Skip to main content
SpringerLink
Log in

Hydrodesulfurization (HDS) Process Based on Nano-catalysts: The Role of Supports

  • Chapter
  • First Online:
Nanotechnology in Oil and Gas Industries

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

  • 1295 Accesses

Abstract

Nowadays, market demand of middle distillate such as naphtha, kerosene, and diesel fractions with low sulfur content is augmented. Sulfur oxides which are released to the air by combustion of this kind of fuels are one of the critical problems of the environment. Hydrodesulfurization (HDS) is one of the most important catalytic processes which have been offered for solving these kinds of difficulties.

Conventional HDS catalysts are MoS2 together with some metals from the transition metal series supported on γ-Al2O3 that are promoted by either cobalt or nickel.

A lot of research has been focused on HDS catalysts improvement for different industries, where they investigated various catalyst supports, active phases, and catalyst synthesis methods.

Recently, nano-materials are extensively used for catalytic HDS process. Carbon nanostructures such as carbon nanotubes (CNTs) draw scientists’ attention because of their high mechanical strengths, purities, and thermal stability.

In this work, an overview of HDS process and various types of catalysts for removal of sulfur compounds from fuels is indicated. In addition, improved catalysts using nanotechnology including carbon nanotubes, graphene, and nano-alumina are investigated.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 99.00
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 129.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 199.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

References

  • Aghabozorg HR, Sadegh Hassani S, Rashidi AM (2015) Nanocatalysts preparation, characterization, and their application in oil and gas processes. In: Kharisov BI, Kharissova OV, Ortiz-Mendez U (eds) CRC encyclopedia. Taylor and Fransis, Boca Raton, FL, pp 100–107

    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 

  • Bigdeli S, Fatemi S (2015) Fast carbon nanofiber growth on the surface of activated carbon by microwave irradiation; a modified nano-adsorbent for deep desulfurization of liquid fuels. Chem Eng J 269:306–315

    Article  Google Scholar 

  • Caero LC, Romero AR, Ramirez J (2003) Niobium sulfide as a dopant for Mo/TiO2 catalysts. Catal Today 78:513–518

    Article  Google Scholar 

  • Campos-Martin JM, Rojas S, Oyama ST, Gott T, Zhao H, Lee Y-K (2009) Transition metal phosphide hydroprocessing catalysts: a review. Catal Today 143:94–107

    Article  Google Scholar 

  • Castillo-Araiza CO, Chávez G, Dutta A, de los Reyes JA, Nuñez S, García-Martínez JC (2015) Role of Pt–Pd/γ-Al2O3on the HDS of 4,6-DMBT: Kinetic modeling & contribution analysis. Fuel Process Technol 132:164–172

    Article  Google Scholar 

  • Chen H, Zhou X, Shang H, Liu C, Qiu J, Wei F (2004) Study of dibenzothiophene adsorption over carbon nanotube supported CoMo HDS catalysts. J Nat Gas Chem 13:209–217

    Google Scholar 

  • Coelho TL, Licea YE, Palacio LA, Faro AC Jr (2014) Heptamolybdate-intercalated CoMgAl hydrotalcites as precursors for HDS selective hydrotreating catalysts. Catal Today 250:38–46

    Article  Google Scholar 

  • Cui Q, Zhou Y, Wei Q, Yu G, Zhu L (2013) Performance of Zr- and P-modified USY-based catalyst in hydrocracking of vacuum gas oil. Fuel Process Technol 106:439–446

    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 

  • Dhar GM, Srinivas BN, Rana MS, Kumar M, Maity SK (2003) Mixed oxide supported hydrodesulfurization catalysts—a review. Catal Today 86:45–60

    Article  Google Scholar 

  • Dumeignil F, Sato K, Imamura M, Matsubayashi N, Payen E, Shimada H (2006) Characterization and hydrodesulfurization activity of CoMo catalysts supported on sol-gel prepared Al2O3. Appl Catal A Gen 315:18–28

    Article  Google Scholar 

  • El Kady FYA, Abd El Wahed MG, Shaban S, Abo El Naga AO (2010) Hydrotreating of heavy gas oil using CoMoc-Al2O3 catalyst prepared by equilibrium deposition filtration. Fuel 89:3193–3206

    Article  Google Scholar 

  • Escobar J, Barrera MC, De Los Reyes JA, Cortés MA, Santes V, Gómez E, Pacheco JG (2008) Effect of Mo and Co loading in HDS catalysts supported on solvo-thermally treated ZrO2–TiO2 mixed oxides. Catal Today 133–135:282–291

    Article  Google Scholar 

  • Eswaramoorthi I, Sundaramurthy V, Das N, Dalai AK, Adjaye J (2008) Application of multi-walled carbon nanotubes as efficient support to NiMo hydrotreating catalyst. Appl Catal A Gen 339:187–195

    Article  Google Scholar 

  • Faro AC Jr, dos Santos ACB (2006) Cumene hydrocracking and thiophene HDS on niobia-supported Ni, Mo and Ni–Mo catalysts. Catal Today 118:402–409

    Article  Google Scholar 

  • Ferdous D, Dalai AK, Adjaye J (2004) A series of NiMo/Al2O3 catalysts containing boron and phosphorus Part I. Synthesis and characterization. Appl Catal A Gen 260:137–151

    Article  Google Scholar 

  • Fontaine C, Romero Y, Daudin A, Devers E, Bouchy C, Brunet S (2010) Insight into sulphur compounds and promoter effects on Molybdenum-based catalysts for selective HDS of FCC gasoline. Appl Catal A Gen 388:188–195

    Article  Google Scholar 

  • Graham UM, Dozier A, Khatri RA, Bahome MC, Jewell LL, Mhlanga SD, Coville NJ, Davis BH (2009) Carbon nanotube docking stations: a new concept in catalysis. Catal Lett 129:39–45

    Article  Google Scholar 

  • Guo C, Wu Y, Wang X, Yang B (2013) Effect of the support calcination temperature on selective hydrodesulfurization of TiO2 nanotubes supported CoMo catalysts. J Energy Chem 22:517–523

    Article  Google Scholar 

  • Gutiérrez OY, Klimova T (2011) Effect of the support on the high activity of the (Ni)Mo/ZrO2–SBA-15 catalyst in the simultaneous hydrodesulfurization of DBT and 4,6-DMDBT. J Catal 281:50–62

    Article  Google Scholar 

  • Hajjar Z, Kazemeini M, Rashidi AM, Bazmi M (2015) In situ and simultaneous synthesis of a novel graphene-based catalyst for deep hydrodesulfurization of naphtha. Catal Lett 145:1660–1672

    Article  Google Scholar 

  • Hajjar Z, Kazemeini M, Rashidi A, Tayyebi S (2016a) Artificial intelligence techniques for modeling and optimization of the HDS process over a new graphene based catalyst. Phosphorus Sulfur Silicon Relat Elem 191:1256–1261

    Article  Google Scholar 

  • Hajjar Z, Kazemeini M, Rashidi AM, Bazmi M (2016b) Graphene based catalysts for deep hydrodesulfurization of naphtha and diesel fuels: a physiochemical study. Fuel 165:468–476

    Article  Google Scholar 

  • Hatanaka S (2005) Hydrodesulfurization of selective catalytic cracked gasoline. Catal Surv Asia 9:87–93

    Article  Google Scholar 

  • Khorami P, Kalbasi M (2011) Hydrodesulfurization activity of CoMo catalyst supported on multi wall carbon nanotube: sulphur species study. J Exp Nanosci 6:349–361

    Article  Google Scholar 

  • Kiani M, Aghabozorg H, Jafari Jozani K, Rashidi AM, Mohsennia M (2013) Preparation and characterization of carbon nanotubes supported Ni2P for hydrodesulfurization (HDS) of naphtha. Phosphorus Sulfur Silicon 188:1254–1261

    Article  Google Scholar 

  • Klimova T, Vara PM, Lee IP (2010) Development of new NiMo/g-alumina catalysts doped with noble metals for deep HDS. Cataly Today 150:171–178

    Article  Google Scholar 

  • Krebs E, Silvi B, Daudin A, Raybaud P (2008) A DFT study of the origin of the HDS/HydO selectivity on Co(Ni)MoS active phases. J Catal 260:276–287

    Article  Google Scholar 

  • Lee X, Feng J, Guo J, Wang A, Prins R, Duan X, Chen Y (2016) Preparation of Ni2P/ Al2O3 by temperature programmed reduction of a phosphate precursor with a low P/Ni ratio. J Catal 334:116–119

    Article  Google Scholar 

  • Liu X, Li X, Yan Z (2012) Facile route to prepare bimodal mesoporous γ-Al2O3 as support for highly active CoMo-based hydrodesulfurization catalyst. Appl Catal B Environ 121–122:50–56

    Article  Google Scholar 

  • Mey D, Brunet S, Canaff C, Maugé F, Bouchy C, Diehl F (2004) HDS of a model FCC gasoline over a sulfided CoMo/Al2O3 catalyst: effect of the addition of potassium. J Catal 227:436–447

    Article  Google Scholar 

  • Michel V, Dorothée L, Christophe G (2012) Use of competitive kinetics for the understanding of deep hydrodesulfurization and sulfide catalysts behavior. Appl Catal B Environ 128:3–9

    Article  Google Scholar 

  • Mohammadi Meman N, Pourkhalil M, Rashidi AM, Zare Nezhad B (2014) Synthesis, characterization and operation of a functionalized multi-walled CNT supported MnOx nanocatalyst for deep oxidative desulfurization of sour petroleum fractions. J Ind Eng Chem 20:4054–4058

    Article  Google Scholar 

  • Morales-Ortũno JC, Ortega-Domínguez RA, Hernández-Hipólito P, Bokhimi X, Klimova TE (2015) HDS performance of NiMo catalysts supported on nanostructured materials containing titania. Catal Today 271:127–139

    Article  Google Scholar 

  • Nakhaei Pour A, Rashidi AM, Jafari Jozani K, Mohajeri A, Khorami P (2010) Support effects on the chemical property and catalytic activity of Co-Mo HDS catalyst in sulfur recovery. J Nat Gas Chem 19:91–95

    Article  Google Scholar 

  • Nikulshin PA, Salnikov VA, Mozhaev AV, Minaev PP, Kogan VM, Pimerzin AA (2014) Relationship between active phase morphology and catalytic properties of the carbon–alumina-supported Co(Ni)Mo catalysts in HDS and HYD reactions. J Catal 309:386–396

    Article  Google Scholar 

  • Nikulshin P, Mozhaev A, Lancelot C, Blanchard P, Payen E, Lamonier C (2016) Hydroprocessing catalysts based on transition metal sulfides prepared from Anderson and dimeric Co2Mo10-heteropolyanions, a review. C R Chim 19:1276–1285

    Article  Google Scholar 

  • Okamoto Y (2008) A novel preparation-characterization technique of hydrodesulfurization catalysts for cleaner fuels. Catal Today 132:9–17

    Article  Google Scholar 

  • Parviz D, Kazemeini M, Rashidi AM, Jafari Jozani K (2011) Naphtha hydrodesulfurization over micro and nanostructure MoO3 catalysts. Sci Iran C 18:479–485

    Article  Google Scholar 

  • Pawelec B, La Parola V, Navarro RM, Murcia-Mascarós S, Fierro JLG (2006) On the origin of the high performance of MWNT-supported PtPd catalysts for the hydrogenation of aromatics. Carbon 44:84–98

    Article  Google Scholar 

  • Rao CNR, Sood AK, Subrahmanyam KS, Govindaraj A (2009) Graphene: the new two-dimensional nanomaterial. Angew Chem Int Ed 48:7752–7777

    Article  Google Scholar 

  • Rashidi F, Nemati Kharat A, Rashidi AM, Lima E, Lara V, Valente JS (2010) Fractal geometry approach to describe mesostructured boehmite and Gamma-alumina nanorods. Eur J Inorg Chem:1544–1551

    Google Scholar 

  • Rashidi F, Lima E, Rashidi H, Rashidi AM, Guzmane A (2012) Cooperative effect of gold nanoparticles with CUS aluminum from nanoalumina support in the catalysis of an electron transfer reaction. Appl Catal A Gen 417–418:129–136

    Article  Google Scholar 

  • Rashidi F, Sasakia T, Rashidi AM, Nemati Kharat A, Jafari Jozani K (2013) Ultra deep hydrodesulfurization of diesel fuels using highly efficient nanoalumina-supported catalysts: impact of support, phosphorus, and/or boron on the structure and catalytic activity. J Catal 299:321–335

    Article  Google Scholar 

  • Ren S, Li J, Feng B, Wang Y, Zhang W, Wen G, Zhang Z, Shen B (2016) A novel catalyst of Ni,W-surface-Ti-rich-ETS-10/Al2O3: its role and potential of HDS performance for steric hindered sulfur compound 4,6-DMDBT. Catalysis Today 263:136–140

    Article  Google Scholar 

  • Robles JM, Castellón ER, López AJ (1999) Characterization of Ni, Mo and Ni–Mo catalysts supported on alumina-pillared a-zirconium phosphate and reactivity for the thiophene HDS reaction. J Mol Catal A Chem 145:169–181

    Article  Google Scholar 

  • Saih Y, Nagata M, Funamoto T, Masuyama Y, Segawa K (2005) Ultra deep hydrodesulfurization of dibenzothiophene derivatives over NiMo/TiO2-Al2O3. Appl Catal A 295:11–22

    Article  Google Scholar 

  • Santes V, Herbert J, Cortez MT, Zárate R, Díaz L, Swamy PN, Aouine M, Vrinat M (2005) Catalytic hydrotreating of heavy gasoil FCC feed on alumina–titania-supported NiMo catalysts. Appl Catal A Gen 281:121–128

    Article  Google Scholar 

  • Schuman SC, Shalit H (1971) Hydrodesulfurization. Catal Rev Sci Eng 4(1):245–318

    Article  Google Scholar 

  • Shang H, Liu C, Xu Y, Qiu J, Wei F (2007) States of carbon nanotube supported Mo-based HDS catalysts. Fuel Process Technol 88:117–123

    Article  Google Scholar 

  • Soghrati E, Kazemeini M, Rashidi AM, Jafari Jozani K (2012) Preparation and characterization of Co-Mo catalyst supported on CNT coated cordierite monoliths utilized for naphtha HDS process. Proc Eng 42:1484–1492

    Article  Google Scholar 

  • Song CS, Ma XL (2003) New design approaches to ultra-clean diesel fuels by deep desulfurization and deep dearomatization. Appl Catal B Environ 41:207–238

    Article  Google Scholar 

  • Souchay P (1969) Ions mineraux condenses. Masson

    Google Scholar 

  • Stanislaus A, Marafi A, Rana MS (2010) Recent advances in the science and technology of ultra sulfur diesel (ULSD) production. Catal Today 153:1

    Article  Google Scholar 

  • Sun Z, Masa J, Weide P, Fairclough SM, Robertson AW, Ebbinghaus P, Warner JH, Tsang SCE, Muhlerb M, Schuhmann W (2015) High-quality functionalized few-layer graphene: facile fabrication and doping with nitrogen as a metal-free catalyst for the oxygen reduction reaction. J Mater Chem A 3:15444–15450

    Article  Google Scholar 

  • Thi Vu TH, Thi Nguyen TT, Thi Nguyen PH, Do MH, Au HT, Nguyen TB, Nguyen DL, Park JS (2012) Fabrication of photo catalytic composite of multi-walled carbon nanotubes/TiO2 and its application for desulfurization of diesel. Mater Res Bull 47:308–314

    Article  Google Scholar 

  • Toledo-Antonio JA, Cotres-Jacome MA, Angeles-Chavez C, Escobar J, Barrera MC, Lopez-Salinas E (2009) Highly active CoMoS phase on titania nanotubes as new hydrodesulfurization catalysts. Appl Catal B Environ 90:213–223

    Article  Google Scholar 

  • Toulhoat H, Raybaud P (2013) Catalysis by transition metal sulfides, from molecular theory to industrial application. Editions Technip, Paris, p 151

    Google Scholar 

  • Trejo F, Rana MS, Ancheyta J (2008) CoMo/MgO–Al2O3 supported catalysts: an alternative approach to prepare HDS catalysts. Catal Today 130:327–336

    Article  Google Scholar 

  • Valencia D, Klimova T (2011) Effect of the support composition on the characteristics of NiMo and CoMo/(Zr)SBA-15 catalysts and their performance in deep hydrodesulfurization. Catal Today 166:91–101

    Article  Google Scholar 

  • Villarroel M, Baeza P, Gracia F, Escalona N, Avila P, Gil-Llambías FJ (2009) Phosphorus effect on Co//Mo and Ni//Mo synergism in hydrodesulphurization catalysts. Appl Catal A Gen 364:75–79

    Article  Google Scholar 

  • Von Pope MT (1983) Heteropoly and isopoly oxometalates. Springer, Berlin

    Book  Google Scholar 

  • Vrinat M, Hamon D, Breysse M, Durand D, Courieres T (1994) Zirconia and alumina supported molebdenum based catalysts: a comparative study in hydrodesulfurization and hydrogenation reactions. Catal Today 20:273–282

    Article  Google Scholar 

  • Vrinat M, Bacaud R, Laurenti D, Cattenot M, Escalona N, Gamez S (2005) New trends in the concept of catalytic sites over sulfide catalysts. Catal Today 107–108:570–577

    Article  Google Scholar 

  • Wang X, Zhao Z, Zheng P, Chen Z, Duan A, Xu C, Jiao J, Zhang H, Cao Z, Ge B (2016) Synthesis of NiMo catalysts supported on mesoporous Al2O3 with different crystal forms and superior catalytic performance for the hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene. J Catal 344:680–691

    Article  Google Scholar 

  • Yu Z, Fareid LE, Moljord K, Blekkan EA, Walmsley JC, Chen D (2008) Hydrodesulfurization of thiophene on carbon nanofiber supported Co/Ni/Mo catalysts. Appl Catal B Environ 84:482–489

    Article  Google Scholar 

  • Yuezeng S, Zhang Y, Zhuang X, Li S, Wu D, Zhang F, Feng X (2013) Low-temperature synthesis of nitrogen/sulfur co-doped three-dimensional graphene frameworks as efficient metal-free electrocatalyst for oxygen reduction reaction. Carbon 62:296–301

    Article  Google Scholar 

  • Zhu Y, Murali S, Cai W, Li X, Suk JW, Potts JR, Ruoff RS (2010) Graphene and Graphene Oxide: Synthesis, Properties, and Applications. Adv. Mater. 22:3906–3924

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Nanotechnology Research Center, Research Institute of Petroleum Industry, Tehran, Iran

    Alimorad Rashidi & Sedigheh Sadegh Hassani

  2. Process Engineering Section, Petroleum Engineering Department, Iranian Offshore Oil Company, Tehran, Iran

    Fatemeh Mohammadzadeh

Authors
  1. Alimorad Rashidi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Fatemeh Mohammadzadeh
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Sedigheh Sadegh Hassani
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Alimorad Rashidi .

Editor information

Editors and Affiliations

  1. Chemistry Department, and Center of Excellence in Nanotechnology (CENT), King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia

    Tawfik Abdo Saleh

Rights and permissions

Reprints and permissions

Copyright information

© 2018 Springer International Publishing AG

About this chapter

Cite this chapter

Rashidi, A., Mohammadzadeh, F., Sadegh Hassani, S. (2018). Hydrodesulfurization (HDS) Process Based on Nano-catalysts: The Role of Supports. 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_7

Download citation

  • DOI: https://doi.org/10.1007/978-3-319-60630-9_7

  • Published:

  • Publisher Name: Springer, Cham

  • Print ISBN: 978-3-319-60629-3

  • Online ISBN: 978-3-319-60630-9

  • eBook Packages: EngineeringEngineering (R0)

Publish with us

Policies and ethics

Search

Navigation