Fuel Oil Production from Two-Stage Pyrolysis-Catalytic Reforming of Brominated High Impact Polystyrene Using Zeolite and Iron Oxide Loaded Zeolite Catalysts


The experiments of two-stage pyrolysis and catalytic reforming of high impact polystyrene (HIPS) containing brominated flame retardants and antimony trioxide (Sb2O3) were conducted in the presence of four zeolite catalysts in order to remove the bromine content from the derived oil products. The four catalysts used were natural zeolite (NZ), iron oxide loaded natural zeolite (Fe-NZ), HY zeolite (YZ) and iron oxide loaded HY zeolite (Fe-NZ). The effect of catalyst types on the product yield, the gas and oil product composition and the debromination efficiency of the oil products was evaluated in details. The results showed that the loading of iron oxides reduced the pore size and surface areas of natural zeolite and HY zeolite. Regardless of the presence of catalysts, the single-ring aromatic compounds were the main components of the oil products, such as ethylbenzene, toluene, styrene and cumene. Meanwhile, when YZ and Fe-YZ were used, the two-ring and multi-ring aromatic compounds in the oils, as well as the yield of gas products, significantly increased at the expense of valuable single-ring aromatic compounds. Furthermore, in terms of the debromination performance of the oil products, Fe-NZ and Fe-YZ were better than NZ and YZ, duo to the loading of iron oxide, which could react with derived HBr and then remove more bromine from the oil products.

Share and Cite:

Wu, H. , Shen, Y. , Ma, D. , An, Q. , Harada, N. and Yoshikawa, K. (2015) Fuel Oil Production from Two-Stage Pyrolysis-Catalytic Reforming of Brominated High Impact Polystyrene Using Zeolite and Iron Oxide Loaded Zeolite Catalysts. Open Journal of Ecology, 5, 136-146. doi: 10.4236/oje.2015.54012.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] Yang, X.N., Sun, L.S., Xiang, J., Hu, S. and Su, S. (2013) Pyrolysis and Dehalogenation of Plastics from Waste Electrical and Electronicequipment (WEEE): A Review. Waste Management, 33, 462-473.
[2] Martinho, G., Pires, A., Saraiva, L. and Ribeiro, R. (2012) Composition of Plastics from Waste Electrical and Electronic Equipment (WEEE) by Direct Sampling. Waste Management, 32, 1213-1217.
[3] Ongondo, F.O., Williams, I.D. and Cherrett, T.J. (2011) How Are WEEE Doing? A Global Review of the Management of Electrical and Electronic Wastes. Waste Management, 31, 714-730.
[4] Jakab, E., Uddin, Md.A., Bhaskar, T. and Sakata, Y. (2003) Thermal Decomposition of Flame-Retarded High Impact Polystyrene. Journal of Analytical and Applied Pyrolysis, 68-69, 83-99.
[5] Hall, W.J. and Williams, P.T. (2008) Removal of Organobromine Compounds from the Pyrolysisoils of Flame Retarded Plastics Using Zeolite Catalysts. Journal of Analytical and Applied Pyrolysis, 81, 139-147.
[6] Hall, W.J., Miskolczi, N., Onwudili, J. and Williams, P.T. (2008) Thermal Processing of Toxic Flame-Retarded Polymers Using a Waste Fluidized Catalytic Cracker (FCC) Catalyst. Energy & Fuels, 22, 1691-1697.
[7] Miskolczi, N., Hall, W.J., Angyal, A., Bartha, L. and Williams, P.T. (2008) Production of Oil with Low Organobromine Content from the Pyrolysisof Flame Retarded HIPS and ABS Plastics. Journal of Analytical and Applied Pyrolysis, 83, 115-123.
[8] Bhaskar, T., Matsui, T., Azhar Uddin, Md., Kaneko, J., Muto, A. and Sakata, Y. (2003) Effect of Sb2O3 in Brominated Heating Impact Polystyrene (HIPS-Br) on Thermal Degradation and Debromination Byiron Oxide Carbon Composite Catalyst (Fe-C). Applied Catalysis B: Environmental, 43, 229-241.
[9] Bhaskar, T., Matsui, T., Kaneko, J., Uddin, Md.A., Muto, A. and Sakata, Y. (2002) Novel Calcium Based Sorbent (Ca-C) for the Dehalogenation (Br, Cl) Process during Halogenated Mixed Plastic (PP/PE/PS/PVC and HIPS-Br) Pyrolysis. Green Chemistry, 4, 372-375.
[10] Terakado, O., Ohhashi, R. and Hirasawa, M. (2011) Thermal Degradation Study of Tetrabromobisphenol A under the Presence Metaloxide: Comparison of Bromine Fixation Ability. Journal of Analytical and Applied Pyrolysis, 91, 303-309.
[11] Terakado, O., Ohhashi, R. and Hirasawa, M. (2013) Bromine Fixation by Metal Oxide in Pyrolysis of Printed Circuit Board Containing Brominated Flame Retardant. Journal of Analytical and Applied Pyrolysis, 103, 216-221.
[12] Castano, P., Elordi, G., Olazar, M., Aguayo, A.T., Pawelec, B. and Bilbao, J. (2011) Insights into the Coke Deposited on HZSM-5, Hβ and HY Zeolites during the Cracking of Polyethylene. Applied Catalysis B: Environmental, 104, 91-100.
[13] Park, Y., Namioka, T., Sakamoto, S., Min, T.J., Roh, S.A. and Yoshikawa, K. (2010) Optimum Operating Conditions for a Two-Stage Gasification Process Fueled by Polypropylene by Means of Continuous Reactor over Ruthenium Catalyst. Fuel Processing Technology, 91, 951-957.
[14] Adam, F., Wong, J.T. and Ng, E.P. (2013) Fast Catalytic Oxidation of Phenol over Iron Modified Zeolite L Nanocrystals. Chemical Engineering Journal, 214, 63-67.
[15] Joshi, P.N., Awate, S.V. and Shiralkar, V.P. (1993) Partial Isomorphous Substitution of Fe3+ in the LTL Framework. The Journal of Physical Chemistry, 97, 9749-9753.
[16] Lee, S.Y., Yoon, J.H., Kim, J.R. and Park, D.W. (2001) Catalytic Degradation of Polystyrene over Natural Clinoptilolite Zeolite. Polymer Degradation and Stability, 74, 297-305.
[17] Dawood, A. and Miura, K. (2002) Catalytic Pyrolysis of γ-Irradiated Polypropylene (PP) over HY Zeolite for Enhancing the Reactivity and the Product Selectivity. Polymer Degradation and Stability, 76, 45-52.
[18] Bagri, R. and Williams, P.T. (2002) Catalytic Pyrolysis of Polyethylene. Journal of Analytical and Applied Pyrolysis, 63, 29-41.
[19] Botas, J.A., Serrano, D.P., García, A., de Vicente, J. and Ramos, R. (2012) Catalytic Conversion of Rapeseed Oil into Raw Chemicals and Fuels over Ni-and Mo-Modified Nanocrystalline ZSM-5 Zeolite. Catalysis Today, 195, 59-70.
[20] Lee, S.Y., Yoon, J.H., Kim, J.R. and Park, D.W. (2002) Degradation of Polystyrene Using Clinoptilolite Catalysts. Journal of Analytical and Applied Pyrolysis, 64, 71-83. http://dx.doi.org/10.1016/S0165-2370(01)00171-1
[21] Ukei, H., Hirose, T., Horikawa, S., Takai, Y., Taka, M., Azuma, N. and Ueno, A. (2000) Catalytic Degradation of Polystyrene into Styrene and a Design of Recyclable Polystyrene with Dispersed Catalysts. Catalysis Today, 62, 67-75.
[22] Jung, S.H., Kim, S.J. and Kim, J.S. (2013) The Influence of Reaction Parameters on Characteristics of Pyrolysis Oils from Waste High Impact Polystyrene and Acrylonitrile-Butadiene-Styrene Using a Fluidized Bed Reactor. Fuel Processing Technology, 116, 123-129.
[23] Jung, S.H., Kim, S.J. and Kim, J.S. (2012) Fast Pyrolysis of a Waste Fraction of High Impact Polystyrene (HIPS) Containing Brominated Flame Retardants in a Fluidized Bed Reactor: The Effects of Various Ca-Based Additives (CaO, Ca(OH)2 and Oyster Shells) on the Removal of Bromine. Fuel, 95, 514-520.
[24] Seo, Y.H., Lee, K.H. and Shin, D.H. (2003) Investigation of Catalytic Degradation of High-Density Polyethylene by Hydrocarbon Group Type Analysis. Journal of Analytical and Applied Pyrolysis, 70, 383-393.

Copyright © 2021 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.