8 figures, 3 tables.-- Supplementary information available., 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., This work is part of the BLACKCYCLE project (For the circular economy of tyre domain: recycling end of life tyres into secondary raw materials or tyres and other product applications) which has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 869625. The authors would also like to thank the Regional Government of Aragon (DGA) for the support provided under the research groups support programme and CSIC for the interdisciplinary thematic platform SUSPLAST., Peer reviewed

7 figures, 2 tables., 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., This work is part of the BLACKCYCLE project (for the circular economy of tyre domain: recycling end-of-life tires into secondary raw materials or tires and other product applications), which has received funding from the European Union’s Horizon 2020 research and innovation program under Grant agreement no. 869625. [...] The authors would also like to thank the Regional Government of Aragon (DGA) for the support provided under the research group support program, and CSIC for the interdisciplinary thematic platform SUSPLAST., Peer reviewed

Under a Creative Commons license BY-NC 4.0, Table S1. TPG Composition. All data in volume percentage. Table S2. CTT Sulphur mass balance. All data in weight percentage. Table S3. PCT Sulphur mass balance. All data in weight percentage., This work is part of the BLACKCYCLE project (For the circular economy of tyre domain: recycling end of life tyres into secondary raw materials or tyres and other product applications) which has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 869625. The authors would also like to thank the Regional Government of Aragon (DGA) for the support provided under the research groups support programme and CSIC for the interdisciplinary thematic platform SUSPLAST., Peer reviewed

11 figures, 2 tables., This work describes the key features involved in the design and operation of a pilot scale distillation column for the recovery of value-added products from tire pyrolysis oil (TPO), as part of the BLACKCYCLE project. The distillation unit was designed using engineering heuristic rules, simulated distillation (SimDist) data and Aspen Hysys ® modeling. The distillation plant consists of a packed column with a nominal throughput of 20 kg/h, and is classified at the fifth technology readiness level (TRL-5). The commissioning and results of long-term experimental campaigns for validation purposes are also presented. In this way, important information is gathered for the design of larger plants. The distillation unit was tested and validated using TPO produced from a pilot scale continuous single-auger pyrolysis plant. A first distillation was performed yielding a heavy fraction (HF-1) with properties suitable for carbon black production, while the light fraction (LF-1) includes the presence of value-added chemicals such as benzene, toluene, ethylbenzene and xylenes (BTEX) and limonene. The LF-1 was also used for a second distillation, producing a stream high in limonene at the bottom (HF-2), and another one high in BTEX compounds at the top (LF-2), which are valuable raw materials for polymer production and petrochemicals, respectively. The key results obtained here are expected to provide an outstanding impetus for the circular economy of complex streams such as end-of-life tires (ELTs) by combining pyrolysis and distillation technologies., This work is part of the BLACKCYCLE project (For the circular economy of tyre domain: recycling end of life tyres into secondary raw materials or tyres and other product applications) which has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement N° 869625. The authors would also like to thank the Regional Government of Aragon (DGA) for the support provided under the research groups support programme and CSIC for the interdisciplinary thematic platform SUSPLAST., Peer reviewed

Under a Creative Commons license BY NC ND 4.0., Figure S1: Calibration mix chromatogram obtained for ASTM D2887 method. Figure S2: Calibration curve obtained for ASTM D2887 method. Figure S3: Chromatograms obtained for the a) TPO, the first distillation of TPO b) light fraction (LF), c) heavy fraction (HF) and the second distillation of the light fraction of TPO d) LF and e) HF. Table S1: Percentage of relative area obtained with the quantification ion (m/z) for the TPO by GC-MS according to the NIST2020 library (BTEX=benzene, toluene, ethylbenzene, xylenes; CC= cyclic compounds, AAA= alkanes, alkenes, alkynes, SB= Substituted benzenes, no BTEX, HC= heterocyclic compounds, I= indenes, PAH= polycyclic aromatic hydrocarbons, O= others). Table S2: Percentage of relative area obtained with the quantification ion (m/z) for the first distillation of the TPO, LF-1, by GC-MS according to the NIST2020 library. Table S3: Percentage of relative area obtained with the quantification ion (m/z) for the first distillation of the TPO, HF-1, by GC-MS according to the NIST2020 library. Table S4: Percentage of relative area obtained with the quantification ion (m/z) for the second distillation of the TPO, LF-2, by GC-MS according to the NIST2020 library. Table S5: Percentage of relative area obtained with the quantification ion (m/z) for the second distillation of the TPO, HF-2, by GC-MS according to the NIST2020 library., This work is part of the BLACKCYCLE project (For the circular economy of tyre domain: recycling end of life tyres into secondary raw materials or tyres and other product applications) which has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement N° 869625. The authors would also like to thank the Regional Government of Aragon (DGA) for the support provided under the research groups support programme and CSIC for the interdisciplinary thematic platform SUSPLAST., Peer reviewed

6 figures, 5 tables., This work, carried out within the framework of the BlackCycle project, demonstrates the robustness of an auger reactor for the pyrolysis of end-of-life tires (ELTs) to be considered within the seventh level of technology readiness (TRL-7). For this purpose, the resulting pyrolysis products are compared with those obtained from a pilot scale facility ranging within the fifth technology readiness level (TRL-5). Using the same type of ELTs, tire trucks (TTs), operating conditions used at the TRL-5 plant are attempted to mimic those expected at a semi-industrial plant: tailored temperature profile (450, 550, and 775 °C) and residence time for vapors (30 s) and solids (15 min). The feed mass rate is 4 and 400 kg/h for the pilot and semi-industrial plants, respectively. The yields of tire pyrolysis oil (TPO), tire pyrolysis gas (TPG), and raw recovered carbon black (RRCB) from both plants, as well as their key properties and characteristics, are in good agreement with each other. The TPO produced by both plants contains comparable concentrations of value-added chemicals such as benzene, toluene, xylene, ethylbenzene, and limonene. There is also a very similar pattern between the simulated distillation curves. The TPG obtained from both plants is also very rich in H2 and CH4 and has a lower calorific value of 52-54 MJ/Nm3 (N2 free basis). Although the RRCBs produced by the two plants are more demanding and require more labor, they do have a number of comparable characteristics. All this information demonstrates not only the reliability of the experimental campaigns to scale up the pyrolysis process but also the robustness of the semi-industrial scale plant based on the auger technology to be classified at TRL-7., This work is part of the BLACKCYCLE project (For the circular economy of tire domain: recycling end of life tires into secondary raw materials or tires and other product applications) which has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 869625. The authors would also like to thank the Regional Government of Aragon (DGA) for the support provided under the research groups support programme and CSIC for the interdisciplinary thematic platforms SusPlast and SosEcoCir., Peer reviewed

1 table, 15 figures., The recovery of waste-based feedstocks is an important step in the defossilization of the petrochemical industry and thus in the circular economy for petroleum-based products that have reached the end of their useful life such as end-of-life tires (ELT). This work is part of the European BLACKCYCLE project, and focuses on the distillation performance of tire pyrolysis oil (TPO) obtained from an industrial scale plant, ranked at the ninth technology readiness level (TRL-9). The influence of different reboiler temperatures and reflux ratios on the yields and characteristics of the resulting streams was investigated using a pilot scale packed distillation column under industrially relevant conditions, classified within the fifth technology readiness level (TRL-5). The distillation process was shown to be capable of continuously producing a light fraction (LF) with a very high concentration of benzene, toluene, ethylbenzene and xylenes (BTEX) suitable for high value chemicals. Similarly, a heavy fraction (HF) with a high C/H ratio, high flash point and high presence of polycyclic aromatic hydrocarbons (PAH) is obtained, making it an attractive alternative to carbon black oil. These results are quite outstanding to accomplish the recovery of waste-based value-added feedstocks in such a way that the carbon embedded in the ELT is retained in the petrochemical industry. This work is committed to the development of green, affordable and practical recycling processes to fill the gap in the production of sustainable chemical commodities, while paving the way to address one of the industry's greatest challenges: the defossilization of the petrochemical industry., This work is part of the BLACKCYCLE project (For the circular economy of tyre domain: recycling end of life tyres into secondary raw materials or tyres and other product applications) which has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement no. 869625. The authors would also like to thank the Regional Government of Aragon (DGA) for the support provided under the research groups support program and CSIC for the interdisciplinary thematic platforms SusPlast (Sustainable Plastics) and SosEcoCir (Sustainability and Circular Economy)., Peer reviewed

Under a Creative Commons license CC-BY 3.0, https://creativecommons.org/licenses/by/3.0/, Tables: Table S1. Experimental campaign and detailed GC characterization of the light fraction.--Table S2. Experimental campaign and detailed GC characterization of the heavy fraction.-- Tale S3. BTEX concentrations reported in the literature from the pyrolysis of ELTs.-- Table S4. Elemental and calorific analyses of the resulting heavy fraction.-- Table S5. GC/MS results of the resulting heavy fraction.-- Figures: Fig. S1. Steady-state temperature profile of the column (run # 1).-- Fig. S2. Steady-state temperature profile of the column (runs 2 and 7).-- Fig. S3. Steady-state temperature profile of the column (runs 3 and 8).-- Fig. S4. Steady-state temperature profile of the column (runs 4 and 9).-- Fig. S5. Steady-state temperature profile of the column (runs 5 and 10).-- References, This work is part of the BLACKCYCLE project (For the circular economy of tyre domain: recycling end of life tyres into secondary raw materials or tyres and other product applications) which has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement no. 869625. The authors would also like to thank the Regional Government of Aragon (DGA) for the support provided under the research groups support program and CSIC for the interdisciplinary thematic platforms SusPlast (Sustainable Plastics) and SosEcoCir (Sustainability and Circular Economy)., Peer reviewed

10 figures, 7 tables., Pyrolysis contributes to the transition of the tyre industry towards a circular economy model. Tyre rubber is a complex blend of polymers, inorganic additives and grades of carbon black, depending on the tyre type and section. The products of the end-of-life tyres (ELTs) pyrolysis are heavily influenced by the original composition, so separation prior to pyrolysis could be an important step in optimising the recycling process. However, recyclers often ignore the composition of ELTs. This study aims to develop a simple methodology for evaluating the potential resource recovery of ETLs samples from a set of thermogravimetric experiments applying a Distributed Activation Energy Model (DAEM). Pyrolysis experiments were also carried out in a fixed-bed reactor to analyse the composition of the products. Direct linear relations were identified between specific values of the initial mass fraction parameter of the DAEM and the natural and synthetic rubber content, and notably with the limonene content in the pyrolysis oils. A high 12 wt% limonene in the oil product was obtained from the sample with the 83 wt% natural rubber content at 450 ºC. In addition, significant differences in the ash content were observed in the raw recovered carbon black from the tread sections (31 wt%-55 wt%) to the non-tread sections of the ELTs (7 wt%-16 wt%), which had a positive effect on its quality. This work demonstrates that the application of a straightforward methodology on separated types and sections of ELTs can greatly enhance the economic and environmental sustainability of their recycling processes., The authors would like to thank the Regional Government of Aragon (DGA) for the support provided through the Research Groups Support Program. The CSIC Interdisciplinary Thematic Platforms (PTI) SusPlast (Sustainable Plastics) and SosEcoCir (Sustainability and Circular Economy) are also recognised. The authors also thank the financial support of European BLACKCYCLE Project under Grant agreement no. 869625., Peer reviewed

Under a Creative Commons BY-NC-ND 4.0 license, 2. Materials and methods
2.4.2 Tyre pyrolysis oil
Fig. A1. Plot of the compound calibration curve for 0.02 – 0.2 wt.% apart from styrene (0.05-0.5 wt.%) and limonene (0.02-1 wt.%).
3. Results and discussion
3.1 Thermogravimetric analysis
Fig. A2. Conversion rate comparison at: a) 10 °C/min, b) 20 °C/min and c) 50 °C/min
3.2 Kinetic analysis using DAEM
Fig. A.3. Comparison between experimental data and theoretical data generated with DAEM at 5 °C/min and 10 °C/min
3.3 Pyrolysis experiments
3.3.4. Raw recovered carbon black
Table A1.
TPO elemental characterisation
Table A2.
Carbon balance, The authors would like to thank the Regional Government of Aragon (DGA) for the support provided through the Research Groups Support Program. The CSIC Interdisciplinary Thematic Platforms (PTI) SusPlast (Sustainable Plastics) and SosEcoCir (Sustainability and Circular Economy) are also recognised. The authors also thank the financial support of European BLACKCYCLE Project under Grant agreement no. 869625., Peer reviewed