Modification of acidic and textural properties of a sulphated zirconia catalyst for efficient conversion of high-density polyethylene into liquid fuel

  • Muhammad N. Almustapha
  • Muhammad FarooqEmail author
  • Misbahu L. Mohammed
  • Muhammad Farhan
  • Muhammad Imran
  • John M. Andresen
Current trends in Economy, Sustainable Development, and Energy


Consumption of plastic has a rapid increase of about 8% per annum and reached to 400 million per tonnes approximately, where about 50% of plastic was disposed after using only once. Different techniques for treating this increased waste faced a number of issues related to cost and environmental and sustainable development. Catalytic conversion has been found as one of the most viable solutions to solve this problem. Sulphated zirconia (SZ) catalyst modified with calcium carbide (CC) was found to improve high-density polyethylene (HDPE) conversion into liquid fuel. The liquid content was improved from 39.0wt% to 66.0wt% at 410 °C. HDPE was converted 100% by weight using, SZ/CC with 66wt% liquid yield as compared to the conversion of approximately 98wt% with about 40wt% only liquid yield for the pure SZ. The composition of hydrocarbon liquid product was significantly changed from paraffin (16%) and aromatic (58%) to olefin (74%) and naphthenic (23%) compounds. This significant increase in liquid was related to changes in the acidic and textural characteristics of the new hybrid catalyst, SZ/CC where the total ammonia desorption of 337.0 μm NH3/g for the SZ was modified to 23.4 μm NH3/g for the SZ/CC. Both SZ and SZ/CC catalysts showed characteristics of mesoporous material, where the internal pore volume of SZ had reduced from 0.21 mL/g for SZ to 0.04 mL/g for SZ/CC. Furthermore, XRD analysis indicated the presence of a new compound, CaZrO3 in the SZ/CC, which confirmed a chemical interaction between the SZ and CC through sintering of ZrO2 and CaO. Therefore, the SZ/CC catalyst improves the liquid yield significantly and the selectivity towards olefinic and naphthenic compounds.


Catalytic conversion Sulphated zirconia Calcium carbide HDPE Plastic waste 



The Authors remain indebted to MEL Chemicals and equally thankful to the Petroleum Technology Development Fund for providing sponsorship for the PhD. We are also thankful to Professor Mercedes Maroto-Valer in whose laboratory some of the analyses were conducted.


  1. Aguado J, Serrano DP, Vicente G, Sánchez N (2007) Enhanced production of α-olefins by thermal degradation of high-density polyethylene (HDPE) in decalin solvent: effect of the reaction time and temperature. Ind Eng Chem Res 46(11):3497–3504CrossRefGoogle Scholar
  2. Aguado J, Serrano DP, Escola JM (2008) Fuels from waste plastics by thermal and catalytic processes: a review. Ind Eng Chem Res 47(21):7982–7992CrossRefGoogle Scholar
  3. Aguado J, Serrano DP, Escola JM, Peral A (2009) Catalytic cracking of polyethylene over zeolite mordenite with enhanced textural properties. J Anal Appl Pyrolysis 85(1–2):352–358CrossRefGoogle Scholar
  4. Ahmed AI, El-Hakam SA, Samra SE, El-Khouly AA, Khder AS (2008) Structural characterization of sulfated zirconia and their catalytic activity in dehydration of ethanol. Colloids Surf A Physicochem Eng Asp 317(1–3):62–70CrossRefGoogle Scholar
  5. Akpanudoh NS, Gobin K, Manos G (2005) Catalytic degradation of plastic waste to liquid fuel over commercial cracking catalysts - effect of polymer to catalyst ratio/acidity content. J Mol Catal Chem 235(1–2):67–73CrossRefGoogle Scholar
  6. Almustapha MN, Andrésen JM (2012) Recovery of valuable chemicals from high density polyethylene (HDPE) polymer: a catalytic approach for plastic waste recycling. Int J Environ Sci Dev 3(3):263–267CrossRefGoogle Scholar
  7. Almustapha MN, Farooq M, Andresen JM (2017) Sulphated zirconia catalysed conversion of high density polyethylene to value-added products using a fixed-bed reactor. J Anal Appl Pyrolysis 125:296–303CrossRefGoogle Scholar
  8. Al-Salem SM, Lettieri P, Baeyens J (2009) Recycling and recovery routes of plastic solid waste (PSW): a review. Waste Manag 29(10):2625–2643CrossRefGoogle Scholar
  9. Angyal A, Miskolczi N, Bartha L, Valkai I (2009) Catalytic cracking of polyethylene waste in horizontal tube reactor. Polym Degrad Stab 94(10):1678–1683CrossRefGoogle Scholar
  10. Arandes JM, Azkoiti MJ, Torre I, Olazar M, Castano P (2007) Effect of HZSM-5 catalyst addition on the cracking of polyolefin pyrolysis waxes under FCC conditions. Chem Eng J 132(1–3):17–26CrossRefGoogle Scholar
  11. Arata K, Matsuhashi H, Hino M, Nakamura H (2003) Synthesis of solid superacids and their activities for reactions of alkanes. Catal Today 81(1):17–30CrossRefGoogle Scholar
  12. Barthos R, Lónyi F, Onyestyák G, Valyon J (2001) An NH3-TPD and -FR study on the acidity of sulfated zirconia. Solid State Ionics 141–142:253–258CrossRefGoogle Scholar
  13. Clark JH (2002) Solid acids for green chemistry. Acc Chem Res 35(9):791–797CrossRefGoogle Scholar
  14. Donohue MD, Aranovich GL (1999) A new classification of isotherms for Gibbs adsorption of gases on solids. Fluid Phase Equilib 158–160(0):557–563CrossRefGoogle Scholar
  15. Elordi G, Olazar M, Lopez G, Amutio M, Artetxe M, Aguado R, Bilbao J (2009) Catalytic pyrolysis of HDPE in continuous mode over zeolite catalysts in a conical spouted bed reactor. J Anal Appl Pyrolysis 85(1–2):345–351CrossRefGoogle Scholar
  16. Farooq M, Almustapha M, Imran M, Saeed M, Andresen JM (2018) In-situ regeneration of activated carbon with electric potential swing desorption (EPSD) for the H2S removal from biogas. Bioresour Technol 249:125–131CrossRefGoogle Scholar
  17. Gobin K, Manos G (2004a) Polymer degradation to fuels over microporous catalysts as a novel tertiary plastic recycling method. Polym Degrad Stab 83(2):267–279CrossRefGoogle Scholar
  18. Gobin K, Manos G (2004b) Thermogravimetric study of polymer catalytic degradation over microporous materials. Polym Degrad Stab 86(2):225–231CrossRefGoogle Scholar
  19. Hernandez MD, Garcia AN, Gomez A, Agullo J, Marcilla A (2006) Effect of residence time on volatile products obtained in the HDPE pyrolysis in the presence and absence of HZSM-5. Ind Eng Chem Res 45(26):8770–8778CrossRefGoogle Scholar
  20. Hino M, Kurashige M, Matsuhashi H, Arata K (2006) The surface structure of sulfated zirconia: studies of XPS and thermal analysis. Thermochim Acta 441(1):35–41CrossRefGoogle Scholar
  21. Hopewell J, Dvorak R, Kosior E (2009) Plastics recycling: challenges and opportunities. Philos Trans R Soc B Biol Sci 364(1526):2115–2126CrossRefGoogle Scholar
  22. Huang WC, Huang MS, Huang CF, Chen CC, Ou KL (2010) Thermochemical conversion of polymer wastes into hydrocarbon fuels over various fluidizing cracking catalysts. Fuel 89(9):2305–2316CrossRefGoogle Scholar
  23. Katada N, Igi H, Kim J-H (1997) Determination of the acidic properties of zeolite by theoretical analysis of temperature-programmed desorption of ammonia based on adsorption equilibrium. J Phys Chem B 101(31):5969–5977CrossRefGoogle Scholar
  24. Keane MA (2009) Catalytic transformation of waste polymers to fuel oil. Chemsuschem 2(3):207–214CrossRefGoogle Scholar
  25. Lin YH, Yen HY (2005) Fluidised bed pyrolysis of polypropylene over cracking catalysts for producing hydrocarbons. Polym Degrad Stab 89(1):101–108CrossRefGoogle Scholar
  26. Lin YH, Sharratt PN, Garforth AA, Dwyer J (1998) Catalytic conversion of polyolefins to chemicals and fuels over various cracking catalysts. Energy Fuel 12(4):767–774CrossRefGoogle Scholar
  27. Liu X, Smith KJ (2008) Acidity and deactivation of Mo2C/HY catalysts used for the hydrogenation and ring opening of naphthalene. Appl Catal A Gen 335(2):230–240CrossRefGoogle Scholar
  28. López A, de Marco I, Caballero BM, Laresgoiti MF, Adrados A, Aranzabal A (2011) Catalytic pyrolysis of plastic wastes with two different types of catalysts: ZSM-5 zeolite and red mud. Appl Catal B Environ 104(3–4):211–219CrossRefGoogle Scholar
  29. Marcilla A, Beltrán MI, Navarro R (2009) Thermal and catalytic pyrolysis of polyethylene over HZSM5 and HUSY zeolites in a batch reactor under dynamic conditions. Appl Catal B Environ 86(1–2):78–86CrossRefGoogle Scholar
  30. Mishra MK, Tyagi B, Jasra RV (2003) Effect of synthetic parameters on structural, textural, and catalytic properties of nanocrystalline sulfated zirconia prepared by sol−gel technique. Ind Eng Chem Res 42(23):5727–5736CrossRefGoogle Scholar
  31. Miskolczi N, Bartha L, Deák G, Jóver B, Kalló D (2004) Thermal and thermo-catalytic degradation of high-density polyethylene waste. J Anal Appl Pyrolysis 72(2):7CrossRefGoogle Scholar
  32. Miskolczi N, Bartha L, Deak G (2006) Thermal degradation of polyethylene and polystyrene from the packaging industry over different catalysts into fuel-like feed stocks. Polym Degrad Stab 91(3):517–526CrossRefGoogle Scholar
  33. Miskolczi N, Angyal A, Bartha L, Valkai I (2009) Fuels by pyrolysis of waste plastics from agricultural and packaging sectors in a pilot scale reactor. Fuel Process Technol 90(7–8):1032–1040CrossRefGoogle Scholar
  34. Oh J, Dash S, Lee H (2011) Selective conversion of glycerol to 1,3-propanediol using Pt-sulfated zirconia. Green Chem 13(8):2004–2007CrossRefGoogle Scholar
  35. Panda AK, Singh RK, Mishra DK (2010) Thermolysis of waste plastics to liquid fuel: a suitable method for plastic waste management and manufacture of value added products-a world prospective. Renew Sustain Energy Rev 14(1):233–248CrossRefGoogle Scholar
  36. Reddy MM, Vivekanandhan S, Misra M, Bhatia SK, Mohanty AK (2013) Biobased plastics and bionanocomposites: current status and future opportunities. Prog Polym Sci 38(10–11):1653–1689CrossRefGoogle Scholar
  37. Rezaei M, Alavi SM, Sahebdelfar S, Yan Z-F (2006) Tetragonal nanocrystalline zirconia powder with high surface area and mesoporous structure. Powder Technol 168(2):59–63CrossRefGoogle Scholar
  38. Saha B, Chowdhury P, Ghoshal AK (2008) Al-MCM-41 catalyzed decomposition of polypropylene and hybrid genetic algorithm for kinetics analysis. Appl Catal B Environ 83(3–4):265–276CrossRefGoogle Scholar
  39. Serrano DP, Aguado J, Escola JM (2000a) Catalytic conversion of polystyrene over HMCM-41, HZSM-5 and amorphous SiO2-Al2O3: comparison with thermal cracking. Appl Catal B Environ 25(2–3):181–189CrossRefGoogle Scholar
  40. Serrano DP, Aguado J, Escola JM (2000b) Catalytic cracking of a polyolefin mixture over different acid solid catalysts. Ind Eng Chem Res 39(5):1177–1184CrossRefGoogle Scholar
  41. Serrano DP, Aguado J, Rodriguez JM, Peral A (2007) Catalytic cracking of polyethylene over nanocrystalline HZSM-5: catalyst deactivation and regeneration study. J Anal Appl Pyrolysis 79(1–2):456–464CrossRefGoogle Scholar
  42. Shah J, Jan MR, Mabood F, Jabeen F (2010a) Catalytic pyrolysis of LDPE leads to valuable resource recovery and reduction of waste problems. Energy Convers Manag 51(12):2791–2801CrossRefGoogle Scholar
  43. Shah SH, Khan ZM, Raja IA, Mahmood Q, Bhatti ZA, Khan J, Farooq A, Rashid N, Wu D (2010b) Low temperature conversion of plastic waste into light hydrocarbons. J Hazard Mater 179(1–3):15–20CrossRefGoogle Scholar
  44. Sharratt PN, Lin YH, Garforth AA, Dwyer J (1997) Investigation of the catalytic pyrolysis of high-density polyethylene over a HZSM-5 catalyst in a laboratory fluidized-bed reactor. Ind Eng Chem Res 36(12):5118–5124CrossRefGoogle Scholar
  45. Shent HT, Pugh RJ, Forssberg E (1999) A review of plastics waste recycling and the flotation of plastics. Resour Conserv Recycl 25(2):85–109CrossRefGoogle Scholar
  46. Shi W, Li J (2013) A new deactivation mechanism of sulfate-promoted Iron oxide. Catal Lett 143(12):1285–1293CrossRefGoogle Scholar
  47. Singhabhandhu A, Tezuka T (2010) The waste-to-energy framework for integrated multi-waste utilization: waste cooking oil, waste lubricating oil, and waste plastics. Energy 35(6):2544–2551CrossRefGoogle Scholar
  48. Tarrío-Saavedra J, Naya S, Francisco-Fernández M, Artiaga R, Lopez-Beceiro J (2011) Application of functional ANOVA to the study of thermal stability of micro-nano silica epoxy composites. Chemom Intell Lab Syst 105(1):114–124CrossRefGoogle Scholar
  49. Walendziewski J, Steininger M (2001) Thermal and catalytic conversion of waste polyolefins. Catal Today 65(2–4):323–330CrossRefGoogle Scholar
  50. Wei TT, Wu KJ, Lee SL, Lin YH (2010) Chemical recycling of post-consumer polymer waste over fluidizing cracking catalysts for producing chemicals and hydrocarbon fuels. Resour Conserv Recycl 54(11):952–961CrossRefGoogle Scholar
  51. Yadav GD, Nair JJ (1999) Sulfated zirconia and its modified versions as promising catalysts for industrial processes. Microporous Mesoporous Mater 33(1–3):1–48CrossRefGoogle Scholar
  52. Yang X, Zhao B, Zhuo Y, Chen C, Xu X (2012) The investigation of SCR reaction on sulfated CaO. Asia Pac J Chem Eng 7:55–62CrossRefGoogle Scholar
  53. Zadgaonkar A (2004) Environmental protection fron plastic waste. In: GPEC, G.H. Raisoni College of Engineering, Nagpur, India. Nahpur, IndiaGoogle Scholar
  54. Zhao J, Yue Y, Hua W, He H, Gao Z (2008) Catalytic activities and properties of sulfated zirconia supported on mesostructured γ-Al2O3. Appl Catal A Gen 336(1–2):133–139CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Research Centre for Carbon Solutions, Institute of Mechanical, Process and Energy EngineeringHeriot-Watt UniversityEdinburghUK
  2. 2.Department of Pure and Applied ChemistryUsmanu Danfodiyo UniversitySokotoNigeria
  3. 3.Department of Mechanical EngineeringUniversity of Engineering and Technology, KSK CampusLahorePakistan
  4. 4.Department of Mechanical EngineeringTechnical University of DenmarkKongens LyngbyDenmark

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