The synergic effects of highly selective bimetallic Pt-Pd/SAPO-41 catalysts for the n-hexadecane hydroisomerization

Abstract

The hydroisomerization of n-hexadecane over Pt-Pd bimetallic catalysts is an effective way to produce clean fuel oil. This work reports a useful preparation method of bimetallic bifunctional catalysts by a co-impregnation or sequential impregnation process. Furthermore, monometallic catalysts with loading either Pt or Pd are also prepared for comparison. The effects of the metal species and impregnation order on the characteristics and catalytic performance of the catalysts are investigated. The catalytic test results indicate that the maximum iso-hexadecane yield over different catalysts increases as follows: Pt/silicoaluminophosphate SAPO-41<Pd/SAPO-41<Pt*-Pd/SAPO-41 (prepared by sequential impregnation)<Pt-Pd/SAPO-41 (prepared by co-impregnation). Owing to the synergic effects between Pt and Pd, the Pt-Pd/SAPO-41 catalyst prepared by the co-impregnation method demonstrates the effective promotion of (de)hydrogenation activity. Therefore, this catalyst exhibits the highest iso-hexadecane yield of 89.4% when the n-hexadecane conversion is 96.3%. Additionally, the Pt-Pd/SAPO-41 catalyst also presents the highest catalytic activity and best stability even after 150 h long-term tests.

Graphical abstract

Keywords

SAPO-41 molecular sieve / Pt-Pd bimetallic site / bifunctional catalysts / n-hexadecane / hydroisomerization

References

[1] Avinash A, Murugesan A. Prediction capabilities of mathematical models in producing a renewable fuel from waste cooking oil for sustainable energy and clean environment. Fuel, 2018, 216: 322–329

[2] Peng C, Du Y, Feng X, Hu Y, Fang X. Research and development of hydrocracking catalysts and technologies in China. Frontiers of Chemical Science and Engineering, 2018, 12(4): 867–877

[3] Martens J A, Verboekend D, Thomas K, Vanbutsele G, Gilson J P, Perez Ramirez J. Hydroisomerization of emerging renewable hydrocarbons using hierarchical Pt/H-ZSM-22 catalyst. ChemSusChem, 2013, 6(3): 421–425

[4] Liu X, Deng B, Fu J, Xu Z, Liu J, Li M, Li Q, Ma Z, Feng R. The effect of air/fuel composition on the HC emissions for a twin-spark motorcycle gasoline engine: a wide condition range study. Chemical Engineering Journal, 2019, 355: 170–180

[5] Wang Z, Zhang Y, Neyts E C, Cao X, Zhang X, Jang B W L, Liu C J. Catalyst preparation with plasmas: How does it work? ACS Catalysis, 2018, 8(3): 2093–2110

[6] Chen K, Cheng D, Peng C, Wang D, Zhang J. Green catalytic engineering: a powerful tool for sustainable development in chemical industry. Frontiers of Chemical Science and Engineering, 2018, 12(4): 835–837

[7] Li L, Yao Z, You S, Wang C, Chong C, Wang X. Optimal design of negative emission hybrid renewable energy systems with biochar production. Applied Energy, 2019, 243: 233–249

[8] Santamaria L, Lopez G, Arregi A, Amutio M, Artetxe M, Bilbao J, Olazar M. Stability of different Ni supported catalysts in the in-line steam reforming of biomass fast pyrolysis volatiles. Applied Catalysis B: Environmental, 2019, 242: 109–120

[9] Song X, Bai X, Wu W, Kikhtyanin O V, Zhao A, Xiao L, Su X, Zhang J, Wei X. The effect of palladium loading on the catalytic performance of Pd/SAPO-11 for n-decane hydroisomerization. Molecular Catalysis, 2017, 433: 84–90

[10] Corro G, Flores A, Pacheco-Aguirre F, Pal U, Banuelos F, Ramirez A, Zehe A. Biodiesel and fossil-fuel diesel soot oxidation activities of Ag/CeO₂ catalyst. Fuel, 2019, 250: 17–26

[11] Ou X, Wu C, Shi K, Hardacre C, Zhang J, Jiao Y, Fan X. Structured ZSM-5/SiC foam catalysts for bio-oils upgrading. Applied Catalysis A, General, 2020, 599: 117626

[12] Mantovani M, Mandelli D, Gonçalves M, Carvalho W A. Fructose dehydration promoted by acidic catalysts obtained from biodiesel waste. Chemical Engineering Journal, 2018, 348: 860–869

[13] Singh D, Sharma D, Soni S L, Sharma S, Kumari D. Chemical compositions, properties, and standards for different generation biodiesels: a review. Fuel, 2019, 253: 60–71

[14] Wang W, Liu C, Wu W. Bifunctional catalysts for the hydroisomerization of n-alkanes: the effects of metal-acid balance and textural structure. Catalysis Science & Technology, 2019, 9(16): 4162–4187

[15] Li P, Sakuragi K, Makino H. Extraction techniques in sustainable biofuel production: a concise review. Fuel Processing Technology, 2019, 193: 295–303

[16] Jaroszewska K, Fedyna M, Trawczynski J. Hydroisomerization of long-chain n-alkanes over Pt/AlSBA-15+ zeolite bimodal catalysts. Applied Catalysis B: Environmental, 2019, 255: 117756

[17] Mendes P S, Mota F M, Silva J M, Ribeiro M F, Daudin A, Bouchy C. A systematic study on mixtures of Pt/zeolite as hydroisomerization catalysts. Catalysis Science & Technology, 2017, 7(5): 1095–1107

[18] Zhang F, Liu Y, Sun Q, Dai Z, Gies H, Wu Q, Pan S, Bian C, Tian Z, Meng X, Zhang Y, Zou X, Yi X, Zheng A, Wang L, Xiao F S. Design and preparation of efficient hydroisomerization catalysts by the formation of stable SAPO-11 molecular sieve nanosheets with 10–20 nm thickness and partially blocked acidic sites. Chemical Communications (Cambridge), 2017, 53(36): 4942–4945

[19] Li T, Wang W, Feng Z, Bai X, Su X, Yang L, Jia G, Guo C, Wu W. The hydroisomerization of n-hexane over highly selective Pd/ZSM-22 bifunctional catalysts: the improvements of metal-acid balance by room temperature electron reduction method. Fuel, 2020, 272: 117717

[20] Xu O, Su H, Jin X, Chu J. Kinetic model for hydroisomerization reaction of C₈-aromatics. Frontiers of Chemical Science and Engineering, 2008, 2(1): 10–16

[21] Smit B, Maesen T L M. Towards a molecular understanding of shape selectivity. Nature, 2008, 451(7179): 671–678

[22] Xu Y, Cui S. A novel fluid catalytic cracking process for maximizing iso-paraffins: from fundamentals to commercialization. Frontiers of Chemical Science and Engineering, 2018, 12(1): 9–23

[23] Meriaudeau P, Tuan V A, Nghiem V T, Lai S Y, Hung L N, Naccache C. SAPO-11, SAPO-31, and SAPO-41 molecular sieves: synthesis, characterization, and catalytic properties in n-octane hydroisomerization. Journal of Catalysis, 1997, 169(1): 55–66

[24] Park K C, Ihm S K. Comparison of Pt/zeolite catalysts for n-hexadecane hydroisomerization. Applied Catalysis A, General, 2000, 203(2): 201–209

[25] Nghiem V T, Sapaly G, Meriaudeau P, Naccache C. Monodimensional tubular medium pore molecular sieves for selective hydroisomerisation of long chain alkanes: n-octane reaction on ZSM and SAPO type catalysts. Topics in Catalysis, 2000, 14(1/4): 131–138

[26] Yue T, Liu W, Li L, Zhao X, Zhu K, Zhou X, Yang W. Crystallization of ATO silicoaluminophosphates nanocrystalline spheroids using a phase-transfer synthetic strategy for n-heptane hydroisomerization. Journal of Catalysis, 2018, 364: 308–327

[27] Ge L, Yu G, Chen X, Li W, Xue W, Qiu M, Sun Y. Effects of particle size on bifunctional Pt/SAPO-11 catalysts in the hydroisomerization of n-dodecane. New Journal of Chemistry, 2020, 44(7): 2996–3003

[28] Wei X, Kikhtyanin O V, Parmon V N, Wu W, Bai X, Zhang J, Xiao L, Su X, Zhang Y. Synergetic effect between the metal and acid sites of Pd/SAPO-41 bifunctional catalysts in n-hexadecane hydroisomerization. Journal of Porous Materials, 2017, 25(1): 235–247

[29] Kim M Y, Lee K, Choi M. Cooperative effects of secondary mesoporosity and acid site location in Pt/SAPO-11 on n-dodecane hydroisomerization selectivity. Journal of Catalysis, 2014, 319: 232–238

[30] Yang Z, Liu Y, Li Y, Zeng L, Liu Z, Liu X, Liu C. Effect of preparation method on the bimetallic NiCu/SAPO-11 catalysts for the hydroisomerization of n-octane. Journal of Energy Chemistry, 2019, 28: 23–30

[31] Kim J, Han S W, Kim J C, Ryoo R. Supporting nickel to replace platinum on zeolite nanosponges for catalytic hydroisomerization of ndodecane. ACS Catalysis, 2018, 8(11): 10545–10554

[32] Yang Z, Liu Y, Liu D, Meng X, Liu C. Hydroisomerization of n-octane over bimetallic Ni-Cu/SAPO-11 catalysts. Applied Catalysis A, General, 2017, 543: 274–282

[33] Parmar S, Pant K K, John M, Kumar K, Pai S M, Newalkar B L. Hydroisomerization of n-hexadecane over Pt/ZSM-22 framework: effect of divalent cation exchange. Journal of Molecular Catalysis A Chemical, 2015, 404: 47–56

[34] Elangovan S P, Bischof C, Hartmann M. Isomerization and hydrocracking of n-decane over Pt-Pd/AlMCM-41 catalysts. Studies in Surface Science and Catalysis, 2002, 142: 911–918

[35] Song H, Wang N, Song H, Li F. La-Ni modified S₂O₈^2–/ZrO₂-Al₂O₃ catalyst in n-pentane hydroisomerization. Catalysis Communications, 2015, 59: 61–64

[36] Lee J K, Rhee H K. Sulfur tolerance of zeolite beta-supported Pd-Pt catalysts for the isomerization of n-hexane. Journal of Catalysis, 1998, 177(2): 208–216

[37] Bauer F, Ficht K, Bertmer M, Einicke W D, Kuchling T, Glaser R. Hydroisomerization of long-chain paraffins over nano-sized bimetallic Pt-Pd/H-beta catalysts. Catalysis Science & Technology, 2014, 4(11): 4045–4054

[38] Roldan R, Beale A M, Sanchez Sanchez M, Romero Salguero F J, Jimenez Sanchidrian C, Gomez J P, Sankar G. Effect of the impregnation order on the nature of metal particles of bi-functional Pt/Pd-supported zeolite beta materials and on their catalytic activity for the hydroisomerization of alkanes. Journal of Catalysis, 2008, 254(1): 12–26

[39] Schmidt F, Hoffmann C, Giordanino F, Bordiga S, Simon P, Carrillo Cabrera W, Kaskel S. Coke location in microporous and hierarchical ZSM-5 and the impact on the MTH reaction. Journal of Catalysis, 2013, 307: 238–245

[40] Liu J, Zou S, Xiao L, Fan J. Well-dispersed bimetallic nanoparticles confined in mesoporous metal oxides and their optimized catalytic activity for nitrobenzene hydrogenation. Catalysis Science & Technology, 2014, 4(2): 441–446

[41] Yang X, Yang Q, Xu J, Lee C S. Bimetallic PtPd nanoparticles on nafion-graphene film as catalyst for ethanol electro-oxidation. Journal of Materials Chemistry, 2012, 22(16): 8057–8062

[42] Zhang Y, Wang W, Jiang X, Su X, Kikhtyanin O V, Wu W. Hydroisomerization of n-hexadecane over a Pd-Ni₂P/SAPO-31 bifunctional catalyst: synergistic effects of bimetallic active sites. Catalysis Science & Technology, 2018, 8(3): 817–828

[43] Cheng K, van der Wal L I, Yoshida H, Oenema J, Harmel J, Zhang Z, Sunley G, Zečević J, de Jong K P. Impact of the spatial organization of bifunctional metal-zeolite catalysts on the hydroisomerization of light alkanes. Angewandte Chemie International Edition, 2020, 59(9): 3592–3600

[44] Ren F, Wang H, Zhai C, Zhu M, Yue R, Du Y, Yang P, Xu J, Lu W. Clean method for the synthesis of reduced graphene oxide-supported PtPd alloys with high electrocatalytic activity for ethanol oxidation in alkaline medium. ACS Applied Materials & Interfaces, 2014, 6(5): 3607–3614

[45] de Lucas A, Sánchez P, Dorado F, Ramos M J, Valverde J L. Effect of the metal loading in the hydroisomerization of n-octane over beta agglomerated zeolite based catalysts. Applied Catalysis A, General, 2005, 294(2): 215–225

[46] Smirnova M Y, Kikhtyanin O V, Smirnov M Y, Kalinkin A V, Titkov A I, Ayupov A B, Ermakov D Y. Effect of calcination temperature on the properties of Pt/SAPO-31 catalyst in one-stage transformation of sunflower oil to green diesel. Applied Catalysis A, General, 2015, 505: 524–531

[47] Dai P, Zhao X, Xu D, Wang C, Tao X, Liu X, Gao J. Preparation, characterization, and properties of Pt/Al₂O₃/cordierite monolith catalyst for hydrogen generation from hydrolysis of sodium borohydride in a flow reactor. International Journal of Hydrogen Energy, 2019, 44(53): 28463–28470

[48] Fu G, Wu K, Lin J, Tang Y, Chen Y, Zhou Y, Lu T. One-pot water-based synthesis of PtPd alloy nanoflowers and their superior electrocatalytic activity for the oxygen reduction reaction and remarkable methanol-tolerant ability in acid media. Journal of Physical Chemistry C, 2013, 117(19): 9826–9834

[49] Radlik M, Małolepszy A, Matus K, Srebowata A, Juszczyk W, Dłuzewski P, Karpinski Z. Alkane isomerization on highly reduced Pd/Al₂O₃ catalysts. The crucial role of Pd-Al species. Catalysis Communications, 2019, 123: 17–22

[50] Wang W, Wang Z, Wang J, Zhong C, Liu C. Highly active and stable Pt-Pd alloy catalysts synthesized by room-temperature electron reduction for oxygen reduction reaction. Advancement of Science, 2017, 4(4): 1600486

[51] Alvarez F, Ribeiro F R, Perot G, Thomazeau C, Guisnet M. Hydroisomerization and hydrocracking of alkanes 7. Influence of the balance between acid and hydrogenating functions on the transformation of n-decane on PtHY catalysts. Journal of Catalysis, 1996, 162(2): 179–189

[52] Amir A, Pouilloux Y, Patarin J, Bats N, Bouchy C, Daou T J, Pinard L. Impact of extreme downsizing of *BEA-type zeolite crystals on n-hexadecane hydroisomerization. New Journal of Chemistry, 2016, 40(5): 4335–4343

[53] Hengsawad T, Srimingkwanchai C, Butnark S, Resasco D E, Jongpatiwut S. Effect of metal-acid balance on hydroprocessed renewable jet fuel synthesis from hydrocracking and hydroisomerization of biohydrogenated diesel over Pt-supported catalysts. Industrial & Engineering Chemistry Research, 2018, 57(5): 1429–1440

[54] Regali F, Liotta L F, Venezia A M, Boutonnet M, Jaras S. Hydroconversion of n-hexadecane on Pt/silica-alumina catalysts: effect of metal loading and support acidity on bifunctional and hydrogenolytic activity. Applied Catalysis A, General, 2014, 469: 328–339

[55] Weitkamp J. Catalytic hydrocracking-mechanisms and versatility of the process. ChemCatChem, 2012, 4(3): 292–306

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