Characterization of Fresh and Regenerated Industrial Hydrocracking Catalysts; Study Causes of Deactivation

Document Type : Research Article

Authors

1 Chemical Engineering Department, Faculty of Engineering, University of Sistan and Baluchestan, PO Box 98164-161 Zahedan, I.R. IRAN

2 Process Engineer and Project Supervisor, Reserch and Development Department, Abadan Oil Refining Company, PO Box 6316953111 Abadan, I.R. IRAN

Abstract

In this investigation, fresh and regenerated Ni-W-Alumina-Zeolite industrial hydrocracking catalysts are characterized via several analyzing methods, including XRF, XRD, BET adsorption, FT-IR, FESEM-EDS, and TGA-DTA to understand the phenomena affecting trend towards their deactivation. The XRD patterns represented the presence of main phases of Al2O3/Y-zeolite as support and NiWO4/WO3 as active compounds. For the catalysts subjected to a three-year reactor operation/regeneration cycle, the XRF analysis revealed elemental enhancement of Fe, Na, V, Pb, Sb, and S, mostly from an outsourced environment. The BET and BJH analyses represented cylindrical shape mesoporosity for the samples, while the total pore-specific surface area and volume were reduced from 287.73 m2/g  and 0.46 cm3/g to 160.84 m2/g and 0.40 cm3/g for fresh and regenerated samples, respectively. The latter results indicated possibly filling the pores with impurities and/or sintering of pores. By considering FESEM images, the smooth surface of the fresh sample and indented/corroded characteristics of the regenerated one were seen. The variety of analyses portrayed the increasing trend of the poisoning factors and the structural malfunction of the catalysts towards irreversible deactivation.

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Main Subjects


[1] Choudhary N., Saraf D., Hydrocracking: A Review, Ind. Eng. Chem. Prod. Res. Dev, 14(2): 74–83 (1975).
[2] Mohanty S., Kunzru D., Saraf D., Hydrocracking: A Review, Fuel, 69(12): 1467–1473 (1990).
[3] Sahu R., Song B.J., Im J.S., Jeon Y.P., Lee C.W., A Review Of Recent Advances In Catalytic Hydrocracking Of Heavy Residues, Ind. Eng. Chem, 27: 12–24 (1975).
[6] Ward J.W., Hydrocracking Processes and Catalysts, Fuel Process. Technol, 35(1-2): 55–85 (1993).
[8] Minderhoud J., Van Veen J., First-Stage Hydrocracking: Process and Catalytic Aspects, Fuel Process. Technol, 35(1-2): 87–110 (1993).
[9] Furimsky E., Selection of Catalysts and Reactors for Hydroprocessing, Appl. Catal. A Gen, 171(2): 177–206 (1998).
[10] Ferraz S.G., Zotin F.M.Z., Araujo L.R.R., Zotin J.L., Influence of Support Acidity of NiMoS Catalysts in the Activity for Hydrogenation and Hydrocracking ofTetralin, Appl. Catal. A Gen, 384(1-2): 51–57 (2010).
[11] Pookote S., Dranoff J., Butt J., In Hydrogenation Function of Fresh and Deactivated Hydrocracking Catalysts: Cyclohexene Hydrogenation, ACS Symp. Ser., Chem. React. Engng l, ACS, 24: 283-295 (1982).
[12] Fatemi S., Abolhamd G., Mousavian S.M.A., Mortazavi Y.E., The Effect of Coking on Kinetics of HDS Reaction under Steady and Transient States, Iran. J. Chem. Chem. Eng. (IJCCE), 23(2): 1-11 (2004).
[13] Gosselink J., Stork W., Coping with Catalyst Deactivation in Hydrocracking: Catalyst and Process Development, Ind. Eng. Chem. Res, 36(8): 3354–3359 (1997).
[14] Furimsky E., Massoth F.E., Deactivation of Hydroprocessing Catalysts, Catal. Today, 52(4): 381–495 (1999).
[15] Dufresne P., Hydroprocessing Catalysts Regeneration and Recycling, Appl. Catal. A Gen, 322: 67–75 (2007).
[16] Barghi B., Fattahi M., Khorasheh F., Kinetic Modeling of Propane Dehydrogenation over an Industrial Catalyst in the Presence of Oxygenated Compounds, React. Kinet., Mech. Catal, 107(1): 141-155 (2012).
[17] Fattahi M., Khorasheh F., Sahebdelfar S., Zangeneh F.T., Ganji K., Saeedizad M., The Effect of Oxygenate Additives on the Performance of Pt–Sn/γ-Al2O3 Catalyst in the Propane Dehydrogenation Process, Sci. Iran, 18(6): 1377-1383 (2011).
[18] Vogelaar B.M., Gast J., Douma E.M., van Langeveld A.D., Eijsbouts S., Moulijn J.A., Coke Deposition Profiles During Artificial Aging of Hydroprocessing Catalysts, Ind. Eng. Chem. Res, 46(2): 421–429 (2007).
[19] Castaño P., Gutiérrez A., Hita I., Arandes J.M., Aguayo A.s.T., Bilbao J., Deactivating Species Deposited on Pt–Pd Catalysts in the Hydrocracking of Light-Cycle Oil, Energy and Fuels, 26(3): 1509–1519 (2012).
[20] Sahoo S.K., Ray S.S., Singh I., Structural Characterization of Coke on Spent Hydroprocessing Catalysts Used for Processing of Vacuum Gas Oils, Appl. Catal. A Gen, 278(1): 83–91 (2004).
[21] Scherzer J., Gruia, A.J., "Hydrocracking Science and Technology", Crc Press, Des Plaines, Illinois (1996).
[22] Samavati A., Fattahi M., Khorasheh F., Modeling of Pt-Sn/γ-Al2O3 Deactivation in Propane Dehydrogenation with Oxygenated Additives, Korean J. Chem. Eng., 30(1): 55-61 (2013).
[26] Dufresne P., Brahma N., Off‐site Regeneration of Hydroprocessing Catalysts, Bull. Des Sociétés Chim. Belges, 104(4-5): 339–346 (1995).
[27] Teixeira da Silva V., Lima F., Dieguez L., Schmal M., Regeneration of a Deactivated Hydrotreating Catalyst, Ind. Eng. Chem. Res, 37(3): 882–886 (1998).
[28] Brunauer S., Emmett P.H., Teller E., Adsorption of Gases in Multimolecular Layers, J. Am. Chem. Soc, 60(2): 309–319 (1938).
[29] Barrett E.P., Joyner L.G., Halenda P.P., The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms, Am. Chem. Soc, 73(1): 373–380 (1951).
[30] Lazić M., Hadnađev M., Bošković G., Obadović D., Kiss E., Influence of Excess Sodium Ions on the Specific Surface Area Formation in a NiO-Al2O3 Catalyst Prepared by Different Methods, Sci. Sinter, 40(2): 175–184 (2008).
[31] Boscagli C.,Yang C., Welle A., Wang W., Behrens S., Raffelt K., Grunwaldt J-D., Effect of Pyrolysis Oil Components on the Activity and Selectivity of Nickel-Based Catalysts During Hydrotreatment, Appl. Catal. A Gen, 544: 161-172 (2017).
[32] Kohli K., Prajapati R., Maity S., Sau M., Garg M., Deactivation of Hydrotreating Catalyst By Metals in Resin and Asphaltene Parts of Heavy Oil and Residues, Fuel, 175: 264-273 (2016).
[33] Subsadsana M., Kham-or P., Sangdara P., Suwannasom P., Ruangviriyachai C., Synthesis and Catalytic Performance of Bimetallic NiMo-and NiW-ZSM-5/MCM-41 Composites for Production of Liquid biofuels, J. Fuel Chem. Technol, 45(7): 805-816 (2017).
[34] Adhikari S., Fernando S.D., To S.F., Bricka R.M., Steele P.H., Haryanto A., Conversion of Glycerol
to Hydrogen via a Steam Reforming Process over Nickel Catalysts
, Energy and Fuels, 22(2): 1220–1226 (2008).
[35] Xiao Z-q., Mao J.-W., Ji J.-b., Sha R.-y., Yu F., Chuang X., Preparation of Nano-Scale Nickel-Tungsten Catalysts by pH Value Control and Application in Hydrogenolysis of Cellulose to Polyols, J. Fuel Chem. Technol, 45(6): 641-650 (2017).
[36] Xiao Z-q., Zhang Q., Wang X.-L., Ge Q., Gai X.-k., Mao J.-w., Ji J.-b., Organic Nitrogen Promotes Stability of Metallic Catalysts In Conversion of Bamboo Pulp to Low Carbon Polyols, J. Fuel Chem. Technol, 47(6): 675-687 (2019).
[38] Ramesh A., Tamizhdurai P., Krishnan P.S., Ponnusamy V.K., Sakthinathan S., Shanthi K., Catalytic Transformation of Non-Edible Oils to Biofuels Through Hydrodeoxygenation Using Mo-Ni/Mesoporous Alumina-Silica Catalysts, Fuel, 262: 116494 (2020).
[41] Bozdag A.A., Kaynar A.D., Dogu T., Sezgi N., Development of Ceria and Tungsten Promoted Nickel/Alumina Catalysts for Steam Reforming of Diesel, Chem. Eng. J, 377: 120274 (2019).
[43] Wang L., Zhu S., Marinkovic N., Kattel S., Shao M., Yang B., Chen J.G., Insight into the Synergistic Effect Between Nickel and Tungsten Carbide for Catalyzing Urea Electrooxidation in Alkaline Electrolyte, Appl. Catal., B, 232: 365-370 (2018).
[44] El-Kemary M., Nagy N., El-Mehasseb I., Nickel Oxide Nanoparticles: Synthesis and Spectral Studies Of Interactions with Glucose, Mater. Sci. Semicond. Process, 16(6): 1747-1752 (2013).
[45] Díaz-Reyes J., Dorantes-García V., Pérez-Benítez A., Balderas-López J.A., Obtaining of Films of Tungsten Trioxide (WO3) by Resistive Heating of a Tungsten Filament, Superficies Vacio, 21(2): 12-17 (2008).
[46] Cardoso F.P., Nogueira A.E, Patrício P.S.O, and Oliveira L.C.A., Effect of Tungsten Doping on Catalytic Properties of Niobium Oxide, J. Braz. Chem. Soc, 23(4): 702-709 (2012).
[47] Atanasova P., Tabakova T., Vladov C., Halachev T., Agudo A.L., Effect of Phosphorus Concentration and Method of Preparation on the Structure of the Oxide Form of Phosphorus-Nickel-Tungsten/Alumina Hydrotreating Catalysts, Appl. Catal. A Gen, 161(1-2): 105-119 (1997).
[48] Rahdar A., Aliahmad M., Azizi Y., NiO Nanoparticles: Synthesis and Characterization, J. Nanostruct, 5(2): 145-151 (2015).
[49] Davar F., Fereshteh Z., Salavati-Niasari M., Nanoparticles Ni and NiO: Synthesis, Characterization and Magnetic Properties, J. Alloys Compd, 476(1-2): 797-801 (2009).
[50] Hernández I.P., Gochi-Ponce Y., Larios J.L.C., Fernández A.M., Steam Reforming of Ethanol over Nickel-Tungsten Catalyst, Int. J. Hydrogen Energy, 35(21): 12098-12104 (2010).
[51] Pereyma V.Y., Klimov O.V., Prosvirin I.P., Gerasimov E.Y., Yashnik S.A., Noskov A.S, Effect of Thermal Treatment on Morphology and Catalytic Performance of NiW/Al2O3 Catalysts Prepared Using Citric Acid as Chelating Agent, Catal. Today, 305: 162-170 (2018).