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Thermo-kinetic investigation of the multi-step pyrolysis of smoked cigarette butts towards its energy recovery potential

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Abstract

The present study attempts to explore the energy potential of smoked cigarette butts (SCB) through pyrolysis. For the first time, the pyrolysis characteristics, including the kinetic triplet and the thermodynamic parameters, were investigated using non-isothermal thermogravimetry. Firstly, three pseudo-components were successfully deconvoluted from the multiple-step pyrolysis of SCB using the asymmetrical Fraser-Suzuki function, which corresponds to the devolatilization reactions of retained organic volatile components (PS-1), unburned tobacco (PS-2), and cellulose acetate fibers (PS-3). Posteriorly, the isoconversional methods of Friedman, Flynn-Wall-Ozawa, Kissinger-Akahira-Sunose, and Starink were used to obtain the activation energy values, which were lower for PS-1 (from 101.87 to 108.77 kJ mol−1). The frequency factor values for SCB pyrolysis determined by the compensation effect method were 1.77 × 1012 min−1 for PS-1, 9.44 × 1016 min−1 for PS-2, and 9.62 × 1020 min−1 for PS-3. According to the master plot method, the three pseudo-components followed nth-order reaction models. An acceptable correspondence was observed between experimental and reconstructed pyrolysis behavior, proving the representativity and reliability of the obtained kinetic triplets. Both positive values of ΔH and ΔG suggest that the pyrolytic conversion of smoked cigarette butts into biofuels can be considered as a non-spontaneous conversion. These pyrolysis-related findings from SCB can be used to offer a good opportunity for its valorization as an energy commodity instead of a neglected solid residue.

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Abbreviations

A (min−1):

frequency factor

a (dimensionless):

compensation parameter

b (dimensionless):

compensation parameter

c (dimensionless):

contributed fraction in conversion

DTG (wt% min−1):

differential thermogravimetric

(dα/dt)av (min−1):

average of experimental values

(dα/dt)dec (min−1):

values from deconvolution

(dα/dt)exp (min−1):

experimental values measured

E a (kJ mol−1):

apparent activation energy

f(α) (dimensionless):

reaction model

FC (wt%):

fixed carbon

FR:

Friedman

FWO:

Flynn-Wall-Ozawa

g(α) (dimensionless):

integral form of the reaction model

HHV (MJ kg−1):

higher heating value

h (J s−1):

Plank constant

KAS:

Kissinger-Akahira-Sunose

k B (J K−1):

Boltzmann constant

LHV (MJ kg−1):

lower heating value

M (dimensionless):

total number of points used for deconvolution

My (dimensionless):

mean residual

m 0 (g):

initial mass

m ∞ (g):

final mass

N (dimensionless):

total of componets proposed for residue

p(x) (dimensionless):

approximation for temperature integral equation

PS:

pseudo-component

QOF (dimensionless):

quality of fit

R (kJ mol−1 K−1):

gas constant

R 2 (dimensionless):

coefficient of determination

RSS (dimensionless):

residual sum of squares

s (dimensionless):

asymmetry shape parameter

SCB:

smoked cigarette butts

STK:

Starink

t (min):

time

T (K):

temperature

TGA (wt%):

thermogravimetric analysis

T m (K):

maximum temperature peak

T p (K):

peak temperature

VM (wt%):

volatile matter

w (dimensionless):

half-width in the curve

y (dimensionless):

residual

α (dimensionless):

physical parameters of conversion

β (K min−1):

heating rate

η (dimensionless):

contribution of pseudo-component

θ (dimensionless):

amplitude

ΔG (kJ mol−1):

Gibb’s free energy change

ΔH (kJ mol−1):

enthalpy change

ΔS (J mol−1 K−1):

entropy change

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Funding

This work was supported by Brazil’s National Council for Scientific and Technological Development (CNPq/Brazil Process 423869/2016-7) and Brazil’s Coordination for the Improvement of Higher Education Personnel (CAPES/Brazil Finance Code 001). This work was developed in the Laboratory of Activated Carbon (LCA/UFPB) and Laboratory of Control and Polymerization Processes (LCP/UFSC).

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Author notes

  1. José Luiz Francisco Alves and Jean Constantino Gomes da Silva contributed equally to this work and share senior authorship.

Authors and Affiliations

  1. Graduate Program in Chemical Engineering, Department of Chemical Engineering and Food Engineering, Federal University of Santa Catarina, Florianópolis, Santa Catarina, 88040-900, Brazil

    José Luiz Francisco Alves, Jean Constantino Gomes da Silva, Guilherme Davi Mumbach, Valdemar Francisco da Silva Filho, Ariovaldo Bolzan, Ricardo Antonio Francisco Machado & Cintia Marangoni

  2. Department of Engineering, Federal University of Technology–Paraná (UTFPR), Francisco Beltrão, Paraná, 85601-970, Brazil

    Michele Di Domenico

  3. Laboratory of Activated Carbon, Department of Chemical Engineering, Federal University of Paraíba, João Pessoa, Paraíba, 58033-455, Brazil

    Rennio Felix de Sena

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  1. José Luiz Francisco Alves
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Alves, J.L.F., da Silva, J.C.G., Mumbach, G.D. et al. Thermo-kinetic investigation of the multi-step pyrolysis of smoked cigarette butts towards its energy recovery potential. Biomass Conv. Bioref. 12, 741–755 (2022). https://doi.org/10.1007/s13399-020-01077-2

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