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Advances in Nanocatalyzed Hydrodesulfurization of Gasoline and Diesel Fuels

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Part of the book series: Topics in Mining, Metallurgy and Materials Engineering ((TMMME))

Abstract

This chapter is aimed toward providing a general overview of the significant progress that desulfurization technology has brought to the oil and gas industries. Organosulfur compounds are known to release various environmentally harmful sulfur products into the atmosphere from the combustion engines of vehicles, leading to a serious environmental threat. Efficient removal of these sulfur compounds from diesel and gasoline fuels that we inevitably use in various capacities every day is therefore paramount. Various desulfurization technologies have been developed over the years to address this issue, and one of the most efficient and cost-effective approaches is transition metal-catalyzed hydrodesulfurization (HDS). Several nanocatalysts have been designed for this purpose. The chapter encapsulates some of the various ways in which these catalysts are being prepared, including doped nanocatalysts which are relatively unexplored for this application. It also includes a discussion and examples of their activities in the desulfurization reactions. The limitations are discussed, as well as possible ways to improve their sulfur removal efficiency. Furthermore, some of the commercially employed HDS catalysts, including feedstock, the reaction conditions they work best under, the type of reactor, and various factors affecting the hydrodesulfurization reactions are discussed, along with illustrations. The HDS mechanism is another important aspect of desulfurization that was thoroughly reviewed, including a discussion of the suggested pathways for the hydrodesulfurization of dibenzothiophenes (DBTs) and their derivatives, in addition to the toxic processes of HDS catalysts. Finally, the ongoing research on improved desulfurization processes, specifically the deep HDS of diesel and gasoline fuels in order to comply with the current standard for sulfur removal specifications, is also briefly addressed in this chapter.

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References

  • Ackerson MD, Byars MS (2000). US Patents, 6,123,835

    Google Scholar 

  • Andari MK, Abu-Seedo F, Stanislaus A, Qabazard HM (1996) Kinetics of individual sulfur compounds in deep hydrodesulfurization of Kuwait diesel oil. Fuel 75:1664–1670

    Article  Google Scholar 

  • Babich IV, Moulijn JA (2003) Science and technology of novel processes for deep desulfurization of oil refinery streams: a review. Fuel 82:607–631

    Article  Google Scholar 

  • Bartsch R, Taniellian C (1974) Hydrodesulfurization: I. Hydrogenolysis of benzothiophene and dibenzothiophene over CoO, MoO3, Al2O3 catalyst. J Catal 35:353–358

    Google Scholar 

  • Bataille F, Lemberton JL, Michand P, Perot G, Vrinat M, Lemaire M, Schulz E, Breysse M, Kasztelan S (2000) Alkyldibenzothiophenes hydrodesulfurization-promoter effect, reactivity and reaction mechanism. J Catal 191:409

    Article  Google Scholar 

  • Beens J, Tijssen R (1997) The characterization and quantitation of sulfur-containing compounds in (heavy) middle distillates by LC-GC-FID-SCD. J High Resol Chromatogr 20(3):131–137

    Article  Google Scholar 

  • Besenbacher F, Brorson M, Clausen BS, Helveg S, Hinnemann B, Kibsgaard J, Lauritsen J, Moses PG, Nørskov JK, Topsøe H (2008) Recent STM, DFT and HAADF-STEM studies of sulfide-based hydrotreating catalysts: insight into mechanistic, structural and particle size effects. Catal Today 130:86–96

    Article  Google Scholar 

  • Candia R, Clausen BS, Topsøe H (1984) Proceedings of the ninth Iberoamerican symposium on catalysis. Lisbon, Portugal, p 211

    Google Scholar 

  • Carlsson A, Brorson M, Topsøe H (2004) Morphology of WS2 nanoclusters in WS2/C hydrodesulfurization catalysts revealed by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) imaging. J Catal 227:530–536

    Article  Google Scholar 

  • Choi KH, Kunisada N, Korai Y, Mochida I, Nakano K (2003) Facil ultra-deep desulfurization of gas oil through two-stage or layer catalyst bed. Catal Today 86:277–286

    Article  Google Scholar 

  • Cooper BH, Donnis BBL (1996) Aromatic saturation of distillates: an overview. Appl Catal A 137:203–223

    Article  Google Scholar 

  • Costa PD, Manoli JM, Potvin C (2005) Dje’ga-Mariadassou G deep HDS on doped molybdenum carbides: from probe molecules to real feedstocks. Catal Today 107–108:520–530

    Article  Google Scholar 

  • Danmaliki GI, Saleh TA (2017) Effects of bimetallic Ce/Fe nanoparticles on the desulfurization of thiophenes using activated carbon. Chem Eng J 307:914–927

    Article  Google Scholar 

  • Deng Z, Wang T, Wang Z (2010) Hydrodesulfurization of diesel in a slurry reactor. Chem Eng Sci 65:480–486

    Article  Google Scholar 

  • Farag H, Mochida I, Sakanishi K (2000) Fundamental comparison studies on hydrodesulfurization of dibenzothiophenes over CoMo-based carbon and alumina catalysts. Appl Catal A Gen 194–195:147–157

    Article  Google Scholar 

  • Gates BC, Topsoe H (1997) Reactivities in deep catalytic hydrodesulfurization: challenges, opportunities, and the importance of 4-methyldibenzothiophene and 4,6-dimethyl-dibenzothiophene. Polyhedron 16:3213

    Article  Google Scholar 

  • Girgis MJ, Gates BC (1991) Reactivities, reaction networks, and kinetics in high-pressure catalytic hydroprocessing Ind. Eng Chem Res 30(9):2021–2058

    Article  Google Scholar 

  • Gosselink J, Stork WHJ (1987) Catalyst Deactivation. Chem Eng Process 22:157

    Google Scholar 

  • Helveg S, Lauritsen JV, Lægsgaard E, Stensgaard I, Nørskov JK, Clausen BS, Topsøe H, Besenbacher F (2000) Atomic-scale structure of single layer MoS2 nanoclusters. Phys Rev Lett 84:951–954

    Article  Google Scholar 

  • Hinnemann B, Nørskov JK, Topsøe H (2005) A density functional study of the chemical differences between Type I and Type II MoS2-based structures in hydrotreating catalysts. J Phys Chem B 109:2245–2253

    Article  Google Scholar 

  • Hirschon AS, Wilson RB Jr, Laine RM (1987) Ruthenium promoted hydrodenitrogenation catalysts. Appl Catal 34:311–316

    Article  Google Scholar 

  • Ho TC (2004) Deep HDS of diesel fuel: chemistry and catalysis. Catal Today 98:3–18

    Article  Google Scholar 

  • Houalla M, Broderick DH, Sapre AV, Nag NK, de Beer VHJ, Gates BC, Kwart H (1980) Hydrodesulfurization of methyl-substituted dibenzothiophenes catalyzed by sulfided Co-Mo/γ-Al2O3. J Catal 61:523–527

    Article  Google Scholar 

  • Hubaut R, Altafulla J, Rives A, Scott C (2007) Characterization and HDS activities of mixed Fe–Mo sulphides supported on alumina and carbon. Fuel 86:743–749

    Article  Google Scholar 

  • Isoda T, Takase Y, Kusakabe K, Morooka S (2000) Changes in desulfurization reactivity of 4,6-dimethyldibenzothiophene by skeletal isomerization using a Ni-supported Y-type zeolite. Energy Fuels 14:585–590

    Article  Google Scholar 

  • Kabe T, Ishihara A, Tajima H (1992) Hydrodesulfurization of sulfur-containing polyaromatic compounds in light oil. Ind Eng Chem Res 31(6):1577–1580

    Article  Google Scholar 

  • Kabe T, Qian WH, Ogawa S, Ishihara A (1993) Mechanism of hydrodesulfurization of dibenzothiophene on Co-Mo/Al2O3 and Co/Al2O3 catalyst by the use of radioisotope 35S. J Catal 143:239–248

    Article  Google Scholar 

  • Kunisada N, Choi KH, Korai Y, Mochida I, Nakano K (2004a) Effective supports to moderate H2S inhibition on cobalt and nickel molybdenum sulfide catalysts in deep desulfurization of gas. Appl Catal A 260:185–190

    Article  Google Scholar 

  • Kunisada N, Choi KH, Korai Y, Mochida I, Nakano K (2004b) Novel zeolite based support for NiMo sulfide in deep HDS of gas oil. Appl Catal A 269:43–51

    Article  Google Scholar 

  • Lamure-Meille V, Schulz E, Lemaire M, Vrinat M (1995) Effect of experimental parameters on the relative reactivity of dibenzothiophene and 4-methyldibenzothiophene. Appl Catal A Gen 131(1):143–157

    Article  Google Scholar 

  • Landau MV, Berger D, Herskowitz M (1996) Chemical and physical characterization of alumina-supported chromia-based catalysts and their activity in dehydrogenation of isobutane. J Catal 158(1):236–250

    Article  Google Scholar 

  • Lauritsen JV, Kibsgaard J, Olesen GH, Moses PG, Hinnemann B, Helveg S, Nørskov JK, Clausen BS, Topsøe H, Lægsgaard E, Besenbacher F (2007) Location and coordination of promoter atoms in Co- and Ni-promoted MoS2-based hydrotreating catalysts. J Catal 249(2):220–233

    Article  Google Scholar 

  • Li K, Hou B, Wang L, Cui Y (2014) Application of carbon nanocatalysts in upgrading heavy crude oil assisted with microwave heating. Nano Lett 14:3002–3008

    Article  Google Scholar 

  • Logadottir A, Moses PG, Hinnemann B, Topsoe NY, Knudsen KG, Topsoe H, Norskov JK (2006) A density functional study of inhibition of the HDS hydrogenation pathway by pyridine, benzene, and H2S on MoS2-based catalysts. Catal Today 111:44

    Article  Google Scholar 

  • Ma X, Sakanishi K, Mochida I (1994) Hydrodesulfurization reactivities of various sulfur compounds in diesel fuel. Ind Eng Chem Res 33(2):218–222

    Article  Google Scholar 

  • Ma X, Sakanishi K, Isoda T, Mochida I (1995) Quantum chemical calculation on the desulfurization reactivities of heterocyclic sulfur compounds. Energy Fuel 9:33–37

    Article  Google Scholar 

  • Mochida I, Sakanishi K, Ma X, Nagao S, Isoda T (1996) Deep hydrodesulfurization of diesel fuel: design of reaction process and catalysts. Catal Today 29:185–189

    Article  Google Scholar 

  • Moses PG, Hinnemann B, Topsøe H, Nørskov JK (2008) Corrigendum to the hydrogenation and direct desulfurization reaction pathway in thiophene hydrodesulfurization over MoS2 catalysts at realistic conditions: a density functional study. J Catal 260:202–203

    Article  Google Scholar 

  • Moses PG, Hinnemann B, Topsøe H, Nørskov JK (2009) The effect of co-promotion on MoS2 catalysts for hydrodesulfurization of thiophene: a density functional study. J Catal 268:201–208

    Article  Google Scholar 

  • Nagai M, Sato T, Aiba A (1986) Poisoning effect of nitrogen compounds on dibenzothiophene hydrodesulfurization on sulfided NiMoAl2O3 catalysts and relation to gas-phase basicity. J Catal 97(1):52–58

    Article  Google Scholar 

  • Nava R, Ortega RA, Alonso G, Ornelas C, Pawelec B, Fierro JLG (2007) CoMo/Ti-SBA-15 catalysts for dibenzothiophene desulfurization. Catal Today 127:70–84

    Article  Google Scholar 

  • Ng FTT, Milad IK (2000) Catalytic desulphurization of benzothiophene in an emulsion via in situ generated H2. Appl Catal A 200:243–254

    Article  Google Scholar 

  • Papadopoulou C, Vakros J, Matralis HK, Kordulis C, Lycourghiotis A (2003) On the relationship between the preparation method and the physicochemical and catalytic properties of the CoMo/γ-Al2O3 hydrodesulfurization catalysts. J Colloid Interface Sci 261:146–153

    Article  Google Scholar 

  • Pecoraro TA, Chianelli RR (1981) Hydrodesulfurization catalysis by transition metal sulfides. J Catal 67:430–445

    Article  Google Scholar 

  • Pedernera E, Reimert R, Nguyen NL, van Buren V (2003) Deep desulfurization of middle distillates: process adaptation to oil fractions’ compositions. Catal Today 79–80:371–381

    Article  Google Scholar 

  • Rodriguez-Castellon E, Jimenez-Lopez A, Eliche-Quesada D (2008) Nickel and cobalt promoted tungsten and molybdenum sulfide mesoporous catalysts for hydrodesulfurization. Fuel 87:1195–1206

    Article  Google Scholar 

  • Sakanishi K, Nagamatsu T, Mochida I, Whitehurst DD (2000) Hydrodesulfurization kinetics and mechanism of 4,6-dimethyldibenzothiophene over NiMo catalyst supported on carbon. J Mol Catal A Chem 155:101–109

    Article  Google Scholar 

  • Saleh TA, Danmaliki GI (2016a) Influence of acidic and basic treatments of activated carbon derived from waste rubber tires on adsorptive desulfurization of thiophenes. J Taiwan Inst Chem Eng 60:460–468

    Article  Google Scholar 

  • Saleh TA, Danmaliki GI (2016b) Adsorptive desulfurization of dibenzothiophene from fuels by rubber tyres-derived carbons: kinetics and isotherms evaluation. Process Saf Environ Prot 102:9–19

    Article  Google Scholar 

  • Saleh TA, Sulaiman KO, AL-Hammadi SA, Dafalla H, Danmaliki GI (2017) Adsorptive desulfurization of thiophene, benzothiophene and dibenzothiophene over activated carbon manganese oxide nanocomposite: with column system evaluation. J Clean Prod 154:401–412

    Article  Google Scholar 

  • Satterfield CN, Modell M, Mayer JF (1975) Interactions between catalytic hydrodesulfurization of thiophene and hydrodenitrogenation of pyridine. AIChE J 21(6):1100–1107

    Article  Google Scholar 

  • Schmitz C, Datsevitch L, Jess A (2004) Deep desulfurization of diesel oil: kinetic studies and process-improvement by the use of a two-phase reactor with pre-saturator. Chem Eng Sci 59:2821–2829

    Article  Google Scholar 

  • Sertic-Bionda T, Gomzi Z, Šaric T (2005) Testing of hydrodesulfurization process in small trickle-bed reactor. Chem Eng J 106:105–110

    Article  Google Scholar 

  • Shih SS, Mizrahi S, Green LA, Sarli MS (1992) Deep desulfurization of distillates. Ind Eng Chem Res 31(4):1232–1235

    Article  Google Scholar 

  • Shin S, Yang H, Sakanishi K, Mochida I, Grudoski DA, Shinn JH (2001) Inhibition and deactivation in staged hydrodenitrogenation and hydrodesulfurization of medium cycle oil over NiMoS/Al2O3 catalyst. Appl Catal A 205:101–108

    Article  Google Scholar 

  • Sie ST (1995) Proceedings of the 210th ASC symposium on deactivation and testing of hydrocarbon-processing catalysts, Chicago, August 20–25, 6

    Google Scholar 

  • Song C (1999) Designing sulfur-resistant, noble-metal hydrotreating catalysts. Chemtech 29(3):26–30

    Google Scholar 

  • Song C (2003) An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel. Catal Today 86:211–263

    Article  Google Scholar 

  • Song C, Hsu CS, Mochida I (2000a) Chemistry of diesel fuels. Taylor & Francis, New York, 294 pp

    Google Scholar 

  • Song C, Yoneyama Y, Kondam MR (2000b) Method for preparing a highly active, unsupported high-surface-area MoS2 catalyst. U.S. Patent No. 6156693

    Google Scholar 

  • Srivastava VC (2012) An evaluation of desulfurization technologies for sulfur removal from liquid fuels. RSC Adv 2:759–783

    Article  Google Scholar 

  • Topsøe H, Clausen BS (1986) Active sites and support effects in hydrodesulfurization catalysts. Appl Catal 25:273–293

    Article  Google Scholar 

  • Topsøe H, Clausen BS, Candia R, Wivel C, Mørup S (1981) In situ Mössbauer emission spectroscopy studies of unsupported and supported sulfided Co-Mo hydrodesulfurization catalysts: evidence for and nature of a Co-Mo-S phase. J Catal 68:433–452

    Article  Google Scholar 

  • Topsøe H, Clausen BS, Massoth FE (1996) Hydrotreating catalysis. In: Anderson JR, Boudart M (eds) Catalysis-science and technology, vol 11. Springer, Berlin

    Google Scholar 

  • Trakarnpruk W, Seentrakoon B (2007) Hydrodesulfurization activity of MoS2 and bimetallic catalysts prepared by in situ decomposition of thiosalt. Ind Eng Chem Res 46:1874–1882

    Article  Google Scholar 

  • Trakarnpruk W, Seentrakoon B, Porntangjitlikit S (2008) Hydrodesulfurization of diesel oils by MoS2 catalyst prepared by in situ decomposition of ammonium thiomolybdate. Silpakorn U Sci Tech J 2(1):7–13

    Google Scholar 

  • Turaga UT, Song C (2003) MCM-41-supported Co-Mo catalysts for deep hydrodesulfurization of light cycle oil. Catal Today 86:129–140

    Article  Google Scholar 

  • van Looij F, van der Laan P, Stork WHJ, DiCamillo DJ, Swain J (1998) Key parameters in deep hydrodesulfurization of diesel fuel. Appl Catal A Gen 170:1–12

    Article  Google Scholar 

  • Vasudeven PT, Fierro JLG (1996) A review of deep hydrodesulfurization catalysis. Catal Rev Sci Eng 38(2):161–188

    Article  Google Scholar 

  • Venezia AM, Parola VL, Deganello G, Cauzzi D, Leonardi G, Predieri G (2002) Influence of the preparation method on the thiophene HDS activity of silica supported CoMo catalysts. Appl Catal A 229:261–271

    Article  Google Scholar 

  • Vradman L, Landau MV, Herskowitz M (1999) Deep desulfurization of diesel fuels: kinetic modeling of model compounds in trickle-bed. Catal Today 48:41–48

    Article  Google Scholar 

  • Whitehurst DD, Isoda I, Mochida I (1998) Present state of the art and future challenges in the hydrodesulfurization of polyaromatic compounds. Adv Catal 42:345–357

    Google Scholar 

  • Wivel C, Candia R, Clausen BS, Mørup S, Topsøe H (1981) On the catalytic significance of a Co-Mo-S phase in Co-MoAl2O3 hydrodesulfurization catalysts: combined in situ Mössbauer emission spectroscopy and activity studies. J Catal 68(2):453–463

    Article  Google Scholar 

  • Yitzhaki D, Landau MV, Berger D, Herskowitz M (1995) Deep desulfurization of heavy atmospheric gas oil with CoMoAl catalysts effect of sulfur adsorption. Appl Catal A 122:99–110

    Article  Google Scholar 

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Acknowledgement

The authors acknowledge the support of the chemistry department, and King Fahd University of Petroleum and Minerals, (KFUPM) Dhahran, Saudi Arabia.

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Correspondence to Tawfik Abdo Saleh .

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Saleh, T.A., Abdullahi, I.M. (2018). Advances in Nanocatalyzed Hydrodesulfurization of Gasoline and Diesel Fuels. In: Saleh, T. (eds) Nanotechnology in Oil and Gas Industries. Topics in Mining, Metallurgy and Materials Engineering. Springer, Cham. https://doi.org/10.1007/978-3-319-60630-9_3

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  • DOI: https://doi.org/10.1007/978-3-319-60630-9_3

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