Application of impregnated biocarbon produced from soybean hulls in dye decolorization

Main Article Content

Aleksandra Kulić Mandić
Milena Bečelić Tomin
Gordana Pucar Milidrag
Milena Rašeta
Đurđa Kerkez


Waste soybean hulls (WSH) were investigated as a Fe-support in two forms: raw and carbonized (i.e. biocarbon, BC), as possible value-added materials. Fe-impregnation was implemented in order to produce heterogeneous Fenton catalysts for Reactive Blue 4 dye degradation. Materials characterization demonstrated a rise in the specific surface area due to decomposition of WSH constituents during carbonization (to obtain BC) and thermal activation (to obtain Fe-WSH and Fe-BC), thus producing catalysts with high mesoporosity and hematite as the active site for Fenton reaction. Among the investigated materials, Fe‑WSH showed the greatest ability for OH production in acidic medium. Next, the hetero­geneous Fenton process was optimized by using response surface methodology, which resulted in selection of the following reaction conditions: 3 mM H2O2, 100 mg Fe-WSH, reaction time of 180 min, at a constant pH 3, RB4 concentration of 50 mg dm-3 and at room temperature. The achieved dye removal and mineralization were 85.7 and 66.8 %, respec­ti­vely, while the catalyst showed high stability and the reaction intermediates formed during the oxidation process had a low inhibitory effect on Vibrio fischeri bacteria.


Download data is not yet available.

Article Details

How to Cite
Kulić Mandić, A., Bečelić Tomin, M., Pucar Milidrag, G., Rašeta, M., & Kerkez, Đurđa. (2021). Application of impregnated biocarbon produced from soybean hulls in dye decolorization. HEMIJSKA INDUSTRIJA (Chemical Industry), 75(5), 307–320.
Applied Chemistry


Holkar CR, Jadhav AJ, Pinjari DV, Mahamuni NM, Pandit AB. A critical review on textile wastewater treatments: Possible approaches. J. Environ. Manage. 2016; 182: 351–366.

Gözmen B, Kayan B, Gizir M, Heresnov A. Oxidative degradations of reactive blue 4 dye by different advanced oxidation methods. J. Hazard. Mater. 2009; 168: 129–136.

Hassan H, Hameed BH. Fe-Natural Zeolite as Highly Active Heterogeneous Catalyst in Decolorization of Reactive Blue 4. Int. J. Environ. Sci. Dev. 2020; 11: 133–137.

Fatma NY, Riyanti F, Hariani PL, Nurbaiti B. Synthesis of chitosan/alumina composite by sol gel method for adsorption of procion blue MX-R dye from wastewater songket industry. J. Phys. Conf. Ser. 2019; 1282: 012080.

da Silva RG, de Andrade AR. Degradation of the Dye Reactive Blue 4 by Coupled Photoassisted Electrochemistry at DSA®-Type Electrode. J. Brazil. Chem. Soc. 2016; 27: 857–865.

Tomin MB, Kulic A, Kerkez D, Prica M, Rapajic S, Pilipovic DT, Pesic V. Reactive dye degradation using Fe-loaded bentonite as a Fenton-like catalyst: From process optimization to effluent acute toxicity. Fresen. Environ. Bull. 2017; 26: 8184–8198.

Zhang M, Dong H, Zhao L, Wang D, Meng D. A review on Fenton process for organic wastewater treatment based on optimization perspective. Sci. Total Environ. 2019; 670: 110–121.

Eloussaief M, Hamza W, Ghorbali G, Kallel N, Benzina M. Fe-Rich Aragonite Concretion Applied to Industrial Dye Purification Using Fenton and Photo-Fenton Technologies. Waste Biomass Valori. 2021; 12: 3303-3313.

Wang N, Zheng T, Zhang G, Wang P. A review on Fenton-like processes for organic wastewater treatment. J. Environ. Chem. Eng. 2016; 4: 762–787.

Javaid R, Qazi UY. Catalytic oxidation process for the degradation of synthetic dyes: An overview. Int. J. Environ. Res. Public Health. 2019; 16: 2066.

Zhu Y, Zhu R, Xi Y, Zhu J, Zhu G, He H. Strategies for enhancing the heterogeneous Fenton catalytic reactivity: A review. Appl. Catal. B Environ. 2019; 255: 117739.

Bello M, Raman AA, Asghar A. A review on approaches for addressing the limitations of Fenton oxidation for recalcitrant wastewater treatment. Process Saf. Environ. Prot. 2019; 126: 119-140.

Nidheesh PV. Heterogeneous Fenton catalysts for the abatement of organic pollutants from aqueous solution: A review. RSC Adv. 2015; 5: 40552–40577.

Wang J, Bai Z. Fe-based catalysts for heterogeneous catalytic ozonation of emerging contaminants in water and wastewater. Chem. Eng. J. 2017; 312: 79–98.

Girish CR. Various impregnation methods used for the surface modification of the adsorbent: A review. Int. J. Eng. Technol. 2018; 7: 330–334.

Elías VR, Rodriguez PAO, Vaschetto EG, Pecchi GA, Huck-Iriart C, Casuscelli SG, Eimer GA. Tailoring the stability and photo-Fenton activity of Fe-modified nanostructured silicates by tuning the metal speciation from different synthesis conditions. Mol. Catal. 2020; 481: 110217.

Setiawan WK, Chiang KY. Crop Residues as Potential Sustainable Precursors for Developing Silica Materials: A Review. Waste Biomass Valori. 2020; 2207-2236.

Campbell-Johnston K, Vermeulen WJV, Reike D, Brullot S. The Circular Economy and Cascading: Towards a Framework. Resour. Conserv. Recycl. X. 2020; 7: 100038.

Xiang W, Zhang X, Chen J, Zou W, He F, Hu X, Tsang DCW, Ok YS, Gao B. Biochar technology in wastewater treatment: A critical review. Chemosphere. 2020; 252: 126539.

Enaime G, Baçaoui A, Yaacoubi A, Lübken M. Biochar for wastewater treatment-conversion technologies and applications. Appl. Sci. 2020; 10: 3492.

Pan X, Gu Z, Chen W, Li Q. Preparation of biochar and biochar composites and their application in a Fenton-like process for wastewater decontamination: A review. Sci. Total Environ. 2021; 754: 142104.

Statistical Office of the Republic of Serbia. Statistical Release PO16: Realized production of wheat and early fruit and expected yields of late crops, fruit and grapes, 2020. Agric. Stat. 2020; 262: 1-2. ISSN 0353-9555

Barros PJR, Ascheri DPR, Santos MLS, Morais CC, Ascheri JLR, Signini R, dos Santos DM, de Campos AJ, Devilla IA. Soybean hulls: Optimization of the pulping and bleaching processes and carboxymethyl cellulose synthesis. Int. J. Biol. Macromol. 2020; 144: 208–218.

Liu H-M, Li H-Y. Application and Conversion of Soybean Hulls. In: Kasai M, ed. Soybean - The Basis of Yield, Biomass and Productivity. IntechOpen; 2017: 111–132.

Qing Q, Guo Q, Zhou L, Gao X, Lu X, Zhang Y. Comparison of alkaline and acid pretreatments for enzymatic hydrolysis of soybean hull and soybean straw to produce fermentable sugars. Ind. Crops Prod. 2017; 109: 391–397.

Neto WPF, Silvério HA, Dantas NO, Pasquini D. Extraction and characterization of cellulose nanocrystals from agro-industrial residue - Soy hulls. Ind. Crops Prod. 2013; 42: 480–488.

Toro-Trochez JL, Carrillo-Pedraza ES, Bustos-Martínez D, García-Mateos FJ, Ruiz-Rosas RR, Rodríguez-Mirasol J, Cordero T. Thermogravimetric characterization and pyrolysis of soybean hulls. Bioresour. Technol. Reports. 2019; 6: 183–189.

Herde ZD, Dharmasena R, Sumanasekera G, Tumuluru JS, Satyavolu J. Impact of hydrolysis on surface area and energy storage applications of activated carbons produced from corn fiber and soy hulls. Carbon Resour. Convers. 2020; 3: 19–28.

Bečelić-Tomin M, Kulić A, Kerkez Đ, Pilipović DT, Pešić V, Dalmacija B. Synthesis of impregnated bentonite using ultrasound waves for application in the Fenton process. Clay Miner. 2018; 53: 203–212.

Xiao C, Li J, Zhang G. Synthesis of stable burger-like α-Fe2O3 catalysts: Formation mechanism and excellent photo-Fenton catalytic performance. J. Clean. Prod. 2018; 180: 550–559.

Trovó AG, Nogueira RFP, Agüera A, Fernandez-Alba AR, Malato S. Degradation of the antibiotic amoxicillin by photo-Fenton process - Chemical and toxicological assessment. Water Res. 2011; 45: 1394–1402.

Milidrag GP, Prica M, Kerkez D, Dalmacija B, Kulic A, Pilipovic DT, Tomin MB. A comparative study of the decolorization capacity of the solar-assisted Fenton process using ferrioxalate and Al, Fe-bentonite catalysts in a parabolic trough reactor. J. Taiwan Inst. Chem. Eng. 2018; 93: 436–449.

Balint T, Chang BP, Mohanty AK, Misra M. Underutilized Agricultural Co-Product as a Sustainable Biofiller for Polyamide 6,6: Effect of Carbonization Temperature. Molecules. 2020; 25: 1455.

Wu Q, Ouyang J, Xie K, Sun L, Wang M, Lin C. Ultrasound-assisted synthesis and visible-light-driven photocatalytic activity of Fe-incorporated TiO2 nanotube array photocatalysts. J. Hazard. Mater. 2012; 199–200: 410–417.

Nandiyanto ABD, Oktiani R, Ragadhita R. How to read and interpret ftir spectroscope of organic material. Indones. J. Sci. Technol. 2019; 4: 97–118.

Chen Y, Shi J, Du Q, Zhang H, Cui Y. Antibiotic removal by agricultural waste biochars with different forms of iron oxide. RSC Adv. 2019; 9: 14143–14153.

Wang QJ, Liu RJ, Shen XQ, Wu DM, Li HH. Fabrication and methyl blue adsorption kinetics of α-Fe2O3 nanotubes by electrospinning. Adv. Mater. Res. 2013; 699: 302–307.

Galan J, Trilleras J, Zapata PA, Arana VA, Grande-Tovar CD. Optimization of chitosan glutaraldehyde-cross linked beads for reactive blue 4 anionic dye removal using a surface response methodology. Life. 2021; 11: 1–20.

Zhao L, Lin ZR, Ma XH, Dong, YH. Catalytic activity of different iron oxides: Insight from pollutant degradation and hydroxyl radical formation in heterogeneous Fenton-like systems. Chem. Eng. J. 2018; 352: 343–351.

Becelic-Tomin M, Dalmacija B, Rajic L, Tomasevic D, Kerkez D, Watson M, Prica M. Degradation of anthraquinone dye reactive blue 4 in pyrite ash catalyzed fenton reaction. Sci. World J. 2014; 234654.

Schneider JT, Firak DS, Ribeiro RR, Peralta-Zamora P. Use of scavenger agents in heterogeneous photocatalysis: truths, half-truths, and misinterpretations. Phys. Chem. Chem. Phys. 2020; 22: 15723–15733.

Stupar SL, Grgur BN, Radišić MM, Onjia AE, Ivanković ND, Tomašević AV, Mijin D. Oxidative degradation of Acid Blue 111 by electro-assisted Fenton process. J. Water Process Eng. 2020; 36: 101394.