Comparison of Ca-Based Commercial and Natural Catalysts Performance on Olive Pomace Pyrolysis Process

Abstract

Physicochemical treatment was applied with 20 mg/L alum to the marble processing effluents as 5 minutes 200 rpm mixing, 25 minutes 15 rpm mixing and 60 minutes settling and marble sludge (MS) was produced. Catalytic performance of MS in olive pomace (OP) pyrolysis process was evaluated and compared to commercial Ca(OH)2 since it mainly comprises of different AAEMs (especially Ca and its forms such as CaCO3, CaO) functioned as catalyst. Catalytic pyrolysis was conducted at 600°C and 5°C/min heating rate with 5% and 10% catalyst (MS or Ca(OH)2) dosages. Although both catalysts had important effect on pyrolysis product yields, Ca(OH)2 was found as good alternative for higher gas production and MS was introduced as better option for the higher char production comparing to the conventional OP pyrolysis. Pyrolysis biochars produced with MS were in higher thermal strength than the biochars generated with Ca(OH)2. Moreover, biooils of OP+MS include different organic compounds, such as 9 heptadecanol, 1-eicosanol, ethyl linoleate, ethyl oleate, addition to the compounds observed in pyrolysis liquids of OP and OP+ Ca(OH)2. All detected organic components have diverse usage areas. Ca(OH)2 provided more decrement in the percentages of oxygenated compounds as compared to the MS. Consequently, it can be stated that MS can be used successfully as an alternative to Ca-based commercial catalyst in OP pyrolysis.

Keywords

• Ca-based catalyst
• Marble waste
• Olive pomace
• Pyrolysis

Supporting Institution

TUBITAK

Project Number

TUBITAK-CAYDAG-118Y475

Thanks

This study was financially supported by Bilateral Joint Research Project The Scientific and Technological Research Council of Turkey–TUBITAK with the Japan Society for the Promotion of Science (JSPS) under Grant Code in Turkish side: CAYDAG-118Y475

References

1. Ayadi, M., Awad, S., Villot, A., Abderrabba, M., & Tazerout, M. (2021). Heterogeneous acid catalyst preparation from olive pomace and its use for olive pomace oil esterification. Renewable Energy, 165, 1-13. Doi: https://doi.org/10.1016/j.renene.2020.11.031.
2. Aysu, T., Durak, H., Güner, S., Bengü, A. Ş., & Esim, N. (2016). Bio-oil production via catalytic pyrolysis of Anchusa azurea: Effects of operating conditions on product yields and chromatographic characterization. Bioresource technology, 205, 7-14. Doi: https://doi.org/10.1016/j.biortech.2016.01.015.
3. Ban, Y., Jin, L., Liu, F., Zhu, J., Li, Y., Yang, H., & Hu, H. (2022). Pyrolysis behaviors of model compounds with representative oxygen-containing functional groups in coal over calcium. Fuel, 310, 122247.
4. Çaglar, A., & Demirbaş, A. (2002). Hydrogen rich gas mixture from olive husk via pyrolysis. Energy Conversion and Management, 43(1), 109-117. Doi: https://doi.org/10.1016/S0196-8904(01)00012-7.
5. Dinc, G., & Yel, E. (2018). Self-catalyzing pyrolysis of olive pomace. Journal of analytical and applied pyrolysis, 134, 641-646. Doi: https://doi.org/10.1016/j.jaap.2018.08.018.
6. Edeh, I., Overton, T., & Bowra, S. (2019). Catalytic hydrothermal deoxygenation of fatty acids over palladium on activated carbon catalyst (Pd/C) for renewable diesel production. Biofuels,12(9),1075-1082.
7. Encinar, J., Gonzalez, J., Martínez, G., Roman, S. (2009). Catalytic pyrolysis of exhausted olive oil waste. Journal of Analytical and Applied Pyrolysis, 85 (1), 197-203.
8. Goktepeli, G. (2023). Upcycling approaches with olive and marble processing wastes symbiosis. PhD Thesis, Konya Technical University, Institute of Graduate Studies, Department of Environmental Engineering.

9. Khachani, M., El Hamidi, A., Halim, M., & Arsalane, S. (2014). Non-isothermal kinetic and thermodynamic studies of the dehydroxylation process of synthetic calcium hydroxide Ca (OH) 2. J. Mater. Environ. Sci, 5(2), 615-624.
10. Ko, G. A., & Cho, S. K. (2018). Ethyl linoleate inhibits α-MSH-induced melanogenesis through Akt/GSK3β/β-catenin signal pathway. The Korean journal of physiology & pharmacology: official journal of the Korean Physiological Society and the Korean Society of Pharmacology, 22(1), 53.
11. Kumar, A., Chakraborty, J. P., & Singh, R. (2017). Bio-oil: the future of hydrogen generation. Biofuels, 8(6), 663-674. Doi: https://doi.org/10.1080/17597269.2016.1141276.
12. Li, H., Wang, Y., Zhou, N., Dai, L., Deng, W., Liu, C., Cheng, Y., Liu, Y., Cobb, Y., Chen, P., Ruan, R. (2021). Applications of calcium oxide–based catalysts in biomass pyrolysis/gasification–a review. Journal of Cleaner Production, 291, 125826.
13. Liu, C., Wang, H., Karim, A. M., Sun, J., & Wang, Y. (2014). Catalytic fast pyrolysis of lignocellulosic biomass. Chemical Society Reviews, 43(22), 7594-7623.
14. Lu, Q., Chen, X., Li, K., Meng, L., Xie, X., Yuan, S., Gao, Y., Zhou, X. (2022). Synergistic effect of volatile inherent minerals on catalytic pyrolysis of wheat straw over a Fe–Ca–Ni catalyst. Energy, 253, 124216.
15. Luo, W., Su, Y. F., Hu, Q., Yin, H. L., Wang, S., Ao, L. J., Zhou, Z. (2020). Effect of calcium-based catalysts on pyrolysis liquid products from municipal sludge. BioEnergy Research, 13(3), 887-895. Doi: https://doi.org/10.1007/s12155-020-10109-8.
16. Mohammed, I. Y., Abakr, Y. A., Kazi, F. K., & Yusuf, S. (2017). Effects of pretreatments of napier grass with deionized water, sulfuric acid and sodium hydroxide on pyrolysis oil characteristics. Waste and biomass valorization, 8(3), 755-773. Doi: https://doi.org/10.1007/s12649-016-9594-1.
17. Mutlu, Ü. (2012). Pyrolysis of different biomass samples and characterisation of the products. Master of Science Thesis, Anadolu University.
18. Onen, V., Beyazyuz, P., & Yel, E. (2018). Removal of turbidity from travertine processing wastewaters by coagulants, flocculants and natural materials. Mine Water and the Environment, 37(3), 482-492.
19. Onen, V., Ozgan, A., Goktepeli, G., Kalem, M., Ahmetli, G.,Yel,E. (2022). Marble processing effluent treatment sludge in waste PET pyrolysis. International Journal of Environmental Science and Technology. Doi: https://doi.org/10.1007/s13762-022-04262-0.
20. Osorio, J., & Chejne, F. (2016). Effect of calcium oxide on yield and composition of bio-oil obtained from sugarcane bagasse fast pyrolysis. 21st International Symposium on Analytical and Applied Pyrolysis PYRO.
21. URL 1. National Center for Biotechnology Information (2022). PubChem Compound Summary for CID 5364509, 1-Eicosanol. Retrieved March 14, 2023 from https://pubchem.ncbi.nlm.nih.gov/compound/1-Eicosanol#section=Uses.
22. Wang, Z., Wang, F., Cao, J. and Wang, J. (2010). Pyrolysis of pine wood in a slowly heating fixed-bed reactor: potassium carbonate versus calcium hydroxide as a catalyst, Fuel Processing Technology, 91 (8), 942-950.
23. Xu, T., Zheng, X., Xu, J., & Wu, Y. (2022). Hydrogen-rich gas production from two-stage catalytic pyrolysis of pine sawdust with nano-NiO/Al2O3 catalyst. Catalysts, 12(3), 256.
24. Yang, H., Wang, D., Li, B., Zeng, Z., Qu, L., Zhang, W., & Chen, H. (2018). Effects of potassium salts loading on calcium oxide on the hydrogen production from pyrolysis-gasification of biomass. Bioresource technology, 249, 744-750. Doi: https://doi.org/10.1016/j.biortech.2017.10.083.
25. Yel, E. (2022). Atık Mermer Çamuru, Plastikler ve Pirinadan Geliştirilmiş Geri Dönüşüm (Upgraded Recycle) ile Faydalı Ürünlerin Kazanılabilirliği. TÜBİTAK- Bilateral Cooperation Project.
26. Zhang, H., Luo, B., Wu, K., Wu, H., Yu, J., & Wang, S. (2022). Enhancing aromatic yield from catalytic pyrolysis of Ca2+-loaded lignin coupled with metal-modified HZSM-5. Applications in Energy and Combustion Science, 9, 100049.
27. Zhao, X., Liu, C., Wang, L., Zuo, L., Zhu, Q., & Ma, W. (2019). Physical and mechanical properties and micro characteristics of fly ash-based geopolymers incorporating soda residue. Cement and Concrete Composites, 98, 125-136.