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Experimental and Kinetic modeling of In-situ Catalytic (Fe/Cu) Pyrolytic Degradation of Water Hyacinth

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Abstract

Water hyacinth is recognized as a harmful plant, it extracts heavy metals from water bodies, and its disposal is quite challenging. The metal-impregnated samples can be effectively utilized to generate bio-oil and carbon hybrids by pyrolysis along with metal recovery in char. XRD, FESEM, and TEM analyzed the Fe/Cu-impregnated samples with an average particle size of 15.3 and 116 nm for Fe and Cu. Pyrolysis experiments were conducted at the optimum conditions to attain a maximum conversion of 68 and 48% for Fe and Cu-impregnated biomass and validated by kinetic modeling. The kinetic study of raw and metal-loaded samples was performed by modeling with Friedman, FWO, KAS, Kissinger, and Starink isoconversional processes at distinct heating rates of 10 to 25 °C min−1 to estimate optimum conditions for pyrolytic conversion. The average activation energy for raw, Fe, and Cu-impregnated samples was maximum with the Friedman method 173.9, 89.1, and 97.4 kJ mol−1, respectively. The metal-impregnated water hyacinth resulted in lower activation energy for reaction in comparison with the raw water hyacinth. The ΔHα (168.9 kJ mol−1) and ΔGα (164.9 kJ mol−1) are maximum for the raw water hyacinth in comparison with metal-impregnated samples, signifying the higher energy requirement for breaking reactant bonds. Model prediction was done by the Z-Master plot, which concluded that as the conversion (α) ≤ 0.5, the thermal degradation follows the second- and third-order reaction mechanism, and a further increase in conversion (α) > 0.5 follows the first-order reaction mechanism.

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Abbreviations

WH:

Water hyacinth

Cu-WH:

Cu-impregnated water hyacinth

Fe-WH:

Fe-impregnated water hyacinth

TGA:

Thermogravimetric analysis

DTG:

Derivative thermogravimetric

KAS:

Kissinger–Akahira–Sunose

FWO:

Flynn–Wall–Ozawa

DAEM:

Simplified distributed activation energy method

\(E_{\alpha }\) :

Activation energy (kJ mol−1)

\(A\) :

Frequency factor (s−1)

\(\alpha\) :

Degree of conversion

\(i\) :

Temperature program (°C)

\(\beta\) :

Heating rate (°C min−1)

\(\Delta H_{\alpha }\) :

Change in enthalpy (kJ mol−1)

\(\Delta G_{\alpha }\) :

Gibbs free energy (kJ mol−1)

\(\Delta S_{\alpha }\) :

Change in entropy (kJ mol−1)

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Funding

The researchers are thankful to Science and Engineering Research Board, Government of India (Grant Number: CRG/2020/000360) for the financial support to perform the experiments under Core Research Grant.

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  1. Department of Chemical Engineering, Indian Institute of Technology Roorkee, Roorkee, 247 667, Uttarakhand, India

    Priyanka Yadav & Sivamohan N. Reddy

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PY: She is a Ph.D. Student who have conducted experiments, kinetics and thermogravimetric study, analysis of the obtained data, preparation of figures and tables along with the manuscript. SNR: Development of concept, pyrolysis, Analysis of the generated data, and manuscript editing.

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Correspondence to Sivamohan N. Reddy.

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Yadav, P., Reddy, S.N. Experimental and Kinetic modeling of In-situ Catalytic (Fe/Cu) Pyrolytic Degradation of Water Hyacinth. J Therm Anal Calorim 148, 12761–12780 (2023). https://doi.org/10.1007/s10973-023-12573-8

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