The role of temperature profile during the pyrolysis of end-of-life-tyres in an industrially relevant conditions auger plant.

Pyrolysis is a chemical recycling process of interest as a means to achieve a sustainable circular economy for end-of-life tyres (ELTs). In the pyrolysis process, ELTs are converted into tyre pyrolysis gas (TPG), tyre pyrolysis oil (TPO) and raw recovered carbon black (RRCB). This work investigates for the first time the effect of different temperature profiles by using a single-auger pyrolysis reactor in an industrially relevant scale (TRL-5). Since the development of this process at this representative scale is quite limited and the temperature profile has not been previously studied, the results achieved in this work can provide a useful database for the development of this process at industrial scale. For this purpose, two different sources of ELTs, commercial truck tyres (CTTs) and passenger car tyres (PCTs), were used. Accordingly, the experimental campaign was conducted using two different incremental temperature profiles (425-550-775 °C and 600-700-800 °C) based on those that can be replicated in an industrial-scale auger pyrolysis plant. For the sake of comparison, two isothermal heating conditions (500-500-500 °C and 600-600-600 °C) were also tested. The results confirmed the remarkable influence of temperature profile on both the distribution and properties of products. The 425-550-775 °C temperature profile was found to enhance limonene production, which is associated with the minimisation of secondary reactions in the first heating zone of the reactor. Additionally, there were very low carbonaceous deposits found in the RRCB because of the high severity of devolatilisation conditions in the third heating zone of the reactor. On the other hand, when the temperature profile was raised, the production of single-ring aromatics, particularly benzene, toluene, ethylbenzene and xylenes (BTEX) significantly increased in the TPO at the expense of limonene. Thus, from this strategy, it is possible to tune the properties of the products depending on the requirements of the application in a single step, getting closer for circular economy in the ELT recycling domain.

On Fractioning the Tire Pyrolysis Oil in a Pilot-Scale Distillation Plant under Industrially Relevant Conditions.

Tire pyrolysis oil (TPO) is one of the most interesting products derived from the pyrolysis of end-of-life tires. Among others, it contains valuable chemicals, such as benzene, toluene, ethylbenzene, and xylene (BTEX), as well as limonene. In order to recover these chemicals, a pilot-scale distillation plant has been designed, erected, and operated using TPO derived from an industrial-scale pyrolysis plant. The distillation facility consists of a packed column (20 kg/h) and is within the fifth technological readiness level. This work describes for the first time the fractioning of the TPO in a continuous operational mode under industrially relevant conditions. For this purpose, different reboiler temperatures (250-290 °C) and reflux ratios (up to 2.4) were preliminarily assessed on the yields and properties of the resulting products: light fraction (LF) and heavy fraction (HF). Thus, the distillation plant is capable of producing 27.0-36.7 and 63.3-73.0 wt % of LF and HF, respectively. The highest BTEX concentration in the LF (55.2 wt %) was found using a reboiler temperature of 250 °C and a reflux ratio of 2.4. Contrarily, the highest limonene concentration (4.9 wt %) in the LF was obtained at 290 °C in the reboiler without reflux. In this sense, the lower the reboiler temperature, the higher the BTEX, and the lower the limonene concentration in the LF. The main results herein obtained serve to gain key insights to operate packed distillation columns using complex and promising hydrocarbons as TPO in order to recover valuable products. In addition, this work provides significant information for optimizing the recovery efficiencies of both BTEX and limonene, as well as their potential applications including that for the resulting HF.

Pyrolysis of tea and coffee wastes: effect of physicochemical properties on kinetic and thermodynamic characteristics.

Physicochemical properties, kinetic pyrolysis and thermodynamic study of spent green tea, pure spent coffee grounds, spent coffee grounds blended with 50% torrefied barley and coffee husk were experimentally investigated using thermogravimetric analysis under an inert atmosphere to evaluate their thermochemical application. Five isoconversional methods were applied to determine effective activation energy (E a) of the pyrolysis processes. All methods showed good agreement by determining fluctuating E a values (150-500 kJ mol-1). Complex E a profiles with conversion were divided into four stages corresponding to thermal degradation of main biomass constituents (extractives, hemicellulose, cellulose and lignin), indicating that extractives decomposition was the least demanding reaction while lignin decomposition was the most demanding. The kinetic process was verified by reconstruction according to the Friedman parameters. The thermodynamic parameters were evaluated to determine the energy demand and efficiency throughout the process. The values obtained for physicochemical properties such as volatile matter (> 68%) and higher heating value (> 17 MJ kg-1), average E a (223-319 kJ mol-1) and significant energy efficiency implied that these types of biomass waste have significant reactivity and consequently the highest potential for the production of bioenergy and a range of high-value chemicals and materials. Supplementary Information: The online version contains supplementary material available at 10.1007/s10973-022-11878-4.

A pyrolysis process coupled to a catalytic cracking stage: A potential waste-to-energy solution for mattress foam waste.

Pyrolysis coupled to either thermal or catalytic cracking of mattress foam waste was performed in a laboratory-scale facility consisting of a fixed-bed reactor joined to a tubular cracking reactor. The results showed a great potential for the production of syngas specially at high cracking temperatures. Particularly, fixing 800 °C in the cracking reactor, a CO and CH4 rich gas with a remarkable amount of H2 was obtained. The addition of catalysts (dolomite, olivine or HiFUEL®) significantly decreased undesirable tar formation, (below 10 wt%), simultaneously increasing the gas yield and keeping CO and CH4 as the main components in the stream, becoming a preferable route that the non-catalytic process. Accordingly, this stream could be used preferably for further applications in energy generation because its heating value ranged between 15.7 MJ/Nm3 and 19.6 MJ/Nm3. In particular, the gas obtained by the use of dolomite could be advantageous for the production of organic compounds such as dimethyl ether (DME) as well as its use an engine or boiler to generate electricity in small facilities. In addition, the solid fraction obtained after de process could be used as a medium quality refused derived fuel (LHV ~ 12 MJ/kg) in order to support the internal energy requirements of the process.

A combined two-stage process of pyrolysis and catalytic cracking of municipal solid waste for the production of syngas and solid refuse-derived fuels.

Pyrolysis combined to either thermal cracking or catalytic cracking of municipal solid waste was performed in a laboratory-scale facility consisting of a fixed-bed reactor followed by a tubular cracking reactor. The results showed great potential for the production of syngas. The incorporation of inexpensive and widely available dolomite in the cracking reactor (with a constant feedstock to calcined dolomite ratio of 5:1) favoured the catalytic cracking of the primary pyrolysis products towards H2 and CO in a temperature range of 800-900 °C. More particularly, it was possible at 900 °C to achieve a syngas consisting of more than 80 vol% CO and H2 with a heating value of 16 MJ/Nm3. Additionally, a homogeneous solid fuel was obtained as a solid residue, which can be used to provide additional energy to support the process or as a refuse-derived fuel. Thus, the great potential of this process was demonstrated for turning municipal solid waste into a valuable gas fraction that can be used directly as a fuel or as a source of different value-added products.

Porosity-Acidity Interplay in Hierarchical ZSM-5 Zeolites for Pyrolysis Oil Valorization to Aromatics.

The properties of crude bio-oils attained by the pyrolysis of lignocellulosic biomass can be greatly enhanced by means of catalytic upgrading. Here, we demonstrate an efficient process concept coupling the production of pyrolysis oil from pine wood with a consecutive catalytic upgrading step over hierarchically structured ZSM-5 zeolites to attain aromatic-rich bio-oils. The selective upgrading of these complex mixtures is shown to be tightly connected to the extent of mesopore development and the density of Brønsted acid sites at the mesopore surface. A full product analysis enables elucidation of the impact of mesopore introduction and the acidic properties on the complex reaction network. The preferential occurrence of decarbonylation reactions in hierarchical zeolites versus dehydration transformations in the bulk counterparts is believed to be decisive in promoting increased aromatics formation.

Demonstration of the waste tire pyrolysis process on pilot scale in a continuous auger reactor.

This work shows the technical feasibility for valorizing waste tires by pyrolysis using a pilot scale facility with a nominal capacity of 150 kWth. A continuous auger reactor was operated to perform thirteen independent experiments that conducted to the processing of more than 500 kg of shredded waste tires in 100 h of operation. The reaction temperature was 550°C and the pressure was 1 bar in all the runs. Under these conditions, yields to solid, liquid and gas were 40.5 ± 0.3, 42.6 ± 0.1 and 16.9 ± 0.3 wt.% respectively. Ultimate and proximate analyses as well as heating value analysis were conducted for both the solid and liquid fraction. pH, water content, total acid number (TAN), viscosity and density were also assessed for the liquid and compared to the specifications of marine fuels (standard ISO 8217). Gas chromatography was used to calculate the composition of the gaseous fraction. It was observed that all these properties remained practically invariable along the experiments without any significant technical problem. In addition, the reaction enthalpy necessary to perform the waste tire pyrolysis process (907.1 ± 40.0 kJ/kg) was determined from the combustion and formation enthalpies of waste tire and conversion products. Finally, a mass balance closure was performed showing an excellent reliability of the data obtained from the experimental campaign.