang RT (2007) Desulfurization of liquid fuels by adsorption on carbon based sorbents and ultrasound-assisted sorbent regeneration. Langmuir 23:3825–2831. https://doi.org/10.1021/la063364z
Xiong J, Zhu W, Li H, Ding W, Chao Y, Wu P, Xun S, Zhang M, Li H (2015) Few-layered graphene-like boron nitride induced a remarkable adsorption capacity for dibenzothiophene in fuels. Green Chem 17:1647–1656. https://doi.org/10.1039/C4GC02053G
Xu CZ, Zheng MQ, Keng CHEN, Hui HU, Chen XH (2016) CeOx doping on a TiO2-SiO2 supporter enhances Ag based adsorptive desulfurization for diesel. J Fuel Chem Technol 44:943–953. https://doi.org/10.1016/S1872-5813(16)30042-1
Ye M, Chen Z, Wang W, Zhen L, Shen J (2008) Large-scale synthesis and characterization of fan-shaped rutile TiO2 nanostructures. Mater Lett 62:3404–3406. https://doi.org/10.1016/j.matlet.2008.03.019
Zarrabi M, Entezari MH, Goharshadi EK (2015) Photocatalytic oxidative desulfurization of dibenzothiophene by C/TiO2@ MCM-41 nanoparticles under visible light and mild conditions. RSC Adv 5:34652–34662. https://doi.org/10.1039/C5RA02513C
Zhang M, Zhu W, Xun S, Li H, Gu Q, Zhao Z, Wang Q (2013) Deep oxidative desulfurization of dibenzothiophene with POM-based hybrid materials in ionic liquids. Chem Eng J 220(2013):328–336. https://doi.org/10.1016/j.cej.2012.11.138
Zhang Y, Lü H, Wang L, Zhang Y, Liu P, Han H, Jiang Z, Li C (2010) The oxidation of benzothiophene using the Keggin-type lacunary polytungstophosphate as catalysts in emulsion. J Mol Catal A Chem 332:59–64. https://doi.org/10.1016/j.molcata.2010.08.021
Zhu W, Xu Y, Li H, Dai B, Xu H, Wang C, Chao Y, Liu H (2014) Photocatalytic oxidative desulfurization of dibenzothiophene catalyzed by amorphous TiO2 in ionic liquid. Korean J Chem Eng 31:211–217. https://doi.org/10.1007/s11814-013-0224-3
Zhu Y, Zhu M, Kang L, Yu F, Dai B (2015) Phosphotungstic acid supported on mesoporous graphitic carbon nitride as catalyst for oxidative desulfurization of fuel. Ind Eng Chem Res 54:2040–2047. https://doi.org/10.1021/ie504372p
Acknowledgments
The authors would like to thank Mr. A. Mojaverian Kermani for his help with the spectrophotometer measurements.
Funding
The project was supported by the Iranian National Science Foundation (NSF) under grant number 93024631 that are greatly acknowledged.
Author information
Authors and Affiliations
Corresponding author
Additional information
Responsible Editor: Vítor Pais Vilar
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
ESM 1
(DOCX 128 kb)
Rights and permissions
About this article
Cite this article
Ghahramaninezhad, M., Ahmadpour, A. A new simple protocol for the synthesis of nanohybrid catalyst for oxidative desulfurization of dibenzothiophene. Environ Sci Pollut Res 27, 4104–4114 (2020). https://doi.org/10.1007/s11356-019-07048-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-019-07048-z