Estimation of pyrolysis product of LDPE degradation using different process parameters in a stirred reactor

Pyrolysis of low density polyethylene (LDPE) by equilibrium fluid catalytic cracking (FCC) was studied in a stirred reactor under different process parameters. In this work, the effect of process parameters such as degradation temperature (420-510°C), catalyst/polymer ratio (0-60%), carrier gas type (H2, N2, ethylene, propylene, Ar and He), residence time and agitator speed (0-300 rpm) on the condensate yield (liquid, gas and coke) and product composition were considered. Reaction products were determined by GC analysis and shown to contain naphthenes (cycloalkanes), paraffins (alkanes), olefins (alkenes) and aromatics. Higher temperature and more catalyst amount enhanced LDPE cracking. The maximum “fuel like” condensed product yield was attained at 450°C and 10% catalyst, respectively and gaseous products increased with increases in temperature. Hydrogen as a reactive carrier gas increased the condensed and paraffinic product yield. Appropriate heat transfer (by stirring) increased the catalyst efficiency in a stirred reactor

Effect of temperature, heating rate and zeolite-based catalysts on the pyrolysis of high impact polystyrene (HIPS) waste to produce fuel-like products

Pyrolysis of high impact polystyrene (HIPS) waste has been investigated under different process parameters, such as temperature, heating rate and types of zeolitic catalysts to produce valuable liquid products. Liquid, gas and coke as products of pyrolysis and aromatic, naphthene, olefin and paraffin as liquid components were obtained and their molecular weight distributions were studied with changing the process parameters in a stirred reactor. Aromatic-rich hydrocarbons within the gasoline range were the main pyrolysis products. Type of zeolitic catalysts, temperature and heating rate had significant effects on the products quality and quantity. Non-isothermal mass losses of high impact polystyrene were measured using a thermo-gravimetric analyzer (TGA) at heating rates of 5, 15, 30, 45 and 90°C min-1 until the furnace wall temperature reached 600°C. The DTG (differential thermal gravimetric) curves showed that heating rate had no obvious effect on the degradation trends in the studied range, and by increasing heating rate, the activation energies were decreased obviously from 222.5 to183.6 kJ mol-1

CeO2 and La2O3 promoters in the steam reforming of polyolefinic waste plastic pyrolysis volatiles on Ni-based catalysts

[EN] Based on the promising results of La2O3 and CeO2 promoted Ni/Al2O3 catalysts in the reforming of biomass pyrolysis volatiles, the performance of these catalysts and the non-promoted one was 2 evaluated in the pyrolysis and in-line steam reforming of polypropylene (PP). The experiments were carried out in a continuous bench scale pyrolysis-reforming plant using two space times of 4.1 and 16.7 gcat min gplastic−1 and a steam/PP ratio of 4. The prepared catalysts and the deposited coke were characterized by N2 adsorption-desorption, X-ray fluorescence (XRF), X-ray diffraction (XRD), temperature programmed oxidation (TPO) and transmission electron microscopy (TEM). The Ni/Al2O3 catalyst showed suitable performance regarding pyrolysis product conversion and hydrogen production, and led to moderate coke deposition. It is to note that La2O3 incorporation remarkably improved catalyst performance compared to the other two catalysts in terms of conversion (> 99 %), hydrogen production (34.9 %) and coke deposition (2.24 wt%).This work was carried out with the financial support from Spain’s ministries of Economy and Competitiveness (CTQ2016-75535-R (AEI/FEDER, UE), Science, Innovation and Universities (RTI2018-101678-B-I00 (MCIU/AEI/FEDER, UE)) and, Science and Innovation PID2019-107357RB-I00 (MCI/AEI/FEDER, UE)), the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No. 823745, and the Basque Government (IT1218-19 and KK-2020/00107)

The production of high efficiency Ziegler–Natta catalyst with dual active sites nature using cyclohexyl chloride as promoter with super activity and produced superior polyethylene with controllable molecular weight distribution

In the previous studies, the several halocarbons (HC) were tested as promoters for a Ti-based Ziegler–Natta (ZN) catalyst at different polymerization conditions. The Results showed that chloro cyclohexane has the best operation in catalyst activity, polymer particle size growth, hydrogen responsibility and wax reduction too. For the first time in this study, the effect of Al/Ti ratio on the optimum HC/Ti ratio has been considered and the results showed that the optimum HC/Ti ratio depends on the Al/Ti ratio directly. In the optimum HC/Ti ratio, the catalyst activity and hydrogen responsibility ratio of the catalyst increase up to 125 and 55% respectively. The acceptable growth of polymer powder up to 46%, lower flow rate ratio (FRR) up to 19% and decrease of wax amount up to 12%, completed the promotion results. Furthermore, in the next part of this study and as key note, a little dose of halocarbon was used in the catalyst preparation to produce the special catalysts with dual active sites. In the catalyst preparation, the concentration of each active sites depends on the halocarbon amount and it can control the molecular weight distribution of the produced polyethylene; because each active sites have different response to hydrogen. The halocarbon based catalysts showed the remarkable effect on the catalyst activity, the molecular weight and especially molecular weight distribution (MWD). The flow rate ratio and MWD could be increased up to 77 and 88% respectively as the main result of halocarbon addition during the catalyst preparation

A comprehensive experimental investigation of plastic waste pyrolysis oil quality and its dependence on the plastic waste composition

Pyrolysis of plastic packaging waste yields a liquid product that can be processed in steam crackers producing light olefins and hence closing the loop towards new virgin plastics. However, there is a lack of knowledge on how the plastic waste composition affects the pyrolysis oil quality regarding hydrocarbon composition and contaminant concentrations. The associated uncertainty is a key reason why thermochemical recycling of contaminated plastic waste is not yet industrially established. In this study, post-consumer plastic packaging waste fractions, namely mixed polyolefins (MPO), polyethylene (PE), and polypropylene (PP) were processed in a continuous pilot-scale pyrolysis unit and the pyrolysis oils subsequently characterized using advanced analytical techniques such as two-dimensional gas chromatography. Substantial amounts of branched olefins (~63 wt%) and diolefins (~20 wt%) were detected in the pyrolysis oil of PP-rich waste, while PE-rich waste produced high amounts of linear paraffins (~34 wt%) and olefins (~26 wt%). Furthermore, significant amounts of nitrogen, oxygen, chlorine, iron, sodium and silicon were detected in the pyrolysis oils exceeding feedstock specifications for industrial steam crackers by orders of magnitude. The results show that next to improved waste sorting and separation processes, pre- and post-treatment techniques are required to produce pyrolysis products suitable for chemical processing

Thermal pyrolysis of waste versus virgin polyolefin feedstocks: The role of pressure, temperature and waste composition

Due to the complexity and diversity of polyolefinic plastic waste streams and the inherent non-selective nature of the pyrolysis chemistry, the chemical decomposition of plastic waste is still not fully understood. Accurate data of feedstock and products that also consider impurities is, in this context, quite scarce. Therefore this work focuses on the thermochemical recycling via pyrolysis of different virgin and contaminated waste-derived polyolefin feedstocks (i.e., low-density polyethylene (LDPE), polypropylene (PP) as main components), along with an investigation of the decomposition mechanisms based on the detailed composition of the pyrolysis oils. Crucial in this work is the detailed chemical analysis of the resulting pyrolysis oils by comprehensive two-dimensional gas chromatography (GC × GC) and ICP-OES, among others. Different feedstocks were pyrolyzed at a temperature range of 430–490 °C and at pressures between 0.1 and 2 bar in a continuous pilot-scale pyrolysis unit. At the lowest pressure, the pyrolysis oil yield of the studied polyolefins reached up to 95 wt%. The pyrolysis oil consists of primarily α-olefins (37–42 %) and n-paraffins (32–35 %) for LDPE pyrolysis, while isoolefins (mostly C9 and C15) and diolefins accounted for 84–91 % of the PP-based pyrolysis oils. The post-consumer waste feedstocks led to significantly less pyrolysis oil yields and more char formation compared to their virgin equivalents. It was found that plastic aging, polyvinyl chloride (PVC) (3 wt%), and metal contamination were the main causes of char formation during the pyrolysis of polyolefin waste (4.9 wt%)