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Clean recovery of phenolic compounds, pyro-gasification thermokinetics, and bioenergy potential of spent agro-industrial bio-wastes

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Abstract

The sequential process of polyphenol extraction from agro-industrial bio-wastes and pyrolysis/gasification of the residual solid fraction (RSF) constitutes an upgrading of the bio-waste to fuel and chemicals processes in the frame of the biorefinery conception. This process can be conducted based on sustainability concepts for bio-waste management, following the premises of the circular economy and the objective of reaching almost zero waste conditions. After the extraction process of apple pomace, grape marc, and grape stalk bio-wastes, three extracts rich in sugar, organic acids, and bioactive compounds were obtained. The polyphenol content was higher in extracts from grape wastes (4990 ± 55 mg gallic acid/100 g in grape marc and 6997 ± 70 mg gallic acid/100 g in grape stalk). However, the apple pomace extraction process was more efficient, since the RSF did not exhibit residual antioxidant capacity. The pyro-gasification kinetics of the RSF was investigated. The results indicated that the Flynn–Wall–Ozawa method presented the best R2, RSME, and SSE values. The Coats–Redfern method was applied to determine the reaction mechanism. For both pyrolysis and gasification processes, it was found that the first-order reaction and three-dimensional diffusion (Ginstling–Brounstein) models properly described the second and third process stages, respectively. The resulting values of the thermodynamic parameters, ΔG, ΔH, and ΔS, were 148.55 kJ/mol, 73.66 kJ/mol, and − 0.11 kJ/K mol, respectively, for pyrolysis and 110.91 kJ/mol, 105.44 kJ/mol, and − 0.01 kJ/K mol for gasification, respectively. According to bioenergy indicators, the RSF from the three bio-wastes had acceptable characteristics as a biofuel feedstock.

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Abbreviations

A:

Pre-exponential Arrhenius’ factor, 1/s

a:

Compensation parameter, mol/kJ

AC:

Antioxidant capacity, mg GAE/100 g d.b.

ACR :

Pre-exponential Arrhenius’ factor by Coats—Redfern, 1/s

ACE :

Pre-exponential Arrhenius’ factor by Compensation Effect, 1/s

aw :

Water activity, dimensionless

b:

Compensation parameter, 1/s

ASH:

Ash content, a percentage of weight

BDLHV, BDHHV :

Bioenergy density on LHV or HHV, respectively, MJ/m3

C:

Content of carbon, wt%

C1 :

Constant depending on the reaction stage and the kinetic model, -

CHL:

Cellulose > hemicellulose > lignin, wt%

CLH:

Cellulose > lignin > hemicellulose, wt%

E:

Activation energy, J/kmol

EDff :

Energy density of gaseous fossil fuel, MJ/m3

EFff :

Emission factor of fossil fuel, kg of CO2/L

ER:

Equivalence ratio, dimensionless

f(α):

Differential function describing the solid mass changes, -

FFE:

Fossil fuel equivalence, m3 fossil fuel/m3 biomass

g(α):

Integral function describing the solid mass changes, -

ΔG:

Free energy of Gibbs change, kJ/mol

H:

Content of hydrogen, wt%

ΔH:

Enthalpy change, kJ/mol

HHV:

Higher heating value, MJ/kg

HCL:

Hemicellulose > cellulose > lignin, wt%

HLC:

Hemicellulose > lignin > cellulose, wt%

k:

Kinetic coefficient, dimension depending on the model expression

LCH:

Lignin > cellulose > hemicellulose, wt%

LHC:

Lignin > hemicellulose > cellulose, wt%

LHV:

Lower heating value, MJ/kg

m:

Mass of the sample at a given time t,

m0 :

Initial mass of the sample,

mf :

Final mass of the sample,

n:

Reaction order, -

PCOR:

Potential CO2 retention, kg of CO2

R:

Universal gas constant, = 8.314 J/(mol K)

RM :

Reactivity, %/°C min

O:

Content of oxygen, = C-H-Ash wt%

ΔS:

Entropy change, kJ/kmol

T:

Temperature, K

TPC:

Total polyphenolic content, mg GAE/100 g d.b.

t:

Time, s

w:

Weight loss at 378 K, total wt

α:

Degree of conversion, -

β:

Heating rate, K/min or K/s

ρ:

Absolute density of bio-waste, kg/m3

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Acknowledgements

The authors wish to thank the support of the following Argentine institutions: the University of San Juan (PDTS Res. 1054/18); the University of Comahue (PIN 2017-04/I223); CONICET -National Scientific and Technical Research Council (PUE PROBIEN 22920150100067); IDEA (Res. 0279/2019); ANPCYT-FONCYT (PICT JI 2017-2047 and PICT-2019-01810) and SYNSOLGAS Project developed in the frame of the Argentinean-French CAFCI collaboration (CNRS-CONICET-MINCyT). Anabel Fernandez has a post-doctoral fellowship from CONICET. Paula Sette, José Soria, Daniela Salvatori, Rosa Rodriguez, and Germán Mazza are Research Members of CONICET, Argentina.

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  1. Instituto de Ingeniería Química, Facultad de Ingeniería (UNSJ), Grupo Vinculado Al PROBIEN (CONICET-UNCo), 1109 (O) Libertador General San Martín- Oeste- St, J5400ARL, San Juan, Argentina

    Anabel Fernandez, Marcelo Echegaray & Rosa Rodriguez

  2. Instituto de Investigación Y Desarrollo en Ingeniería de Procesos, Biotecnología Y Energías Alternativas, PROBIEN (CONICET-UNCo), 1400 Buenos Aires St, 8300, Neuquén, Argentina

    Paula Sette, José Soria, Daniela Salvatori & Germán Mazza

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  1. Anabel Fernandez
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Fernandez, A., Sette, P., Echegaray, M. et al. Clean recovery of phenolic compounds, pyro-gasification thermokinetics, and bioenergy potential of spent agro-industrial bio-wastes. Biomass Conv. Bioref. 13, 12509–12526 (2023). https://doi.org/10.1007/s13399-021-02197-z

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