Al-Salem, S; (2013) Thermo-Chemical Treatment (TCT) of Polymers in Multi-Scale Reactors: A Kinetics and Life Cycle Assessment (LCA) Study. Doctoral thesis (Ph.D), UCL (University College London).

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Abstract

The main reasons behind the success of the petrochemicals industry are not only the vast array of products that it provides - considered vital to our daily functions - but also the added value that it brings to the crude oil barrel price, making it a reliable venture for any concerned party. However, the industry is now faced with a fluctuating market and an unstable economy, which makes it imperative to find a more abundant and sustainable feedstock. Of all petrochemical derivatives, polymers (and their related industries) occupy the major share, and this makes the plastics industry a growing sector in terms of processing and conversion. Both virgin and waste plastics represent an attractive source of energy and product recovery. The main objective of this work was to investigate the thermo-chemical treatment (TCT) of polymers at different scales, and the reactors studied ranged from micro laboratory scale to industrial units suitable for covering large market demands. Within this framework, the degressive behaviour of polyolefin polymers (three virgin grades and two recyclate ones) was investigated alongside the products yielded (gases (C1-C4), liquids (non-aromatic C5-C10), aromatics (single ring structures) and waxes (> C11). This was achieved in a micro scale isothermal pyrolysis process, using 15 mg in a laboratory thermogravimetric analyser covering the temperature range of 500-600°C. The analysis led to the development of an nth order novel model on the basis of lumped products yielded by pyrolysis. The degradation mechanism was used to develop the mathematical breakdown of the primary, secondary and tertiary reactions. The model developed predicts the yield of the four different products and the polymer residual fraction at any operating condition proving to be a useful tool for reactor design and simulation, where the production of a specific chemical at a certain operating condition is paramount. In addition, laboratory scale isothermal pyrolysis experiments on end of life tyres (ELTs) were also conducted. This was achieved as a means to demonstrate the application of the concept previously applied to the polyolefins. A thermal cracking (degradation) scheme was proposed based on the global yielded products, which were lumped into four categories, namely gases (C1-C4), liquids (non-aromatic C5-C10), single ring aromatics (C5-C10), and char. The depolymerization kinetics (from primary, secondary and tertiary reactions) evaluation showed a high match with the experimental results obtained in this work. Finally, a life cycle assessment (LCA) was conducted for three integrated scenarios that reflect the current (2012) treatment of waste plastics in the Greater London area. The scenarios studied utilised a fraction of the polymers treated as a feedstock for two industrial scale TCT technologies; namely a low-temperature pyrolysis reactor that works using BP® technology and a hydrocracking unit that utilises the Veba-Combi Cracking (VCC®) concept. The scenarios studied also include transfer stations, a dry materials recovery facility (MRF) and a combined heat and power (CHP) incineration unit. The energy recovered via the different processes studied, as well as the chemicals and petrochemicals recovered, were all considered as credits in the LCA conducted. Chemicals obtained by the TCT units are very valuable and can replace refinery cuts and petrochemicals (e.g. syncrude (crude oil), naphtha, heavy (waxes) fraction (comparable to atmospheric residue), gases (C3 and C4) refinery cuts, etc.). This led to a technoeconomic analysis of the three integrated scenarios in order to assess the overall profitability. The analysis included capital, operating and maintenance costs, gate fees, transportation costs and corporation tax. The eligibility for governmental incentives (i.e. renewable obligation certificates (ROCs), levy exemption certificates (LECs) and packaging recovery notes (PRNs)) was also considered. The results obtained from the work carried out and reported in this thesis point towards ideal strategies for the treatment of polymers within the urban environment. It also provides a detailed understanding of potential products from polymers introduced to TCT units. This also aids the optimum recovery of petrochemicals, chemicals and energy from different TCT processes, and could help the UK Government in meeting its energy policy targets. It can also contribute to the energy security through diversification of supply. Finally, it provides a perspective on the integration between the crude oil upstream industry and different petrochemical complexes and oil refineries, through the use of different TCT units to increase the production of petrochemicals in existing plants.

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