Enhanced HDN Performance of Al, Zr and Ti Modified NiW Catalysts by Using Co-Impregnation Method

Document Type: Research Article


1 College of Chemistry and Chemical Engineering, Jinzhong University, Jinzhong 030600, P.R. CHINA

2 College of chemistry and chemical engineering, Jinzhong University, Jinzhong 030600, P.R. CHINA

3 College of Environment and Safety, Taiyuan University of Science and Technology, Taiyuan 030024, P.R. CHINA

4 College of chemistry and chemical engineering, Xi’an University of Petroleum, Xi’an 710065, P.R. CHINA

5 Laboratory of Applied Catalysis and Green Chemical Engineering, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, P.R. CHINA


The Al, Zr, and Ti modified MCM-41 materials were prepared by the post-synthesis method, and then the Ni-W species were introduced on them by using the co-impregnation method in order to obtain high-performance hydrodenitrogenation (HDN) catalysts. The activity of the catalysts was evaluated by the HDN reaction of quinoline. The optimum HDN activity was observed on the catalyst supported on the Al modified MCM-41. The high performance of the NiW/Al catalyst was due to the higher dispersion of Ni, W species, the more density of acid sites, the more appropriate nature of W species, and the lower reduction temperature of W species. Moreover, the catalysts prepared by co-impregnation method showed better performance than the catalysts prepared by the sequential impregnation method in the HDN of quinoline.


Main Subjects

[1] Kanda Y., Temma C., Nakata, K., Kobayashi T., Sugioka M., Uemichi Y., Preparation and Performance of Noble Metal Phosphides Supported on Silica as New Hydrodesulfurization Catalysts, Appl. Catal. A: Gen., 386: 171-178 (2010). 

[2] Yu G.L., Zhou Y.S., Wei Q., Tao X.J., Cui Q.Y., A Novel Method For Preparing Well Dispersed and Highly Sulfided Niw Hydrodenitrogenation Catalyst, Catal. Commun., 23: 48-53 (2012).

[3] Klimova T., Gutiérrez O., Lizama L., Amezcua J., Advantages of ZrO2- and TiO2–SBA-15 Mesostructured Supports for Hydrodesulfurization Catalysts over Pure TiO2, ZrO2 and SBA-15, Micropor. Mater., 133: 91-99 (2010). 

[4] Gutiérrez O.Y., Ayala E., Puente I., Klimova T., Application of New ZrO2-SBA-15 Materials as Catalytic Supports: Study of Intrinsic Activity of Mo Catalysts in Deep HDS, Chem. Eng. Comm., 196: 1163-1177 (2009).

[5] Herrera J.M., Reyes J., Roquero P., Klimova T., New hydrotreating NiMo Catalysts Supported on MCM-41 Modified with Phosphorus, Micropor. Mater., 83: 283-291 (2005).

[6] Silva-Rodrigo R., Calderón-Salas C., Melo-Banda J.A., Domínguez J.M., Vázquez-Rodríguez  A. Synthesis, Characterization and Comparison of Catalytic Properties of NiMo- and NiW/Ti-MCM-41 catalysts for HDS of Thiophene and HVGO, Catal. Today, 98: 123-129 (2004).

[7] Klimova T., Calderón M., Ramírez J., Ni and Mo Interaction with Al-Containing MCM-41 Support and Its Effect on the Catalytic Behavior in DBT Hydrodesulfurization, Appl. Catal. A: Gen., 24029-40 (2003).

[8] Rodríguez-Castellõn E., Jimenez-Lõpez A., Eliche-Quesada D., Nickel and Cobalt Promoted Tungsten and Molybdenum Sulfide Mesoporous Catalysts tor Hydrodesulfurization, Fuel, 87: 1195-1206 (2008).

[9] Guo F., Guo S., Wei X.X., Wang X., Xiang H., Qiu Z., Zhao L.,MCM-41 Supports Modified by Al, Zr and Ti for NiW Hydrodenitrogenation Catalysts, Catal. Lett., 144: 1584-1593 (2014).

[10] Salerno P., Mendioroz S., López Agudo A., Al-Pillared Montmorillonite-Based Nimo Catalysts for HDS and HDN of Gas Oil: Influence of the Method and Order of Mo And Ni Impregnation, Appl. Catal. A: Gen., 259: 17-28 (2004).

[11] Sardhar Basha S.J., Vijayan P., Suresh C., Santhanaraj D., Shanthi K.,Effect of Order of Impregnation of Mo and Ni on the Hydrodenitrogenation Activity of Nio-Moo3/Almcm-41 Catalyst, Ind. Eng. Chem. Res., 48: 2774-2780 (2009).

[12] Khder A.E.R.S., Hassan H.M.A., El-Shall M.S. Acid Catalyzed Organic Transformations by Heteropoly Tungstophosphoric Acid Supported on MCM-41, Appl. Catal. A: Gen.,411-412: 77-86 (2012).

[13] Carriazo D., Domingo C., Martín C., Rives V.,Pmo or PW Heteropoly Acids Supported on MCM-41 Silica Nanoparticles: Characterisation and FT-IR Study of the Adsorption of 2-Butanol, J. Solid State Chem., 181: 2046-2057 (2008).

[14] Méndez F.J., Llanos A., Echeverría M., Jáuregui R., Villasana Y., Díza Y., Liendo-Polanco G., Ramos-García M.A., Zoltan T., Brito J.L., Mesoporous Catalysts Based on Keggin-Type Heteropolyacids Supported on MCM-41 and Their Application in Thiophene Hydrodesulfurization, Fuel, 110: 249-258 (2013).

[15] Palcheva R., Spojakina A., Dimitrov L., Jiratova K., 12-Tungstophosphoric Heteropolyacid Supported
on Modified SBA-15 as Catalyst in HDS of Thiophene
, Micropor. Mater., 122: 128-134 (2009).

[16] Luo Y., Hou Z., Li R., Zheng X., Rapid Synthesis of Ordered Mesoporous Silica with the Aid of Heteropoly Acids, Micropor. Mater., 109: 585-590 (2008).

[17] Vradman L., Landau M.V., Kantorovich D., Koltypin Y., Gedanken A., Evaluation of Metal Oxide Phase Assembling Mode Inside the Nanotubular Pores of Mesostructured Silica, Micropor. Mater., 79: 307-318 (2009).

[20] Xiao T., Wang H., York A.P.E., Williams V.C., Green M.L.H.,Preparation of Nickel–Tungsten Bimetallic Carbide Catalysts, J. Catal., 209: 318-330 (2002).

[21] Tayeb K.B., Lamonier C., Lancelot C., Fournier M., Payen E., Bonduelle A., Bertoncini F., Study Of The Active Phase of Niw Hydrocracking Sulfided Catalysts Obtained from an Innovative Heteropolyanion Based Preparation, Catal. Today, 150: 207-212 (2010).

[22] Lei Z., Gao L., Shui H., Chen W., Wang Z., Ren S., Hydrotreatment of Heavy Oil from a Direct Coal Liquefaction Process on Sulfided Ni–W/SBA-15 Catalysts, Fuel Process. Technol.,92: 2055-2060 (2011).

[23] Ding L., Zheng Y., Zhang Z., Ring Z., Chen J., Hydrotreating of Light Cycle Oil Using Wni Catalysts Containing Hydrothermally and Chemically Treated Zeolite Y, Catal. Today, 125: 229-238 (2007).

[24] Salvatl L., Makovsky L.E., Stencel J.M., Brown F.R., Hercules D.M., Surface Spectroscopic Study of Tungsten-Alumina Catalysts Using X-Ray Photoelectron, Ion Scattering, and Raman Spectroscopies, J. Phys. Chem., 85: 3700-3707 (1981).

[25] Wan G., Duan A., Zhang Y., Zhao Z., Jiang G., Zhang D., Liu J., Chung K., Niw/AMBT Catalysts for the Production of Ultra-Low Sulfur Diesel, Catal. Today, 158: 521-529 (2010).

[26] Lizama L.Y., Klimova T.E., SBA-15 Modified with Al, Ti, or Zr as Supports for Highly Active Niw Catalysts for HDS, J. Mater. Sci., 44: 6617-6628 (2009).

[27] Fan Y., Bao X., Wang H., Chen C., Shi G., A Surfactant-Assisted Hydrothermal Deposition Method for Preparing Highly Dispersed W/Γ-Al2O3 Hydrodenitrogenation Catalyst, J. Catal., 245: 477-481 (2007).

[28] Saadatjou N., Jafari A., Sahebdelfar S., Synthesis and Characterization of Ru/Al2O3 Nanocatalyst
for Ammonia Synthesis
, Iran. J. Chem.Chem.Eng. (IJCCE), 34(1): 1-9 (2015).

[29] Wei Q., Zhou Y., Wen S., Xu C., Preparation and Properties of Nickel Preimpregnated CYCTS Supports for Hydrotreating Coker Gas Oil, Catal. Today,149: 76-81 (2010).

Volume 39, Issue 2 - Serial Number 100
March and April 2020
Pages 69-81