Abstract
The dynamics of the activity and selectivity of bifunctional platinum tungstated zirconia PtWZ catalyst in the hydroisomerization of n-heptane and heptane–benzene mixture is discussed in the paper. The change in the properties of the catalyst before and after reaction were characterized using different techniques. The catalyst showed high efficiency for the hydroisomerization of heptane and heptane–benzene mixture, however, deactivation occurred with time on stream, more significantly when benzene was present in the reaction mixture. The carbonaceous matter was deposited on the catalyst (up to 0.8%) during the hydroisomerization reaction. Predominantly aliphatic carbonaceous «poly-CxHy» species, much less oxidized and little aromatic «graphite-like» species were identified by XPS spectra on the catalyst after the heptane isomerization. In the presence of benzene, the formation of «graphite-like» matter increased progressively as temperature increased. However, no appreciable changes in the bulk properties of the t-ZrO2 matrix (phase composition, specific surface area, pore volume, pore size distribution) and in the state of platinum component were revealed, though an increased extent of W6+ to W5+ reduction was detected by XPS spectra irrespectively of the reaction conditions. The deactivation of the PtWZ catalyst was suggested to result from the blocking the active centers by carbonaceous deposits, the deactivation of the acidic centers being more pronounced as compared to metallic ones. All the carbonaceous deposits were burned-off completely below 450–500 °C.
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Anderson GC, Rosin RR, Stine MA, Hunter MJ (2004) NPRA Annual Meeting, M-04-46
Grau JM, Vera CR, Benitez VM, Yori JC (2008) Energy Fuels 22:1680–1686
Benitez VM, Grau JM, Yori JC, Pieck CL, Vera CR (2006) Energy Fuels 20:1791–1798
Shakun AN, Fedorova ML, Karpenko TV, Demidova EV (2016) Technopolis XXI 33:24–26
Hattori H, Ono Y (2015) Solid acid catalysis: from fundamentals to applications. Pan Stanford Publishing, Singapore
Kuznetsova LI, Kazbanova AV, Kuznetsov PN (2012) Pet Chem 52(2):86–90
Ahmad R, Melsheimer J, Jentoft FC, Schlogl R (2003) J Catal 218:365–374
Grau JM, Vera CR, Parera JM (2002) Appl Catal A 227:217–230
Resofszki G, Muhler M, Sprenger S, Wild U, Paal Z (2003) Appl Catal A 240:71–81
Miyaji A, Ohnishi R, Okuhara T (2004) Appl Catal A 262:143–148
Okuhara T (2004) J Jpn Petrol Inst 47(1):1–10
Busto M, Grau JM, Vera CR (2010) Appl Catal A 387:35–44
Smolikov MD, Shkurenok VA, Yablokova SS, Kir’yanov DI, Paukshtis EA, Leontieva NN, Belyi AS, Drozdov VA (2016) Catal Ind 16(5):51–59
Triwahyono S, Yamada T, Hattori H (2003) Appl Catal A 242:101–109
Barton DV, Soled SL, Meitzner GD, Fuentes GA, Iglesia E (1999) J Catal 181:57–72
Ross-Medgaarden EI, Knowles WV, Kim T, Wong MS, Zhou W, Kiely C, Wachs I (2008) J Catal 256:108–125
Cortes-Jacome MA, Toledo-Antonio JA, Armendariz H, Hernandez I, Bokhimi X (2002) J Solid State Chem 164:339–344
Cortes-Jacome MA, Angeles-Chavez C, Lopes-Salinas E (2007) Appl Catal A 318:178–189
Cortes-Jacome MA, Angeles-Chavez C, Bokhimi X, Toledo-Antonio JA (2006) J Solid State Chem 179:2663–2673
Kuznetsov PN, Kazbanova AV, Kuznetsova LI, Kovalchuk VI, Mikhlin YL (2014) Reac Kinet Mech Cat 113:69–84
Kuznetsov PN, Kazbanova AV, Kuznetsova LI, Solovyov LA (2012) Russ J Phys Chem A 86:1609–1612
Song Y, Zhang J, Zhou X, Wang JA, Xu L, Yu G (2011) Catal Today 166:67–72
Kuba S, Lukinskas P, Ahmad R, Jentoft FC, Grasselli RK, Gates BC, Knozinger H (2003) J Catal 219:376–388
Occhiuzzi M, Cordischi D, Gazzoli D, Valigi M, Conceptiòn Heydorn P (2004) Appl Catal A 269:169–177
Ebitani K, Konishi J, Hattori H (1991) J Catal 130:257–267
Vaudagna CSR, Comelli RA, Fígoli NS (1997) Catal Lett 47:259–264
Adeeva V, de Haan JW, Jänchen J, Lei GD, Schünemann G, van de Ven LJM, Sachtler WMH, van Santen RA (1995) J Catal 151:364–372
Yang YC, Weng HS (2009) J Mol Catal A 304:65–70
Manoli JM, Potvin C, Muhler M, Wild U, Resofszki G, Buchholz T, Paal Z (1998) J Catal 178:338–351
Paal Z, Wild U, Muhler M, Manoli JM, Potvin C, Buchholz T, Sprenger S, Resofszki G (1999) Appl Catal A 188:257–266
Grau JM, Yori JC, Parera JM (2001) Appl Catal A 213:247–257
Arribas MA, Márquez F, Martínez A (2000) J Catal 190:309–319
Comelli RA, Canavese SA, Querini CA, Figoli NS (1999) Appl Catal A 182:275–283
Kuznetsova LN, Kazbanova AV, Kuznetsov PN, Tarasova LS (2015) Pet Chem 55(1):57–62
Oka, Nishiguchi T, Kanai H, Utani K, Imamura S (2006) Appl Catal A 309:187–191
Zhorov Yu M (1985) Thermodynamics of chemical processes. Petrochemical synthesis, petroleum refining, coal and natural gas. Khimiya, Moscow, p 464
Vaudagna SR, Canavese SA, Comelli RA, Figoli NS (1998) Appl Catal A 168:93–111
Paal Z, Schlogl R, Ertl G (1992) Catal Lett 12:331–344
Sayari A, Dicko A (1994) J Catal 145:561–564
Barbier J, Churin E, Parera JM, Riviere J (1985) React Kinet Catal Lett 29:323–330
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The authors thank Mrs. L. Tarasova, Krasnoyarsk regional center for collective use, SB of RAS, for differential scanning calorimetry measurements and useful discussion.
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Kuznetsov, P.N., Obukhova, A.V., Kuznetsova, L.I. et al. Dynamics of the Activity and Physicochemical Characteristics of Pt/WO4 2−–ZrO2 Catalysts in the Hydroisomerization of Heptane and Heptane–Benzene Mixtures. Catal Lett 147, 773–784 (2017). https://doi.org/10.1007/s10562-017-1980-1
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DOI: https://doi.org/10.1007/s10562-017-1980-1