Catalysis of sugarcane-bagasse pyrolysis by Co, Ni, and Cu single and mixed oxide nanocomposites

  • Mahmoud Mohamed EmaraEmail author
  • Shrouq Hossam Ali
  • Taher Salah Edin Kassem
  • P. Gregory Van Patten
Research Paper


Pyrolysis of biomass is an important process in which renewable biological waste is converted to energy products and preliminary chemicals. Therefore, various types of catalysts, including metal oxides, have been investigated for more efficient and selective biomass pyrolysis. Co, Ni, and Cu single and mixed metal oxide (SMO and MMO) nanoparticles (NPs) of 3 to 47 nm were synthesized, characterized, and studies for their catalytic activities towards pyrolysis of sugarcane bagasse (PSCB). After mixing the oxide NPs with bagasse, thermogravimetry was performed at a heating rate of 5 °C/min from ambient temperature to 600 °C. Thermogravimetric analysis followed by kinetic calculations of the activation energy through Coats−Redfern model show that all oxide NPs of this study exhibit catalytic activity towards cellulose and hemicellulose thermal degradation during PSCB, in the order MMO > SMO. Cu-containing SMO and MMO NPs show exceptional catalytic activities compared to their analogues. On the other hand, lignin degradation kept proceeding over a wide range of high temperature, just like that of the plain PSCB. This is considered selective enhancement of the catalysis of cellulose and hemicellulose thermal degradation versus lignin degradation, which is promising for improving the composition and quality of PSCB products. Only Cu-containing double and triple MMOs were so catalytically active that they catalyzed lignin degradation along with the cellulose and hemicellulose.


Bagasse Cellulose Oxides Nanocomposites Thermogravimetry Catalysis 





Derivative thermogravimetry


Full width at half maximum


Inductively coupled plasma atomic emission spectroscopy


Joint Committee on Powder Diffraction Standards


Mixed metal oxide




Pyrolysis of sugarcane bagasse


Sugarcane bagasse


Single metal oxide


Transmission electron microscopy




X-ray diffraction


Funding information

Financial support granted by the Ministry of Scientific Research and the Academy of Scientific Research and Technology (ASRT) through the program Scientists of Next Generation-2015 (SNG-5).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11051_2019_4749_MOESM1_ESM.docx (749 kb)
ESM 1 (DOCX 748 kb)


  1. Ahmad J, Majid K, Dar MA (2018) Controlled synthesis of p-type NiO/n-type GO nanocomposite with enhanced photocatalytic activity and study of temperature effect on the photocatalytic activity of the nanocomposite. Appl Surf Sci 457:417–426. CrossRefGoogle Scholar
  2. Ali G, Park YJ, Kim JW, Cho SO (2018) A Green, general, and ultrafast route for the synthesis of diverse Metal oxide nanoparticles with controllable sizes and enhanced catalytic activity. ACS Appl Nano Mater 1:6112–6122. CrossRefGoogle Scholar
  3. Alizadeh-Gheshlaghi E, Shaabani B, Khodayari A, Azizian-Kalandaragh Y, Rahimi R (2012) Investigation of the catalytic activity of nano-sized CuO, Co3O4 and CuCo2O4 powders on thermal decomposition of ammonium perchlorate. Powder Technol 217:330–339. CrossRefGoogle Scholar
  4. Arregi A, Lopez G, Amutio M, Barbarias I, Santamaria L, Bilbao J, Olazar M (2018) Kinetic study of the catalytic reforming of biomass pyrolysis volatiles over a commercial Ni/Al2O3 catalyst. Int J Hydrogen Energy 43:12023–12033. CrossRefGoogle Scholar
  5. Ayoman E, Hosseini SG (2016) Synthesis of CuO nanopowders by high-energy ball-milling method and investigation of their catalytic activity on thermal decomposition of ammonium perchlorate particles. J Therm Anal Calorim 123:1213–1224. CrossRefGoogle Scholar
  6. Balasundram V, Ibrahim N, Kasmani RM, Isha R, Abd Hamid MK, Hasbullah H, Ali RR (2018a) Catalytic upgrading of sugarcane bagasse pyrolysis vapours over rare earth metal (Ce) loaded HZSM-5: effect of catalyst to biomass ratio on the organic compounds in pyrolysis oil. Appl Energy 220:787–799. CrossRefGoogle Scholar
  7. Balasundram V, Zaman KK, Ibrahim N, Kasmani RM, Isha R, Hamid MKA, Hasbullah H (2018b) Catalytic upgrading of pyrolysis vapours over metal modified HZSM-5 via in-situ pyrolysis of sugarcane bagasse: effect of nickel to cerium ratio on HZSM-5. J Anal Appl Pyrolysis 134:309–325. CrossRefGoogle Scholar
  8. Banković-Ilić IB, Miladinović MR, Stamenković OS, Veljković VB (2017) Application of nano CaO–based catalysts in biodiesel synthesis. Renew Sustain Energy Rev 72:746–760CrossRefGoogle Scholar
  9. Bedoic R et al (2019) Green biomass to biogas - a study on anaerobic digestion of residue grass. J Clean Prod 213:700–709. CrossRefGoogle Scholar
  10. Cardoso ART, Conrado NM, Krause MC, Bjerk TR, Krause LC, Caramao EB (2019) Chemical characterization of the bio-oil obtained by catalytic pyrolysis of sugarcane bagasse (industrial waste) from the species Erianthus Arundinaceus. J Environ Chem Eng 7:7. CrossRefGoogle Scholar
  11. Cen HY, Wan L, Zhu J, Li Y, Li X, Zhu Y, Weng H, Wu W, Yin W, Xu C, Bao Y, Feng L, Shou J, He Y (2019) Dynamic monitoring of biomass of rice under different nitrogen treatments using a lightweight UAV with dual image-frame snapshot cameras. Plant Methods 15:16–16. CrossRefGoogle Scholar
  12. Ceylan S, Topçu Y (2014) Pyrolysis kinetics of hazelnut husk using thermogravimetric analysis. Bioresour Technol 156:182–188CrossRefGoogle Scholar
  13. Chang R et al (2018) Production of bio-based p-xylene via catalytic pyrolysis of biomass over metal oxide-modified HZSM-5 zeolites. J Chem Technol Biotechnol 93:3292–3301. CrossRefGoogle Scholar
  14. Dahunsi SO (2019) Mechanical pretreatment of lignocelluloses for enhanced biogas production: methane yield prediction from biomass structural components. Bioresour Technol 280:18–26. CrossRefGoogle Scholar
  15. Deboni TL, Simioni FJ, Brand MA, Lopes GP (2019) Evolution of the quality of forest biomass for energy generation in a cogeneration plant. Renew Energy 135:1291–1302. CrossRefGoogle Scholar
  16. Dhanalakshmi CS, Madhu P (2019) Utilization possibilities of Albizia amara as a source of biomass energy for bio-oil in pyrolysis process. Energy Sources Part A 41:1908–1919. CrossRefGoogle Scholar
  17. Donar YO, Sinag A (2016) Catalytic effect of tin oxide nanoparticles on cellulose pyrolysis. J Anal Appl Pyrolysis 119:69–74. CrossRefGoogle Scholar
  18. Elbaba IF, Williams PT (2013) High yield hydrogen from the pyrolysis-catalytic gasification of waste tyres with a nickel/dolomite catalyst. Fuel 106:528–536. CrossRefGoogle Scholar
  19. El-Sayed SA, Mostafa ME (2015) Kinetic parameters determination of biomass pyrolysis fuels using TGA and DTA techniques. Waste Biomass Valorization 6:401–415CrossRefGoogle Scholar
  20. Garcıa-Perez M, Chaala A, Yang J, Roy C (2001) Co-pyrolysis of sugarcane bagasse with petroleum residue. Part I: thermogravimetric analysis. Fuel 80:1245–1258CrossRefGoogle Scholar
  21. Gawande MB, Pandey RK, Jayaram RV (2012) Role of mixed metal oxides in catalysis science—versatile applications in organic synthesis. Catal Sci Technol 2:1113–1125CrossRefGoogle Scholar
  22. Ghorbannezhad P, Firouzabadi MD, Ghasemian A (2018) Catalytic fast pyrolysis of sugarcane bagasse pith with HZSM-5 catalyst using tandem micro-reactor-GC-MS energy sources part A-recovery. Util Environ Eff 40:15–21. CrossRefGoogle Scholar
  23. Ghorbarmezhad P, Firouzabadi MD, Ghasemian A, de Wild PJ, Heeres HJ (2018) Sugarcane bagasse ex-situ catalytic fast pyrolysis for the production of benzene, Toluene and Xylenes (BTX). J Anal Appl Pyrolysis 131:1–8. CrossRefGoogle Scholar
  24. Gnanasekaran L, Hemamalini R, Saravanan R, Ravichandran K, Gracia F, Agarwal S, Gupta VK (2017) Synthesis and characterization of metal oxides (CeO2, CuO, NiO, Mn3O4, SnO2 and ZnO) nanoparticles as photo catalysts for degradation of textile dyes. J Photochem Photobiol B Biol 173:43–49CrossRefGoogle Scholar
  25. Hassan HB, Tammam RH (2018) Preparation of Ni-metal oxide nanocomposites and their role in enhancing the electro-catalytic activity towards methanol and ethanol. Solid State Ionics 320:325–338. CrossRefGoogle Scholar
  26. Hassan E, Elsayed I, Eseyin A (2016) Production high yields of aromatic hydrocarbons through catalytic fast pyrolysis of torrefied wood and polystyrene. Fuel 174:317–324. CrossRefGoogle Scholar
  27. Hernando H et al (2017) Biomass catalytic fast pyrolysis over hierarchical ZSM-5 and beta zeolites modified with mg and Zn oxides. Biomass Convers Biorefinery 7:289–304. CrossRefGoogle Scholar
  28. Ikaheimo J, Pursiheimo E, Kiviluoma J, Holttinen H (2019) Role of power to liquids and biomass to liquids in a nearly renewable energy system. IET Renew Power Gener 13:1179–1189. CrossRefGoogle Scholar
  29. Ismail AM, Emara MM, El din Kassem TS, Moussa MA (2017) How assembly matters to catalysis and thermal conductivity mediated by CuO nanoparticles. Nanotechnology 28:075705CrossRefGoogle Scholar
  30. Janke L et al (2019) Ensiling fermentation reveals pre-treatment effects for anaerobic digestion of sugarcane biomass: an assessment of ensiling additives on methane potential. Bioresour Technol 279:398–403. CrossRefGoogle Scholar
  31. Jiang TF et al (2018) Cu2O@CuO core-shell nanoparticles as photocathode for p-type dye sensitized solar cell. J Alloys Compd 769:605–610. CrossRefGoogle Scholar
  32. Khan A, Liao Z, Liu Y, Jawad A, Ifthikar J, Chen Z (2017) Synergistic degradation of phenols using peroxymonosulfate activated by CuO-Co3O4@ MnO2 nanocatalyst. J Hazard Mater 329:262–271CrossRefGoogle Scholar
  33. Khiari B, Jeguirim M, Limousy L, Bennici S (2019) Biomass derived chars for energy applications. Renew Sust Energ Rev 108:253–273. CrossRefGoogle Scholar
  34. Kuan WH, Huang YF, Chang CC, Lo SL (2013) Catalytic pyrolysis of sugarcane bagasse by using microwave heating. Bioresour Technol 146:324–329. CrossRefGoogle Scholar
  35. Kumar P, Agrawal KV, Tsapatsis M, Mkhoyan KA (2015) Quantification of thickness and wrinkling of exfoliated two-dimensional zeolite nanosheets. Nat Commun 6:7–7. CrossRefGoogle Scholar
  36. Li J-F, Xiao B, Du L-J, Yan R, Liang TD (2008) Preparation of nano-NiO particles and evaluation of their catalytic activity in pyrolyzing cellulose. J Fuel Chem Technol 36:42–47. CrossRefGoogle Scholar
  37. Li C et al (2017) Shape-controlled CeO2 nanoparticles: stability and activity in the catalyzed HCl oxidation reaction. ACS Catalysis 7:6453–6463CrossRefGoogle Scholar
  38. Li KJ et al (2018) A generic method for preparing hollow mesoporous silica catalytic nanoreactors with metal oxide nanoparticles inside their cavities. Angew Chem-Int Edit 57:16458–16463. CrossRefGoogle Scholar
  39. Li FH, Srivatsa SC, Bhattacharya S (2019) A review on catalytic pyrolysis of microalgae to high-quality bio-oil with low oxygeneous and nitrogenous compounds. Renew Sust Energ Rev 108:481–497. CrossRefGoogle Scholar
  40. Liu Q, Wang S, Luo Z, Cen K (2008) Catalysis mechanism study of potassium salts on cellulose pyrolysis by using TGA-FTIR analysis. J Chem Eng Jpn 41:1133–1142CrossRefGoogle Scholar
  41. Liu FJ et al (2013) Generalized and high temperature synthesis of a series of crystalline mesoporous metal oxides based nanocomposites with enhanced catalytic activities for benzene combustion. J Mater Chem A 1:4089–4096. CrossRefGoogle Scholar
  42. Lopez-Rodriguez M et al (2019) Assessment of multi-step processes for an integral use of the biomass of the marine microalga Amphidinium carterae. Bioresour Technol 282:370–377. CrossRefGoogle Scholar
  43. Ma JG et al (2019) Rare-earth metal oxide hybridized PtFe nanocrystals synthesized via microfluidic process for enhanced electrochemical catalytic performance. Electrochim Acta 299:80–88. CrossRefGoogle Scholar
  44. Marini A, Berbenni V, Flor G (1979) Kinetic parameters from thermogravimetric data. Zeitschrift für Naturforschung A 34:661–663CrossRefGoogle Scholar
  45. Mohapatra S, Mishra SS, Das SK, Thatoi H (2019) Influence of reactors, microbial carbohydrate uptake, and metabolic pathways on ethanol production from grass biomass: a review. Int J Energy Res 43:1615–1646. CrossRefGoogle Scholar
  46. Mortari DA, Ávila I, Santos AM, Crnkovic PCGM (2010) Study of thermal decomposition of ignition temperature of bagasse, coal and their blends. Engenharia Térmica:81–88CrossRefGoogle Scholar
  47. Motaung T, Anandjiwala R (2015) Effect of alkali and acid treatment on thermal degradation kinetics of sugar cane bagasse. Ind Crops Prod 74:472–477CrossRefGoogle Scholar
  48. Mothé CG, de Miranda IC (2009) Characterization of sugarcane and coconut fibers by thermal analysis and FTIR. J Therm Anal Calorim 97:661CrossRefGoogle Scholar
  49. Murugappan K, Mukarakate C, Budhi S, Shetty M, Nimlos MR, Roman-Leshkov Y (2016) Supported molybdenum oxides as effective catalysts for the catalytic fast pyrolysis of lignocellulosic biomass. Green Chem 18:5548–5557. CrossRefGoogle Scholar
  50. Muthuvinothini A, Stella S (2019) Green synthesis of metal oxide nanoparticles and their catalytic activity for the reduction of aldehydes. Process Biochem 77:48–56. CrossRefGoogle Scholar
  51. Nguyen TS, He SB, Raman G, Seshan K (2016) Catalytic hydro-pyrolysis of lignocellulosic biomass over dual Na2CO3/Al2O3 and Pt/Al2O3 catalysts using n-butane at ambient pressure. Chem Eng J 299:415–419. CrossRefGoogle Scholar
  52. Ozbay N, Yargic AS, Sahin RZY, Yaman E (2019) Valorization of banana peel waste via in-situ catalytic pyrolysis using Al-modified SBA-15. Renew Energy 140:633–646. CrossRefGoogle Scholar
  53. Paunovic O, Pap S, Maletic S, Taggart MA, Boskovic N, Sekulic MT (2019) Ionisable emerging pharmaceutical adsorption onto microwave functionalised biochar derived from novel lignocellulosic waste biomass. J Colloid Interface Sci 547:350–360. CrossRefGoogle Scholar
  54. Prager F, Paczkowski S, Sailer G, Derkyi NSA, Pelz S (2019) Biomass sources for a sustainable energy supply in Ghana - a case study for Sunyani. Renew Sust Energ Rev 107:413–424. CrossRefGoogle Scholar
  55. Quang PL, Cuong ND, Hoa TT, Long HT, Hung CM, Le DTT, Hieu NV (2018) Simple post-synthesis of mesoporous p-type Co3O4 nanochains for enhanced H2S gas sensing performance. Sensors Actuators B Chem 270:158–166. CrossRefGoogle Scholar
  56. Said M, John G, Mhilu C, Manyele S (2013) Fast pyrolysis and kinetics of sugarcane bagasse in energy recovery. In: Climate-Smart Technologies. Springer, pp 415–424Google Scholar
  57. Shen DK, Gu S, Bridgwater AV (2010) The thermal performance of the polysaccharides extracted from hardwood: cellulose and hemicellulose. Carbohydr Polym 82:39–45. CrossRefGoogle Scholar
  58. Stefanidis SD, Kalogiannis KG, Iliopoulou EF, Michailof CM, Pilavachi PA, Lappas AA (2014) A study of lignocellulosic biomass pyrolysis via the pyrolysis of cellulose, hemicellulose and lignin. J Anal Appl Pyrolysis 105:143–150CrossRefGoogle Scholar
  59. Thomas P, Lai CW, Bin Johan MR (2019) Recent developments in biomass-derived carbon as a potential sustainable material for super-capacitor-based energy storage and environmental applications. J Anal Appl Pyrolysis 140:54–85. CrossRefGoogle Scholar
  60. Wachs IE, Routray K (2012) Catalysis science of bulk mixed oxides. ACS Catalysis 2:1235–1246. CrossRefGoogle Scholar
  61. Weldekidan H, Strezov V, Kan T, Kumar R, He J, Town G (2019) Solar assisted catalytic pyrolysis of chicken-litter waste with in-situ and ex-situ loading of CaO and char. Fuel 246:408–416. CrossRefGoogle Scholar
  62. Yang Y, Jin Y, He H, Wang Q, Tu Y, Lu H, Ye Z (2010) Dopant-induced shape evolution of colloidal nanocrystals: the case of zinc oxide. J Am Chem Soc 132:13381–13394CrossRefGoogle Scholar
  63. Zhu H, Han D, Meng Z, Wu D, Zhang C (2011) Preparation and thermal conductivity of CuO nanofluid via a wet chemical method. Nanoscale Res Lett 6:181CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2020

Authors and Affiliations

  1. 1.Chemistry Department, Faculty of ScienceAlexandria UniversityAlexandriaEgypt
  2. 2.Department of ChemistryMiddle Tennessee State UniversityMurfreesboroUSA

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