Conversion of polyethylene to gasoline: Influence of porosity and acidity of zeolites

Abstract

Plastic waste is causing serious environmental problems. Developing efficient, cheap and stable catalytic routes to convert plastic waste into valuable products is of great importance for sustainable development, but remains to be a challenging task. Zeolites are cheap and stable, but they are usually not efficient for plastic conversion at a low temperature. Herein a series of microporous and mesoporous zeolites were used to study the influence of porosity and acidity of zeolite on catalytic activity for plastics conversion. It was observed that H-Beta zeolite was an efficient catalyst for cracking high-density polyethylene to gasoline at 240 °C, and the products were almost C₄–C₁₂ alkanes. The effect of porosity and acidity on catalytic performance of zeolites was evaluated, which clearly visualized the good performance of H-Beta due to high surface area, large channel system, large amount accessible acidic sites. This study provides very useful information for designing zeolites for efficient conversion of plastics.

Key words： plastics conversion; polyethylene; zeolites; acidity; porosity

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. 22293015, 22293012, and 22121002) and the Research Funds of Happiness Flower ECNU (2020ST2203).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11708-023-0897-1 and is accessible for authorized users.

Competing interests

The authors declare that they have no competing interests.

References

1 Geyer R, Jambeck J R, Law K L. Production, use, and fate of all plastics ever made. Science Advances, 2017, 3(7): e1700782

2 Jambeck J R, Geyer R, Wilcox C. . Plastic waste inputs from land into the ocean. Science, 2015, 347(6223): 768–771

3 Garcia J M, Robertson M L. The future of plastics recycling. Science, 2017, 358(6365): 870–872

4 Schyns Z O G, Shaver M P. Mechanical recycling of packaging plastics: A review. Macromolecular Rapid Communications, 2021, 42(3): 2000415

5 Fortman D J, Brutman J P, de Hoe G X. . Approaches to sustainable and continually recyclable cross-linked polymers. ACS Sustainable Chemistry & Engineering, 2018, 6(9): 11145–11159

6 Billiet S, Trenor S R. 100th Anniversary of macromolecular science viewpoint: Needs for plastics packaging circularity. ACS Macro Letters, 2020, 9(9): 1376–1390

7 Gandhi N, Farfaras N, Wang N H L. . Life cycle assessment of recycling high-density polyethylene plastic waste. Journal of Renewable Materials, 2021, 9(8): 1463–1483

8 Taghiei M M, Feng Z, Huggins F E. . Coliquefaction of waste plastics with coal. Energy & Fuels, 1994, 8(6): 1228–1232

9 Wang C, Xie T, Kots P A. . Polyethylene hydrogenolysis at mild conditions over ruthenium on tungstated zirconia. JACS Au, 2021, 1(9): 1422–1434

10 Alston S M, Clark A D, Arnold J C. . Environmental impact of pyrolysis of mixed weee plastics part 1: Experimental pyrolysis data. Environmental Science & Technology, 2011, 45(21): 9380–9385

11 Kunwar B, Cheng H N, Chandrashekaran S R. . Plastics to fuel: A review. Renewable & Sustainable Energy Reviews, 2016, 54: 421–428

12 Rorrer J E, Beckham G T, Roman-Leshkov Y. Conversion of polyolefin waste to liquid alkanes with Ru-based catalysts under mild conditions. JACS Au, 2021, 1(1): 8–12

13 Jia X, Qin C, Friedberger T. . Efficient and selective degradation of polyethylenes into liquid fuels and waxes under mild conditions. Science Advances, 2016, 2(6): 1501591

14 Chen L, Meyer L C, Kovarik L. . Disordered, sub-nanometer Ru structures on CeO₂ are highly efficient and selective catalysts in polymer upcycling by hydrogenolysis. ACS Catalysis, 2022, 12(8): 4618–4627

15 Rorrer J E, Troyano-Valls C, Beckham G T. . Hydrogenolysis of polypropylene and mixed polyolefin plastic waste over Ru/C to produce liquid alkanes. ACS Sustainable Chemistry & Engineering, 2021, 9(35): 11661–11666

16 Rorrer J E, Beckham G T, Román-Leshkov Y. Conversion of polyolefin waste to liquid alkanes with Ru-based catalysts under mild conditions. JACS Au, 2021, 1(1): 8–12

17 Kots P A, Liu S, Vance B C. . Polypropylene plastic waste conversion to lubricants over Ru/TiO₂ catalysts. ACS Catalysis, 2021, 11(13): 8104–8115

18 Tennakoon A, Wu X, Paterson A L. . Catalytic upcycling of high-density polyethylene via a processive mechanism. Nature Catalysis, 2020, 3(11): 893–901

19 Liu S, Kots P A, Vance B C. . Plastic waste to fuels by hydrocracking at mild conditions. Science Advances, 2021, 7(17): eabf8283

20 Zhang F, Zeng M, Yappert R D. . Polyethylene upcycling to long-chain alkylaromatics by tandem hydrogenolysis/aromatization. Science, 2020, 370(6515): 437–441

21 Serrano D P, Aguado J, Escola J M. Developing advanced catalysts for the conversion of polyolefinic waste plastics into fuels and chemicals. ACS Catalysis, 2012, 2(9): 1924–1941

22 Vollmer I, Jenks M J F, Mayorga Gonzalez R. . Plastic waste conversion over a refinery waste catalyst. Angewandte Chemie International Edition, 2021, 60(29): 16101–16108

23 Zhang H, Ma Y, Song K. . Nano-crystallite oriented self-assembled ZSM-5 zeolite and its LDPE cracking properties: Effects of accessibility and strength of acid sites. Journal of Catalysis, 2013, 302: 115–125

24 Peral A, Escola J M, Serrano D P. . Bidimensional ZSM-5 zeolites probed as catalysts for polyethylene cracking. Catalysis Science & Technology, 2016, 6(8): 2754–2765

25 Kokuryo S, Tamura K, Miyake K. . LDPE cracking over mono- and divalent metal-doped beta zeolites. Catalysis Science & Technology, 2022, 12(13): 4138–4144

26 Kokuryo S, Miyake K, Uchida Y. . Defect engineering to boost catalytic activity of beta zeolite on low-density polyethylene cracking. Materials Today Sustainability, 2022, 17: 100098

27 Zhang Z, Gora-Marek K, Watson J S. . Recovering waste plastics using shape-selective nano-scale reactors as catalysts. Nature Sustainability, 2019, 2(1): 39–42

28 Gallo J M R, Bisio C, Gatti G. . Physicochemical characterization and surface acid properties of mesoporous [Al]-SBA-15 obtained by direct synthesis. Langmuir, 2010, 26(8): 5791–5800

29 Ungureanu A, Dragoi B, Hulea V. . Effect of aluminium incorporation by the “pH-adjusting” method on the structural, acidic and catalytic properties of mesoporous SBA-15. Microporous and Mesoporous Materials, 2012, 163: 51–64

30 Weitkamp J. Catalytic hydrocracking—Mechanisms and versatility of the process. ChemCatChem, 2012, 4(3): 292–306

31 Hornung U, Hornung A, Bockhorn H. Investigation of thermal degradation of solids in an isothermal, gradient free reactor. Chemical Engineering & Technology, 1998, 21(4): 332–337

32 Lomakin S M, Rogovina S Z, Grachev A V. . Thermal degradation of biodegradable blends of polyethylene with cellulose and ethylcellulose. Thermochimica Acta, 2011, 521(1–2): 66–73

33 Mortezaeikia V, Tavakoli O, Khodaparasti M S. A review on kinetic study approach for pyrolysis of plastic wastes using thermogravimetric analysis. Journal of Analytical and Applied Pyrolysis, 2021, 160: 105340

34 Dong Z, Chen W, Xu K. . Understanding the structure–activity relationships in catalytic conversion of polyolefin plastics by zeolite-based catalysts: A critical review. ACS Catalysis, 2022, 12(24): 14882–14901

35 CormaAOrchillés A V. Current views on the mechanism of catalytic cracking. Microporous and Mesoporous Materials, 2000, 35–36: 21–30

36 Khan N A, Yoo D K, Bhadra B N. . Preparation of SSZ-13 zeolites from beta zeolite and their application in the conversion of ethylene to propylene. Chemical Engineering Journal, 2019, 377: 119546

37 Liu J, Cui L, Wang L. . Alkaline–acid treated mordenite and beta zeolites featuring mesoporous dimensional uniformity. Materials Letters, 2014, 132: 78–81

38 Alam T, Krisnandi Y K, Wibowo W. . Synthesis and characterization hierarchical HY zeolite using template and non template methods. AIP Conference Proceedings, 2018, 2023(1): 020094

39 Kneller J M, Pietraß T, Ott K C. . Synthesis of dealuminated zeolites NaY and MOR and characterization by diverse methodologies: 27Al and 29Si MAS NMR, XRD, and temperature dependent 129Xe NMR. Microporous and Mesoporous Materials, 2003, 62(1–2): 121–131

40 EngelhardtGMichel D. High-resolution Solid-state NMR of Silicates and Zeolites. Chichester: John Wiley & Sons, 1987

41 BaerlocherCMcCusker L B. Database of zeolite structures database—Providing structural information on all of the zeolite framework types. 2017–7–1, available at website of Database of Zeolite Structures

42 Derouane E G, André J M, Lucas A A. A simple van der waals model for molecule-curved surface interactions in molecular-sized microporous solids. Chemical Physics Letters, 1987, 137(4): 336–340

43 Hartmann M, Machoke A G, Schwieger W. Catalytic test reactions for the evaluation of hierarchical zeolites. Chemical Society Reviews, 2016, 45(12): 3313–3330

44 Manos G, Garforth A, Dwyer J. Catalytic degradation of high-density polyethylene over different zeolitic structures. Industrial & Engineering Chemistry Research, 2000, 39(5): 1198–1202

45 Manos G, Garforth A, Dwyer J. Catalytic degradation of high-density polyethylene on an ultrastable-Y zeolite. Nature of initial polymer reactions, pattern of formation of gas and liquid products, and temperature effects. Industrial & Engineering Chemistry Research, 2000, 39(5): 1203–1208

46 Mordi R C, Fields R, Dwyer J. Thermolysis of low density polyethylene catalysed by zeolites. Journal of Analytical and Applied Pyrolysis, 1994, 29(1): 45–55

47 Tian X, Zeng Z, Liu Z. . Conversion of low-density polyethylene into monocyclic aromatic hydrocarbons by catalytic pyrolysis: Comparison of HZSM-5, Hβ, HY, and MCM-41. Journal of Cleaner Production, 2022, 358: 131989

48 Aguado J, Serrano D P, Escola J M. . Catalytic conversion of polyolefins into fuels over zeolite beta. Polymer Degradation & Stability, 2000, 69(1): 11–16

49 Burange A S, Gawande M B, Lam F L Y. . Heterogeneously catalyzed strategies for the deconstruction of high density polyethylene: Plastic waste valorisation to fuels. Green Chemistry, 2015, 17(1): 146–156

50 Christopher F J, Kumar P S, Vo D V N. . Methods for chemical conversion of plastic wastes into fuels and chemicals. A review. Environmental Chemistry Letters, 2022, 20(1): 223–242

51 Post J G, Van Hooff J H C. Acidity and activity of H-ZSM—5 measured with NH₃-t.p.d. and n-hexane cracking. Zeolites, 1984, 4(1): 9–14

52 Ochoa R, Van Woert H, Lee W H. . Catalytic degradation of medium density polyethylene over silica-alumina supports. Fuel Processing Technology, 1996, 49(1–3): 119–136

53 Gallo J M, Bisio C, Gatti G. . Physicochemical characterization and surface acid properties of mesoporous [Al]-SBA-15 obtained by direct synthesis. Langmuir, 2010, 26(8): 5791–5800

54 Wu S, Han Y, Zou Y C. . Synthesis of heteroatom substituted SBA-15 by the “pH-adjusting” method. Chemistry of Materials, 2004, 16(3): 486–492

55 KotrelSKnözinger HGatesB C. The Haag–Dessau mechanism of protolytic cracking of alkanes. Microporous and Mesoporous Materials, 2000, 35–36: 11–20

56 CoelhoACosta LMarquesM M, . The effect of ZSM-5 zeolite acidity on the catalytic degradation of high-density polyethylene using simultaneous DSC/TG analysis. Applied Catalysis A, General, 2012, 413–414: 183–191

57 Parry E P. An infrared study of pyridine adsorbed on acidic solids. Characterization of surface acidity. Journal of Catalysis, 1963, 2(5): 371–379

58 Socci J, Osatiashtiani A, Kyriakou G. . The catalytic cracking of sterically challenging plastic feedstocks over high acid density Al-SBA-15 catalysts. Applied Catalysis A, General, 2019, 570: 218–227

59 Corma A, Fornés V, Forni L. . 2,6-Di-tert-butyl-pyridine as a probe molecule to measure external acidity of zeolites. Journal of Catalysis, 1998, 179(2): 451–458

60 Reiprich B, Tarach K A, Pyra K. . High-silica layer-like zeolites Y from seeding-free synthesis and their catalytic performance in low-density polyethylene cracking. ACS Applied Materials & Interfaces, 2022, 14(5): 6667–6679

61 Elordi G, Olazar M, Lopez G. . Role of pore structure in the deactivation of zeolites (HZSM-5, Hβ and HY) by coke in the pyrolysis of polyethylene in a conical spouted bed reactor. Applied Catalysis B: Environmental, 2011, 102(1–2): 224–231

62 Marcilla A, Beltrán M I, Navarro R. TG/FT-IR analysis of HZSM5 and HUSY deactivation during the catalytic pyrolysis of polyethylene. Journal of Analytical and Applied Pyrolysis, 2006, 76(1–2): 222–229

63 Castaño P, Elordi G, Olazar M. . Insights into the coke deposited on HZSM-5, Hβ and HY zeolites during the cracking of polyethylene. Applied Catalysis B: Environmental, 2011, 104(1–2): 91–100