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Abstract

A mathematical model of waste tyre pyrolysis process is developed in this work. Tyre material decomposition based on a simplified reaction mechanism leads to main product lumps: noncondensable (gas), condensable (pyrolytic oil) and solid (char). The model takes into account kinetics of heat and mass transfer in the grain of the shredded rubber material as well as surrounding gas phase. The main reaction routes were modelled as the pseudo-first order reactions with a rate constant calculated from the Arrhenius type equation using literature values of activation energy determined for main tyre constituents based on TG/DTG measurements and tuned pre-exponential parameter values obtained by fitting theoretical predictions to the experimental results obtained in our laboratory reactor. The model was implemented within the CFD software (ANSYS Fluent). The results of numerical simulation of the pyrolysis process revealed non-uniformity of sample’s porosity and temperature. The simulation predictions were in satisfactory agreement with the experimentally measured mass loss of the tyre sample during pyrolysis process investigated in a laboratory reactor.

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Authors and Affiliations

Leszek Rudniak
Piotr M. Machniewski
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Abstract

There is general agreement that primary pyrolysis products of end-of-life tyres should be valorised to improve the economics of pyrolysis. In this work, tyre pyrolysis char (TPC) is produced in a pyrolysis pilot plant designed and built at our home university. The produced TPC was upgraded to tyre-derived activated carbon (TDAC) by activation with CO2, and then characterised using stereological analysis (SA) and nitrogen adsorption at 77 K. SA showed that the grains of TPC and TDAC were quasi- spherical and slightly elongated with a 25% increase in the mean particle cross-section surface area for TDAC. The textural properties of TDAC demonstrated the BET and micropore surface areas of 259 and 70 m2/g, respectively. Micropore volume and micropore surface area were 5.8 and 6.7 times higher for TDAC than TPC at  2 nm, respectively. The n-hexane adsorption was investigated using experiments and modelling. Eight adsorption isotherms along with three error functions were tested to model the adsorption equilibrium. The optimum sets of isotherm parameters were chosen by comparing sum of the normalized errors. The analysis indicated that the Freundlich isotherm gave the best agreement with the equilibrium experiments. In relation to different activated carbons, the adsorption capacity of TDAC for n-hexane is about 16.2 times higher than that of the worst reference material and 4.3 times lower than that of the best reference material. In addition, stereological analysis showed that activation with CO2 did not change the grain’s shape factors. However, a 25% increase in the mean particle cross-section surface area for TDAC was observed.

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Authors and Affiliations

Tomasz Kotkowski
ORCID: ORCID
Robert Cherbański
ORCID: ORCID
Eugeniusz Molga
ORCID: ORCID
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Abstract

Three activated chars obtained from end-of-life tyre pyrolysis differing in activation time (AC110 – 110 min, AC130 – 130 min, and AC150 – 150 min) were successfully used as adsorbents for the removal of model dye – Rhodamine B (RhB) from aqueous solutions. The effects of solution pH, adsorption kinetics, and equilibrium adsorption were investigated. The results showed that the adsorption was strongly pH-dependent; the highest percentage of RhB dye adsorbed was obtained at pH 2.0 and the removal efficiency decreased with an increase in solution pH. Adsorption kinetics was analyzed using pseudo-first-order, pseudo-second-order, Weber-Morris, and Boyd kinetic models. It was found that the pseudo-second-order kinetic equation was the most appropriate for describing the adsorption kinetics and that the RhB adsorption process was controlled by a film diffusion mechanism. Adsorption equilibrium data were fitted to the Langmuir, Freundlich, Temkin, and Elovich isotherm models. The equilibrium data were best represented by the Langmuir model with the monolayer adsorption capacities of 69.96, 94.34, and 133.3 μmol/g for AC110, AC130, and AC150, respectively. It was concluded that the adsorption of RhB was closely correlated with the specific surface area (and activation time) of the activated chars.
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Authors and Affiliations

Krzysztof Kuśmierek
1
ORCID: ORCID
Andrzej Świątkowski
1
ORCID: ORCID
Tomasz Kotkowski
2
ORCID: ORCID
Robert Cherbański
2
ORCID: ORCID
Eugeniusz Molga
2
ORCID: ORCID

  1. Military University of Technology, Faculty of Advanced Technologies and Chemistry, ul. Kaliskiego 2, 00-908 Warsaw, Poland
  2. Warsaw University of Technology, Faculty of Chemical and Process Engineering, ul. Waryńskiego 1, 00-645 Warsaw, Poland
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Abstract

Waste tyres are among the largest and most problematic sources of waste today, due to the large volume produced and their long-lasting decomposition and resistance to water and extreme temperatures. Since 2000 in Europe the EU Landfill Directive has forbidden the disposal of waste tyres in a landfill. Since then waste tyre derived products (TDP), including whole tyres, tyre bales, shreds, chips, and crumb rubber, have been widely used also in civil engineering applications. The baling is nowadays the best way for the product recycling of waste tyres. Waste tyre bales have considerable potential for use in road applications, particularly where their low density, permeability and ease of handling give them an advantage. Road applications include but are not limited to: embankments construction, slope stabilization and repair (landslides), road foundations over soft ground, backfill material for retaining walls and gravity retaining structures (gabion-type). Several case studies, showing the opportunities to use waste tyre bales in road construction, are presented and illustrated in the paper preceded by providing the engineering properties of waste tyre bales, used within the road structures constructed worldwide. The article also describes the first world application of abutment backfill from the tyre bales in a road bridge, realized in Poland.
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Bibliography


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[8] A. Duda, M. Kida, S. Ziembowicz, P. Koszelnik, “Application of material from used car tyres in geotechnics – an environmental impact analysis”, PeerJ 8:e9546, 2020. https://doi.org/10.7717/peerj.9546
[9] M. Gualtieri, M. Andrioletti, C. Vismara, M. Milani, M. Camatini, “Toxicity of tire debris leachates”, Environment International, 31: pp. 723–730, 2005. https://doi.org/10.1016/j.envint.2005.02.001
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[12] K. Sonti, S. Senadheera. P. W. Jayawickrama, P. T. Nash, D. D. Gransberg, “Evaluate the uses for scrap tires in transportation facilities”. Research Study No 0-1808, Centre for Multidisciplinary Research in Transportation. Texas Tech University, Lubbock, TX, USA, 2000.
[13] I.F. Hodgson, S.P. Beales, M.J. Curd, “Use of tyre bales as lightweight fill for the A421 improvements scheme near Bedford, UK”, Engineering Geology Special Publications, 26: pp. 101–108, 2012. https://doi.org/10.1144/EGSP26.12.
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Authors and Affiliations

Aleksander Duda
1
ORCID: ORCID
Tomasz Siwowski
1
ORCID: ORCID

  1. Rzeszow University of Technology, Faculty of Civil Engineering, Environment and Architecture, Al. Powstanców Warszawy 12, 35-959 Rzeszów, Poland
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Abstract

Activation of tyre pyrolysis char (TPC) can significantly increase its market value. To date, it has been frequently carried out in different reactors. In this work, thermogravimetric analysis was used instead. The performance of activated pyrolysis chars was tested by adsorption of acetone vapour and comparison of the equilibrium adsorption capacities for all samples. The highest equilibrium adsorption capacity was observed for the carbon burn-off of  60%. In addition, the equilibrium adsorption capacity of activated TPC decreases by about 10% after eleven adsorption/desorption cycles. Moreover, activation changed the porous structure of pyrolysis chars from mesoporous to micro-mesoporous.
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Authors and Affiliations

Tomasz Kotkowski
Robert Cherbański
Eugeniusz Molga
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Abstract

This paper presents a systematic thermogravimetric (TG) study on the kinetics of end-of-life tyre (ELT) pyrolysis. In the experimental part of this work, TG results are compared for tyre samples of different mass and size. This shows that the conduction resistance in the milligram scale (up to ~100 mg) tyre sample can be neglected. A comparison of experimental results demonstrates that the characteristic maxima on the DTG curve (the first derivative of TG signal) shift towards higher temperatures for higher heating rates. This phenomenon is explained to have kinetic origin and it is not caused by the internal heat transfer resistance. In the modelling part of this work, the kinetic parameters of the Three-Component Simulation Model (TCSM) are calculated and compared to the literature values. Testing of the kinetic model is carried out using experiments with a varying heating rate. This shows the limitation of the simplified kinetic approach and the appropriate selection method of the kinetic parameters.

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Authors and Affiliations

Robert Cherbański
Eugeniusz Molga
Krzysztof Wróblewski
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Abstract

This paper aims to show the effect of activation method of tyre pyrolysis char (TPC) on adsorption of bisphenol A (BPA) from aqueous solutions. The TPC was produced from end-of-life-tyres (ELT) feedstock in a pilot plant at 773 K. Activation was accomplished using two classical methods: physical activation withCO2 and chemical activation withKOH. The two produced adsorbents had pores ranging from micro- to macropores. Distinct differences in the BET surface areas and pore volumes between the adsorbents were displayed showing better performance of the chemically activated adsorbent for adsorption of BPA from water.

The results of the kinetic studies showed that the adsorption of BPA followed pseudo-second-order kinetic model. The Freundlich, Langmuir, Langmuir–Freundlich and Redlich–Peterson isotherm equations were used for description of the adsorption data. The Langmuir–Freundlich isotherm model best fits the experimental data for the BPA adsorption on both adsorbents. The Langmuir–Freundlich monolayer adsorption capacity, qmLF, obtained for the CO2-activated tyre pyrolysis char (AP-CO2) and KOH-activated tyre pyrolysis char (AP-KOH) were 0.473 and 0.969 mmol g��1, respectively.

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Authors and Affiliations

Krzysztof Kuśmierek
ORCID: ORCID
Andrzej Świątkowski
ORCID: ORCID
Tomasz Kotkowski
ORCID: ORCID
Robert Cherbański
ORCID: ORCID
Eugeniusz Molga
ORCID: ORCID
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Abstract

This work investigates adsorption of n-hexane on activated tyre pyrolysis char (ATPC) and granular activated carbon (GAC) as a reference material in a fixed-bed column. Microwave-assisted regeneration is also considered. The adsorbed amount of n-hexane on ATPC is in the range of 37–58 mg/g. Microwave-assisted desorption of ATPC samples enables the recovery of up to 95% of adsorbed n-hexane in this non-optimized microwave setup with the efficiency of microwave energy conversion into heat of only 5–6%. For the 50% breakthrough time, ATPC and GAC are able to purify the n-hexane gas volumes in the ranges of 20–90 and 935–1240 cm3/g, respectively. While adsorption kinetics is not satisfactorily described by pseudo-first and pseudo-second order kinetic models, it is very well reflected by a family of dynamic adsorption models, which are modelled with a single logistic function. Internal diffusion is likely the rate limiting step during adsorption on ATPC, while external and internal diffusion likely plays a role in adsorption to GAC. Although microwave-assisted regeneration is performed in a general purpose microwave reactor, both adsorbents show excellent performance and are very good candidates for the adsorption process. Preliminary results show that magnetite can further reduce microwave energy consumption.
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Authors and Affiliations

Tomasz Kotkowski
1
ORCID: ORCID
Robert Cherbański
1
ORCID: ORCID
Eugeniusz Molga
1
ORCID: ORCID

  1. Chemical and Process Engineering Department, Warsaw University of Technology, ul. Warynskiego 1, 00-645 Warszawa, Poland

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