Synthesis of a novel green biopolymer-based composites beads for removal of methylene blue from aquatic medium: isotherm, thermodynamic and kinetic investigation

Polymer Bulletin (2024) 81:6603–6640 https://doi.org/10.1007/s00289-024-05164-6 ORIGINAL PAPER Synthesis of a novel green biopolymer‑based composites beads for removal of methylene blue from aquatic medium: isotherm, thermodynamic and kinetic investigation Şerife Parlayici1 · Aslı Aras1 Received: 2 October 2023 / Revised: 8 January 2024 / Accepted: 17 January 2024 / Published online: 15 February 2024 © The Author(s) 2024 Abstract The increase in the world population and the decrease in clean water resources increase people’s interest in water purification technologies. Many industries, such as the textile industry, leather industry, cosmetics and food industry, color their products with substances such as dyes and pigments. In this study, a cheap, useful, innovative, environmentally friendly, and sustainable adsorbent was developed for the removal of Methylene Blue (MB), one of the dyes that is harmful to the environment. In fruit tree cultivation, in addition to the product, very high amounts of byproducts/waste (branches, bark, leaves, fruit seeds, fruit shells, etc.) are produced. In this direction, walnut tree and olive tree wastes were immobilized with chitosan, made magnetic (m-WCH and m-OCH), and the adsorption of MB on the developed adsorbents was examined in a batch system. Characterization of the synthesized biocomposite adsorbents was performed by FT-IR, SEM, EDX and XRD analyzes. It has been thoroughly described how the pH solution of the MB dye compares to the pHPZC of the adsorbent surface. The pHPZC values for m-WCH and m-OCH were 5.2 and 5.5 respectively. MB adsorption of biocomposites depends on the pH of the environment (3–8), amount of adsorbent (2–10 gL−1), contact time (5–360 min), temperature (25–55 °C) and initial dye concentration (10–250 ppm) was examined as a function. The obtained data were evaluated with kinetic and isotherm models. Using adsorption equilibrium data obtained from MB adsorption studies using m-WCH and m-OCH biocomposite adsorbents, their suitability to Langmuir, Freundlich, Stachard, Dubinin–Radushkevich and Temkin models was examined. The empirical data of MB adsorption by m-WCH and m-OCH showed agreement with the Langmuir isotherm model. The maximum adsorption capacity for MB by m-WCH and m-OCH was estimated to be 85.47 mg g−1 and 53.48 mg g−1, respectively. The result showed that a higher adsorption selectivity on m-WCH compares to m-OCH. Among the kinetic models applied, the pseudo-second-order kinetic model was identified with the highest regression coefficients. In the light of these results, it was determined that there are new promising adsorbents of natural origin, Extended author information available on the last page of the article 13 Vol.:(0123456789) 6604 Polymer Bulletin (2024) 81:6603–6640 with higher adsorption capacity, lower cost, and alternatives to commercially used adsorbents in the removal of MB from aqueous media. Graphical abstract Keywords Biowaste · Chitosan · Nano Fe3O4 · Methylene blue · Adsorption Introduction The rapid growth of the industry produces positive results by quickly meeting people’s needs and supporting economic development. However, it also brings environmental pollution. It is estimated that approximately 10–15% of textiles are discharged into wastewater after dyeing [1]. Nearly 10,000 textile colors are sold annually [2]. It is known that textile industry wastewater has a high volume and a complex structure depending on the chemicals and dyestuffs used [3]. In addition, considering that even small amounts of dyestuffs create pollution in a large water 13 Polymer Bulletin (2024) 81:6603–6640 6605 environment, it can be understood that these wastewaters, which have a high color load and are difficult to biodegrade, will be very difficult to purify through natural processes or will take a long time. Besides visible pollution, it can negatively affect biological cycles, especially photosynthesis processes, by blocking the penetration of light through deep water bodies. This toxic property and possible carcinogenic effects of dyes pose a great threat to the environment by negatively affecting biological cycles and ecosystems. Purification of these carcinogenic dyes from wastewater is an important environmental problem [4]. One of the most consumed materials in the dye industry is MB, which is widely used for coloring in the silk, wool, cotton, paper, leather and plastic industries [5]. However, with the release of partially or untreated MB dye laden wastewater from any of the above-mentioned industries, aquatic fauna, beneficial microbes and human life are threatened. One of the reasons for this is the significant toxicity of dyes such as MB at high concentrations [6]. The chemical formula of MB (basic blue 9), a cationic dye, is C 16H18ClN3S·3H2O and its molecular weight is 373.90 gmol−1. MB dye is harmful to human health above a certain concentration due to its significant toxicity [7]. Exposure to MB may cause eye burns, and if swallowed, may cause diarrhea and nausea. Continuous contact with MB concentrated solutions has been reported to have a negative effect on the ability of sperm to move more efficiently in human reproduction [8]. Skin contact may cause skin redness, itching, or skin necrosis. Additionally, when inhaled for a long time, it causes diseases such as methemoglobinemia, cyanosis (bruising disease), convulsion (convulsion disease), and dyspnea (shortness of breath) [9]. Due to the characteristic stability of the aromatic ring in the molecular structure of MB, it is toxic, carcinogenic, non-biodegradable and can pose a serious threat to human health and cause devastating effects on the environment [6, 10]. This chemical compound has been reported to be teratogenic and embryotoxic. Toxic effects were confirmed in a study in which MB was exposed to angelfish and rats, respectively [11]. At the same time, MB generally has a high molar absorption coefficient (664 nm′de, ~ 8,4 × 104 L mol−1 cm−1), which can cause the weakening of sunlight transmittance and therefore reduce oxygen solubility, affecting the biological community [12, 13]. Along with water pollution, water scarcity, climate change and decrease in biodiversity show the necessity of industrial purification. Various specific technologies are focused on for effective removal of dyes. In recent years, coagulation, chemical oxidation, photocatalytic degradation, membrane, and adsorption methods have been used extensively in dyes removal. Since many of these methods have disadvantages such as high investment, operating costs, excessive energy consumption, complex process stages and not being useful, more economical methods need to be designed to remove pollutants from water (Table 1). Among the methods used for purification processes, adsorption has been widely preferred recently because it is one of the most effective and applicable methods due to its high efficiency, easy operation and insensitivi (...truncated)