The time-on-stream stability of some selected bifunctional nanoporous-based catalysts in n-heptane hydroisomerisation

Applied Petrochemical Research - Tập 4 - Trang 189-207 - 2013
Faisal M. Alotaibi1, Raed H. Abudawood2, Hamid A. Al-Megren1, Mohammed C. Al-Kinany1, Arthur A. Garforth3
1Petrochemicals Research Institute, King Abdulazeez City for Science and Technology (KACST), Riyadh, Saudi Arabia
2Research and Development Center Saudi Aramco, Dhahran, Saudi Arabia
3School of Chemical Engineering and Analytical Science, The University of Manchester, Manchester, UK

Tóm tắt

In this work, some commercial nanoporous-based catalysts, such as USY, beta and mordenite zeolites loaded with Platinum metal acting as bifunctional catalysts, were used for hydroisomerisation experiments in a fixed-bed reactor at the atmospheric pressure and at feed space time 5.12 h−1 to hydroisomerise n-heptane over a temperature range of 210–270 °C. The study aimed to evaluate the changes with time-on-stream in the catalytic activity, product selectivity and manner of deactivation of metal-loaded zeolite catalysts, at constant contact time of 5.13 h−1 and a hydrogen-to-n-heptane molar ratio fixed at 9. Various analytical techniques were used to characterise fresh and aged catalysts. Results show that pore architecture is the most important factor affecting coke formation and deactivation in zeolite catalysts, and those catalysts with three-dimensional pore structures lacking cavities or cages were best able to resist deactivation. In addition, it was found that those catalysts with high Si/Al ratios and those which had been acid-leached or steamed showed better activity, higher selectivity towards isomeric products and better time stability. Moreover, the balance between the number of metal sites and the number of acid sites played an important role in determining the activity, selectivity and stability of the bifunctional catalysts.

Tài liệu tham khảo

Guisnet M, Costa L, Ribeiro FR (2009) Prevention of zeolite deactivation by coking. J Mol Catal A Chem 305:69–83 Gopal S (2003) Synthesis, Modification, Characterization and Catalytic Studies of Zeolite based Bifunctional Catalysts for Hydroisomerization Reactions. Dissertation, University of Cincinnati, Cincinnati, Ohio Rollmann LD (1977) Systematics of shape selectivity in common zeolites. J Catal 47:113–121 Rollmann LD, Walsh DE (1979) Shape selectivity and carbon formation in zeolites. J Catal 56:139–140 Guisnet M, Magnoux P (1989) Coking and deactivation of zeolites—influence of the pore structure. Appl Catal 54:1–27 Guisnet M, Magnoux P (1992) Composition of the carbonaceous compounds responsible for zeolite deactivation—modes of formation. Zeolite Microporous Solids Synth Struct React 352:437–456 Gopal S, Smirniotis PG (2002) Deactivation behavior of bifunctional Pt/H-zeolite catalysts during cyclopentane hydroconversion. J Catal 205:231–243 Zhang W, Smirniotis PG (1998) Dealuminated zeolite-based composite catalysts for reforming of an industrial naphthene-rich feedstock. Appl Catal A 168:113–130 Walsh DE, Rollmann LD (1977) Radiotracer experiments on carbon formation in zeolites. Effect of aromatic content of hydrocarbon mixtures. J Catal 49:367–375 Stöcker M (2005) Gas phase catalysis by zeolites. Microporous Mesoporous Mater 82:257–292 Sie ST (2008) Isomerization. In: Ertl G, Knözinger H, Schueth F, Weitkamp J (eds) Handbook of Heterogeneous Catalysis, 2nd edn. Wiley-VCH Verlag GmbH, Weinheim, pp 2809–2829 Akhmedov VM, Al-Khowaiter SH (2007) Recent advances and future aspects in the selective isomerization of high n-alkanes. Catal Rev 49:33–139 Guisnet M, Ribeiro FR (2011) Deactivation and regeneration of zeolite catalysts. Imperial College Press, London Zeolyst International. http://www.zeolyst.com/our-products/standard-zeolite-powders/zeolite-y.aspx. Accessed 29 May 2011 Tosoh Corporation. http://www.tosoh.com/Products/tcdzeo.htm#hzc. Accessed 26 June 2011 Rawlence DJ, Earl GJ (1993) Materials having novel structure factors for catalysis of hydrocarbon transformation and development of selective processes. BRITE-EURAM 4633, 5th Meeting Report, Elf Solaize Abudawood R, Alotaibi F, Garforth A (2011) Hydroisomerization of n-heptane over Pt-loaded USY zeolites. Effect of steaming, dealumination and the resulting structure on catalytic properties. Ind Eng Chem Res 50:9918–9924 Abudawood R (2010) Hydroisomerization of Alkanes over Metal-Loaded Zeolite Catalysts. Dissertation, University of Manchester Weisz PB, Frilette VJ (2002) Intracrystalline and molecular-shape-selective catalysis by zeolite salts. J Phys Chem 64:382 Remy MJ, Stanica D, Poncelet G, Feijen EJP, Grobet PJ, Martens JA, Jacobs PA (1996) Dealuminated H–Y zeolites: relation between physicochemical properties and catalytic activity in heptane and decane isomerization. J Phys Chem 100:12440–12447 Treacy MMJ, Higgins JB (2001) Collection of simulated XRD powder patterns for zeolites. Elsevier, Amsterdam Guisnet M, Ribeiro FR (2011) Deactivation and regeneration of zeolite catalysts. Imperial College Press, London, pp 204–205 Guisnet M, Alvarez F, Giannetto G, Perot G (1987) Hydroisomerization and hydrocracking of n-heptane on PtHzeolites. Effect of the porosity and of the distribution of metallic and acid sites. Catal Today l:415–433 Alvarez F, Rebeiro FR, Perot G, Thomazeau C, Guisnet M (1996) Hydroisomerization and hydrocracking of alkanes—7. Influence of the balance between acid and hydrogenating functions on the transformation of n-decane on PtHY catalysts. J Catal 162:179–189 Morin S, Ayrault P, Gnep NS, Guisnet M (1998) Influence of the framework composition of commercial HFAU zeolites on their activity and selectivity in m-xylene transformation. Appl Catal A 166:281–292 Alvarez F, Giannetto G, Guisnet M, Perot G (1987) Hydroisomerization and hydrocracking of n-alkanes: 2. n-Heptane transformation on a Pt-dealuminated Y zeolite—comparison with a Pt-Y zeolite. Appl Catal 34:353–365 Gauw F (2002) Kinetic Studies of Alkane Hydroisomerization over Solid Acid Catalysts. Dissertation, Eindhoven University of Technology Guisnet M, Ribeiro FR (2011) Deactivation and regeneration of zeolite catalysts. Imperial College Press, London, p 27 Petushkov A, Giorvanni M, Larsen SC (2011) From nanoparticles to hierarchical structures: controlling the morphology of zeolite beta. Microporous Mesoporous Mater 143:97–910 Trombetta M, Busca G, Storaro L, Lenarda M, Casagrande M, Zambon A (2000) Surface acidity modifications induced by thermal treatments and acid leaching on microcrystalline H-BEA zeolite. A FTIR, XRD and MAS-NMR study. Phys Chem Chem Phys 2:3529–3537 Maier SM, Jentys A, Lercher JA (2011) Steaming of zeolite BEA and its effect on acidity: a comparative NMR and IR spectroscopic study. J Phys Chem 15:8005–8013 Park JN, Wang J, Hong SI, Lee CW (2005) Effect of dealumination of zeolite catalysts on methylation of 2-methylnaphthalene in a high-pressure fixed-bed flow reactor. Appl Catal A 292:68–75 Jia C, Massiani P, Barthomeuf DJ (1993) Characterization by infrared and nuclear magnetic resonance spectroscopies of calcined beta zeolite. Chem Soc Faraday Trans 89:3659–3665 Blomsma E, Martens JA, Jacobs PA (1997) Isomerization and hydrocracking of heptane over bimetallic bifunctional PtPd/H-beta and PtPd/USY zeolite catalysts. J Catal 165:241–248 Bowen TC, Vane LM (2006) Ethanol, acetic acid, and water adsorption from binary and ternary liquid mixtures on high-silica zeolites. Langmuir 22:3721–3727 Van Laak ANC, Sagala SL, Zečević J, Friedrich H, de Jongh PE, de Jong KP (2010) Mesoporous mordenites obtained by sequential acid and alkaline treatments—catalysts for cumene production with enhanced accessibility. J Catal 276:170–180 Zhang L, van Laak ANC, de Jongh PE, de Jongh KP (2009) Synthesis of large mordenite crystals with different aspect ratios. Microporous Mesoporous Mater 126:115–124 Van Laak ANC (2011) Post-Synthesis Modifications on Zeolites for Improved Accessibility and Catalytic Performance. Dissertation, Utrecht University Wang ZB, Kamo A, Yoneda T, Komatsu T, Yashima T (1997) Isomerization of n-heptane over Pt-loaded zeolite/beta catalysts. Appl Catal 159:119–132 Lee JK, Rhee HK (1997) Characteristics of Pt/H-beta and Pt/H-mordenite catalysts for the isomerization of n-hexane. Catal Today 38:235–242 Van Donk S (2002). Adsorption, Diffusion and Reaction Studies of Hydrocarbons on Zeolite Catalysts. Dissertation, Utrecht University Chica A, Corma A, Miguel PJ (2001) Isomerization of C5–C7 n-alkanes on unidirectional large pore zeolites: activity, selectivity and adsorption features. Catal Today 65:101–110