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Enhanced removal of Cu(II) and Ni(II) using MnOx-modified non-edible biochar: synthesis, characterization, optimization, thermo-kinetics, and regeneration

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Abstract

The remediation of copper and nickel heavy metals from industrial effluents is crucial to prevent environmental pollution and protect public health. Biosorption, a low-cost and eco-friendly technology, has gained increasing attention as an efficient method for the removal of heavy metals from effluent. In this work, a novel low-cost cocopeat biochar has been developed with appropriate chemical modification using KMnO4 to achieve high removal capacity and cyclic stability. Response surface methodology (RSM) was employed to identify optimal conditions and achieved as 1 g/L adsorbent dosage, 710 mg/L metal concentration, and 20-min contact time for Cu(II), and 2.85 g/L adsorbent dosage, 872 mg/L metal concentration, and 20 min contact time for Ni(II). A maximum adsorption capacity achieved as 291.54 mg/g and 181.16 mg/g for Cu(II) and Ni(II), respectively. Biosorbent exhibited a rapid kinetic process, with 86.44% and 77.61% adsorption occurring within just 20 min for Cu(II) and Ni(II), respectively. Brunauer–Emmett–Teller (BET) analysis showed a well-developed mesoporous molecular structure with an average pore diameter of 42.593 nm. The experimental results were fitted well with the pseudo-second-order and Langmuir isotherm, indicating monolayer adsorption primarily directed by chemisorption. Desorption efficiencies 48.25% and 52.16% for Cu(II) and Ni(II) respectively were achieved after four adsorption–desorption cycles. Furthermore, a preliminary study of chitosan composed of biochar was performed by experimental analysis and determination of optimum conditions of best performing synthesis methods using response surface methodology, biosorbent characterization, and possible mechanism of adsorption, which could potentially complement the removal of heavy metals from wastewater.

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Abbreviations

RSM :

Response surface methodology

q m :

Maximum adsorption capacity (mg/g)

q t :

Adsorption capacity at time (mg/g)

q e :

Equilibrium adsorption capacity (mg/g)

FE-SEM :

Field emission scanning electron microscopy

EDX :

Energy dispersive X-ray

BET :

Brunauer-Emmett-Teller

AAS :

Atomic absorption spectroscopy

TGA :

Thermogravimetric analyzer

FTIR :

Fourier-transform infrared spectroscopy

XPS :

X-ray photoelectron spectroscopy

S a :

Specific surface area (m2/g)

R e :

Adsorption removal efficiency

CBC :

Cocopeat biochar

MnO x -CBC :

MnOx-modified cocopeat biochar

CH :

Chitosan

CH-CBC :

Chitosan-cocopeat biochar composite

CH-H 3 PO 4 -CBC :

Chitosan-modified cocopeat biochar with H3PO4 impregnation

CH-Fe-CBC :

Chitosan-modified cocopeat biochar with FeCl3 impregnation

EDTA :

Ethylenediaminotetraacetic acid

CS/EDTA/CBC :

Chitosan and ethylenediaminotetraacetic acid-blended cotton biochar

DI :

De-ionized water

pH pzc :

Point of zero charge

R des :

Desorption efficiency

\({K}_{L}\), \({K}_{F}\) :

Langmuir constant (L/mg) and Freundlich constant (mg/g)

R L :

Separation factor in Langmuir isotherm

\({K}_{T}\) :

Equilibrium binding constant in Temkin isotherm (\(\left(\mathrm{L}/\mathrm{g}\right)\)

D-R :

Dubinin-Radushkevich isotherm

\(\beta\) and \(\varepsilon\) :

D-R model constant and polany potential

\({n}_{H}\) and \({K}_{H}\) :

Halsey’s constants

\({K}_{j}\) :

Jovanovic constant

\({B}_{HJ}\) and \({A}_{HJ}\) :

Harkin-Jura constants

PFO :

Pseudo-first order

\({k}_{1}\) :

Rate constant in PFO kinetic (min−1)

PSO :

Pseudo-second order

\({k}_{2}\) :

Rate constant in PSO kinetic (g/mg min)

\(\alpha\) and \(\beta\) :

Initial adsorption rate and desorption constants in Elovich kinetic model

\({k}_{W\&M}\) :

Diffusion rate constant in Weber and Morris kinetic model

CCD :

Central composite design

WHO :

World Health Organization

DA :

Degree of chitin acetylation

R 2 :

Regression coefficient

FSBC :

Fe/chitosan/biochar composite produced from soy sauce residue for Cr(VI) removal

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Acknowledgements

The authors are thankful to HBL Power Systems Ltd., Hyderabad (India), for funding the project and Dr. K. L. Anitha to support the work. The authors also extend gratitude to the Birla Institute of Technology & Science, Pilani, Hyderabad campus, for facilitating the work.

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Authors and Affiliations

  1. Department of Chemical Engineering, Birla Institute of Technology & Science, Pilani Hyderabad Campus, Hyderabad, 500078, India

    Khandgave Santosh Sopanrao, Sarthak Gupta, Sadamanti Sireesha, Utkarsh Upadhyay & Inkollu Sreedhar

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  1. Khandgave Santosh Sopanrao
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  2. Sarthak Gupta
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  3. Sadamanti Sireesha
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  4. Utkarsh Upadhyay
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  5. Inkollu Sreedhar
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Contributions

KSS: adsorbent synthesis, metal removal experiments, characterization, drafting, and revision.

SG: methodology.

SS: drafting; Xps characterization.

UU: drafting.

IS: project mentoring and monitoring.

Corresponding author

Correspondence to Inkollu Sreedhar.

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Highlights

1. Highest adsorption capacities achieved are 291.54 mg/g (Cu) and 181.16 mg/g (Ni).

2. Optimal conditions for Cu): 1 g/L sorbent; 710 mg/L metal conc., 20-min time.

3. Optimal conditions for Ni: 2.85 g/L sorbent; 872 mg/L metal conc., 20-min time.

4. Langmuir isotherm and Pseudo-second order kinetic models were best fits.

5. Developed adsorbent found stable up to 4 cycles with suitable regeneration method.

6. Mechanistic studies done for chitosan-biochar composites.

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Supplementary file1 (DOCX 16863 KB)

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Sopanrao, K.S., Gupta, S., Sireesha, S. et al. Enhanced removal of Cu(II) and Ni(II) using MnOx-modified non-edible biochar: synthesis, characterization, optimization, thermo-kinetics, and regeneration. Biomass Conv. Bioref. (2023). https://doi.org/10.1007/s13399-023-04411-6

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  • DOI: https://doi.org/10.1007/s13399-023-04411-6

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