Abstract
A platinum-substituted alumina-promoted sulfated zirconia (PtAu/SZA) was prepared and used for the conversion of isobutane to n-butane, aiming to optimize the ethylene feedstock in the steam thermal cracking process and increase the ethylene yield. PtAu bimetallic catalysts showed higher catalytic activity than Pt-alone catalyst, and the enhancement is attributed to PtAu alloying. By diluting and separating Pt with PtAu alloy agglomerates, continuous Pt agglomerates disappear and hydrogen dissociation on Pt is enhanced. In addition, the reduction temperature of Pt is decreased with the increase in Au content, while the reduction temperature of sulfate was increased which will delay the loss of sulfate according to the results of H2-TPR and NH3-TPD. However, the acidity of the catalyst decreases with the increase in Au, which is due to that PtAu alloy covers the acid sites on the surface. Overall, we found that the Pt0.5Au0.3/SZA showed the highest yield to n-butane (34.69%).
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Ahmed MA (2011) Surface characterization and catalytic activity of sulfated-hafnia promoted zirconia catalysts for n-butane isomerization. Fuel Process Technol 92:1121–1128. https://doi.org/10.1016/j.fuproc.2011.01.008
Alazman A, Belic D, Kozhevnikova EF, Kozhevnikov LV (2018) Isomerisation of, n-hexane over bifunctional Pt-heteropoly acid catalyst: enhancing effect of Au. J Catal 357:80–89. https://doi.org/10.1016/j.jcat.2017.11.001
Alazman A, Belic D, Alotaibi A, Kozhevnikova EF, Kozhevnikov LV (2019) Isomerization of cyclohexane over bifunctional Pt-, Au- and PtAu-heteropoly acid catalysts. ACS Catal. 9:5063–5073. https://doi.org/10.1021/acscatal.9b00592
Awadallah-F A, Hillman F, Al-Muhtaseb SA, Jeong H (2019) On the nanogate-opening pressures of copper-doped zeolitic imidazolate framework ZIF-8 for the adsorption of propane, propylene, isobutane, and n-butane. J Mater Sci 54:5513–5527. https://doi.org/10.1007/s10853-018-03249-y
Chen FR, Coudurier G, Joly JF, Vedrine JC (1993) Superacid and catalytic properties of sulfated zirconia. J Catal 143(1993):616–626. https://doi.org/10.1006/jcat.1993.1304
Clearfield A, Serrette GPD, Khazi-Syed AH (1994) Nature of hydrous zirconia and sulfated hydrous zirconia. Catal Today 20:295–312. https://doi.org/10.1016/0920-5861(94)80008-1
Coq B, Figueras F (2001) Bimetallic palladium catalysts: influence of the co-metal on the catalyst performance. J Mol Catal A Chem 173:117–134. https://doi.org/10.1016/S1381-1169(01)00148-0
Dzhikiya OV, Smolikov MD, Kazantsev KV, Yablokova SS (2017) A study of Pd/SO42−/ZrO2/Al2O3 catalysts in n-hexane isomerization. Inst Phys Conf Ser 1876:020009. https://doi.org/10.1063/1.4998829
Fogash KB, Hong Z, Dumesic JA (1998) Effects of isobutylene on isobutane isomerization over H-Mordenite. J Catal 173(2):519–529. https://doi.org/10.1006/jcat.1997.1948
Föttinger K, Kinger G, Vinek H (2004) In situ IR investigation of n-hexane isomerization over Pt containing sulfated zirconia. Appl Catal A 266:195–202. https://doi.org/10.1016/j.apcata.2004.02.020
Gao F, Goodman DW (2012) Pd–Au bimetallic catalysts: understanding alloy effects from planar models and (supported) nanoparticles. Chem So Rev 41:8009. https://doi.org/10.1039/c2cs35160a
Hagen DI (1976) Somorjai G A (1976) The effect of Au on hydrogenolysis, isomerization, and dehydrocyclization reactions on polycrystalline Pt and iridium foils. J Catal 41:466–481. https://doi.org/10.1016/0021-9517(76)90247-5
Han YF, Wang JH, Kumar D, Yan Z, Goodman DW (2005) A kinetic study of vinyl acetate synthesis over Pd-based catalysts: kinetics of vinyl acetate synthesis over Pd–Au/SiO2 and Pd/SiO2 catalysts. J Catal 232:467–475. https://doi.org/10.1016/j.jcat.2005.04.001
Han J, Jiang G, Han S, Liu J, Zhang Y, Liu Y (2016) The Fabrication of Ga2O3/ZSM-5 Hollow Fibers for Efficient Catalytic Conversion of n-Butane into Light Olefins and Aromatics. Catalysts 6(1):13. https://doi.org/10.3390/catal6010013
Hanrieder EK, Jentys A, Lercher JA (2016) Impact of alkali acetate promoters on the dynamic ordering of PdAu catalysts during vinyl acetate synthesis. J Catal 333:71–77. https://doi.org/10.1016/j.jcat.2015.10.019
Hino M, Kobayashi S, Arata K (1979) Solid Catalyst Treated with Anion. 2. Reactions of butane and isobutane catalyzed by Zirconium Oxide treated with sulfate Ion. Solid Superacid Catalyst. J Am Chem Soc. https://doi.org/10.1021/ja00515a051
Hörnström SE, Johansson L, Flodström A, Nyholm R, Schmidt-May J (1985) Surface and bulk core level binding energy shifts in Pt–Au alloys. Surf Sci 160:561–570. https://doi.org/10.1016/0039-6028(85)90794-0
Hou X, Qiu Y, Yuan E, Zhang X, Liu G (2017) SO42−/TiO2 promotion on HZSM-5 for catalytic cracking of paraffin. Appl Catal A 537:12–23. https://doi.org/10.1016/j.apcata.2017.03.002
Liu P, NøRskov JK (2001) Ligand and ensemble effects in adsorption on alloy surfaces. Phys Chem Chem Phys 3:3814–3818. https://doi.org/10.1039/b103525h
Ma ZM, Meng X, Liu NW (2018) Pd-Ni doped sulfated zirconia: study of hydrogen spillover and isomerization of N-hexane. Mol Catal 449:114–121. https://doi.org/10.1016/j.mcat.2018.02.003
Maiaa AJ, Oliveira BG, Esteves PM, Louisb B, Lamc YL, Pereira MM (2011) Isobutane and n-butane cracking on Ni-ZSM-5 catalyst: effect on light olefin formation. Appl Catal A. https://doi.org/10.1016/j.apcata.2011.06.014
Mcvicker GB, Kramer GM, Ziemiak JJ (1983) Conversion of isobutane over solid acids—a sensitive mechanistic probe reaction. J Catal 83(2):286–300. https://doi.org/10.1016/0021-9517(83)90055-6
Moreno JA, Poncelet G (2001) Isomerization of n-Butane over Sulfated Al- and Ga-Promoted Zirconium Oxide Catalysts. Influence of promoter and preparation method. J Catal 203(2):453–465. https://doi.org/10.1006/jcat.2001.3324
Nand S, Sarkar MK (1979) Kinetics of thermal cracking of light hydrocarbon mixture by pulsed microreactor. Chem Eng J 17(2):183–190. https://doi.org/10.1016/0300-9467(79)85012-1
Park HY, Jeon TY, Jang JH, Yoo SJ, Choi KH, Jung N, Chung YH, Ahn M, Cho YH, Lee KS, Sunga YE (2013) Enhancement of oxygen reduction reaction on PtAu nanoparticles via CO induced surface Pt enrichment. Appl Catal B Environ 129:375–381. https://doi.org/10.1016/j.apcatb.2012.09.041
Poole O, Alharbi K, Belic D, Belic D, Kozhevnikova EF, Kozhevnikov LV (2017) Hydrodeoxygenation of 3-pentanone over bifunctional Pt-heteropoly acid catalyst in the gas phase: enhancing effect of Au. Appl Catal B Environ 202:446–453. https://doi.org/10.1016/j.apcatb.2016.09.044
Rach E, Heitbaum J (1987) Electrochemically induced surface modifications of Pt–Au alloy. Electrochim Acta 32:1173–1180. https://doi.org/10.1016/0013-4686(87)80030-0
Rubin JN, Highlands N, Seufert FB (1980) Process for convertng unsaturated C4 Hydrocarbons into normal butane. US4191845
Schwartz TJ, Lyman SD, Motagamwala AH, Mellmer MA, Dumesic JA (2016) Selective hydrogenation of unsaturated carbon–carbon bonds in aromatic-containing platform molecules. ACS Catal 6:2047–2054. https://doi.org/10.1021/acscatal.6b00072
Seah M, Smith G, Anthony M (1990) AES: energy calibration of electron spectrometers. I—an absolute, traceable energy calibration and the provision of atomic reference line energies. Surf Interface Anal 15:293–308. https://doi.org/10.1002/sia.740150503
Song SX, Kydd RA (1998) Activation of sulfated zirconia catalysts Effect of water content on their activity in n-butane isomerization. J Chem Soc Faraday Trans 94:1333–1338. https://doi.org/10.1039/A706892A
Sun S, Zhang G, Geng D, Chen Y, Li R, Cai M (2011) A highly durable platinum nanocatalyst for proton exchange membrane fuel cells: multiarmed starlike nanowire single crystal. Angew Chem Int Ed. 50:4226. https://doi.org/10.1002/ange.201004631
Sun K, Wilson AR, Thompson ST, Lamb HH (2015) Catalytic Deoxygenation of Octanoic Acid over SupportedPalladium: effects of Particle Size and Alloying with Au. ACS Catal 5:1939–1948. https://doi.org/10.1021/cs501865n
Thommes M, Kaneko K, Neimark AV, Olivier JP, Rodriguez-Reinoso F, Rouquerol J, Sing KSW (2016) Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl Chem. https://doi.org/10.1515/ci-2016-0119
Venezia AM, Parola VL, Nicolı̀ V, Deganello G (2002) Effect of Au on the HDS activity of supported palladium catalysts. J Catal 212:56–62. https://doi.org/10.1006/jcat.2002.3778
Venezia AM, Parola VL, Deganello G, Pawelec B, Fierro JLG (2003) Synergetic effect of Au in Au/Pd catalysts during hydrodesulfurization reactions of model compounds. J Catal 215:317–325. https://doi.org/10.1016/S0021-9517(03)00005-8
Vera CR, Pieck CL, Shimizu K, Parera JM (2002) Tetragonal structure, anionic vacancies and catalytic activity of SO42−–ZrO2 catalysts for n-butane isomerization. Appl Catal A 230:137–151. https://doi.org/10.1016/S0926-860X(01)01002-X
Wang W, Chen CL, Xu NP, Mou CY (2002) Isomerization of n-butane by gallium-promoted sulfated zirconia supported on MCM-41. Geen Chem 4:257–260. https://doi.org/10.1039/b201361b
Wang P, Zhang J, Wang G, Li C, Yang C (2016a) Nature of active sites and deactivation mechanism for n-butane isomerization over alumina-promoted sulfated Zirconia. J Catal 338:124. https://doi.org/10.1016/j.jcat.2016.02.027
Wang PZ, Zhang JY, Han CY, Yang CH, Li CY (2016b) Effect of modification methods on the surface properties and n-butane isomerization performance of La/Ni-promoted SO42−/ZrO2–Al2O3. Appl Surf Sci 378:489–495. https://doi.org/10.1016/j.apsusc.2016.04.043
Wang PZ, Zhang MX, Zhang WF, Yang CH (2017a) Isomerization of n–Butane over SO42–/Al2O3–ZrO2 in a circulated fluidized bed reactor: prospects for commercial application. Ind Eng Chem Res 56:8456–8464. https://doi.org/10.1021/acs.iecr.7b01858
Wang ZP, Zhang WF, Zhang Q, Xu ZS, Yang CH, Li CY (2017b) Comparative study of n-butane isomerization over SO42−/ZrO2–Al2O3, and HZSM-5 zeolites at low reaction temperatures. Appl Catal A 550:98–104. https://doi.org/10.1016/j.apcata.2017.11.006
Wohlrab S, Meyer T, Stöhr M, Hecker C, Lubenau U, Oßmann A (2011) On the performance of customized MFI membranes for the separation of n-butane from methane. J Mater Sci 369:96–104. https://doi.org/10.1016/j.memsci.2010.11.052
Wu H, Pantaleo G, Parola VL, Venezia AM, Collard X, Aprile C, Liotta LF (2014) Bi- and trimetallic Ni catalysts over Al2O3 and Al2O3–MOx (M = Ce or Mg) oxides for methane dry reforming: Au and Pt additive effects. Appl Catal B Environ 156–157:350–361. https://doi.org/10.1016/j.apcatb.2014.03
Wulfers MJ, Jentoft FC (2015) Mechanism of n-butane skeletal isomerization on H-mordenite and Pt/H-mordenite. J Catal 330:507–519. https://doi.org/10.1016/j.jcat.2014.12.035
Xu BQ, Sachtler WMH (1997) Reduction of SO4 = Ions in Sulfated Zirconia Catalysts. J Catal 167(1):224–233. https://doi.org/10.1006/jcat.1997.1553
Song X, Sayari A (1996) Sulfated Zirconia-based strong solid-acid catalysts: recent progress. Catalysis reviews. Cat Rev Sci Eng 38(3):329–412. https://doi.org/10.1080/01614949608006462
Smolikov MD, Kazantsev KV, Zatolokina EV, Kir’yanov DI, Paukshtis EA, Belyi AS (2010) Study of n-hexane isomerization on Pt/SO42−/ZrO2/Al2O3, catalysts: effect of the state of Pt on catalytic and adsorption properties. Kinet Catal+ 51:584–594. https://doi.org/10.1134/S0023158410040191
Yang K, Li H, Zhao SQ, Lai SS, Lai WK, Lian YX, Fang WP (2018) Improvement of activity and stability of CuGa promoted sulfated zirconia catalyst for n-Butane isomerization. Ind Eng Chem Rese 57:3855–3865. https://doi.org/10.1021/acs.iecr.7b04590
Zhang Y, Huang Q, Zou Z, Yang J, Vogel W, Yang H (2010) Enhanced durability of Au cluster decorated pt nanoparticles for the oxygen reduction reaction. J Phys Chem C 114:6860e8. https://doi.org/10.1021/jp100559g
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This work was financially supported by study on the technology of cracking LPG to increase ethylene production of North Huajin Chemical Industries Group Corporation (20190729H).
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Song, S., Sun, M., Cao, M. et al. Conversion of isobutane to n-butane over bifunctional PtAu-solid superacids catalyst. Chem. Pap. 74, 4057–4066 (2020). https://doi.org/10.1007/s11696-020-01225-y
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DOI: https://doi.org/10.1007/s11696-020-01225-y