Crystal violet dye removal from aqueous water using polyacrylonitrile precursor beads

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Abstract

The removal of Crystal Violet (CV) Dye by adsorption has been investigated using Polyacrylonitrile-based beads (PAN) as an adsorbent. The beads wereprepared using the phase inversion method and then characterizedusing SEM, BET, and FTIRanalyzes. Different adsorption parameters were tested, such as pH solution, adsorbent dose, adsorbate concentration, rotating speed, and temperature. The equilibrium data were examined by Langmuir and Freundlich's isotherms. A kinetic study using pseudo-first-order and pseudo-second-order was made to investigate the adsorption mechanism. The maximum removal percentage of thedye was 98% at the optimum condition (pH = 7, Co = 10 mg/l, Bo = 0.4 g, T = 35 °C, and 200 rpm), and the process reached equilibriumtime in 5 hr. The pseudo-second-order gives the best conformity than pseudo-first-order; the data also showed the best fitting to Langmuir isotherm. The thermodynamic study revealed a spontaneous and endothermic process. The adsorbent was regenerated with HCl solution and reused up to 6 times with91%removal.

Introduction

Worldwide, water contamination is a significant concern, lack of safe drinking water may jeopardize many organisms' lives, and therefore, water treatment is an important field. Population growth, urbanization, and industrial growth contribute directly to water pollution, especially from developed countries. Several industries discharge diverse toxic and harmful synthetic and natural chemicals and pollutants such as dyes that have a long-term effect on humans [1], [2]. The first synthetic dye was discovered in 1856 and was produced then on a wide level, with approximately 10,000 commercial dye [3]. Different types of dyes are used in various manufacturing processes, including rubber, textiles, cosmetics, plastics, leather, food, carpet, printing, paper, pulp, dyes manufacture, paint, ink, and pharmaceutical industries [4]. During the last years, industrial development has helped in increasing the production of dyes. Worldwide, the textile industry consumes two-thirds of the dyes, whereas 7x105 tons of dyes are used annually [5]. CV is one of the basic and water-soluble dyes used in dying, biological stain in veterinary medicine, pharmaceutical, and food additives [6].

The effluent of dyes industries contains hazardous and toxic material that threatens the ecosystem by polluting the drinking water. If the dye’s effluent is mixed with clean drinking water resources, it will cause odder and turbidity making it unsuitable for consumption. The colored water also affectsthe sea creatures [7]. Dyes, including CV dye, have serious harm to humans' health; it can irritate the skin and eyes and damage the brain, kidney, liver, and immune system [8]. Furthermore, respiratory problems occur when inhaling effluent contaminants with dyeswhen they evaporate. CV is toxic to mammalian cells and can cause faintness, diarrhea, headache, vomiting, and long-term exposure that may cause cancer [9]. According to the international standard discharge of dye’s effluent, the maximum color should not exceed 1 mg/l, and no toxic chemicals are allowed.

A primary issue with colorings is the large number, stability, and non-biodegradable composition of certain dyes [10].Therefore, serious efforts are devoted to eliminating the damage of the dyes on the ecosystem and living creatures. Different removal techniques have been employed for dye-remediation including the physiochemical methods like membrane filtration [11], coagulation and/ or flocculation [12], Fenton [13], Photo-catalytic [14], and adsorption [15]. Biological Methods using various microorganisms like algae [16], bacteria [17] by aerobic, anaerobic, and sequential anaerobic–aerobic treatment processes. However, Adsorption considers the most commonly used. different types of adsorbents have been used to remove the verity of dyes pollutants like activated carbon [18], Clay [19], zeolites [20], bio-sorbents (living or dead) such as bacteria [21], algae [22], and chitosan [23]. Agricultural and wood by-products also were used for dyes adsorptionbecause they areabundant and cheap such as bamboo wastes [24], Cotton fiber [25], and orange peel [26]. Also, industrial by-products such as red mud[27], furthermore polymeric adsorbents are efficient sorbents [28]. However, activated carbon is considered the most generally used despite the high cost associated with the activation and regeneration.

Several researchers investigated CV adsorption using different adsorbents. Lu et.al studied the dye removal using SrCO3/g-C3N4 nano-composite, at initial dye concentration 1600 mg/l and the removal percentage was 98.56% [29]. Yuan et.al reported that the dye was removed using biocompatible Dex-MA/PAA hydrogel with a fast adsorption ratewhere the removal reached 86.4% within one minuteat an initial concentration of 50 mg/l [30]. Crosslinked grafted xanthan gum (XG) film was used as an adsorbent by Abu Elella et.al [31], the result revealed that the dye removal was 99.7% at 500 mg/l initial concentration. Saad et.al used polyaniline Nanoparticles (PANP) to eliminate the dyewith a removal efficiencyof 94.29% [32]. Biochar from biomass was also used for dye recovery [33]. Furthermore, polymeric materials were also used for dye removal, and they reported good removal efficiency [34], [35], [36].

This research deals with the preparation of polyacrylonitrile beads as an adsorbent to remove CV dye from wastewater. The impact of several adsorption parameters, such as initial dye concentration, adsorbent dose, temperature, pH, and rotation speed, was investigated. Also, isotherm, kinetic,thermodynamic, and adsorbent regeneration have been studies.

Section snippets

Chemicals

Polyacrylonitrile (PAN) ((C3H3N)n, M.wt.avg.150,000 g/mol) was ordered from Macklin, China. Crystal Violet (C25H30N3Cl, Mwt. 407.99 g/mol) and the HCL and NaOH were obtained from Sigma-Aldrich, USA. Dimethylformamide (DMF) has been ordered from Solvochem, UK. All chemicals were used with no further purification.

Adsorbate

The solutions of the required concentration of adsorbate were prepared by diluting the stock solution of1000 mg/lof the dye.The UV/vis spectrophotometer (Thermo Science Genesys 10S) was

Adsorbent characterization

SEM images of the surface and cross-section morphologiesof the prepared precursor beads are displayed in Fig. 2 a and b. Because of the rough morphology of the surface, pores are not visible on the surface. However, the beads' porosity, which isfinger-like openings, are clearly shown in the higher magnification image in Fig. 2b. According to the nitrogen adsorption/desorption PAN bead isotherms,the BET specific surface area and BJH total pore volume of the prepared PAN precursor beads are 25 m2

Conclusion

Polyacrylonitrile- base beads (PAN) adsorbent was synthesized using the phase inversion method and used for CV dye removal. The maximum removal percentage of dye at the optimum condition (pH = 7, Co = 10 mg/l, Bo = 0.4 g, T = 35 °C, and 200 rpm) was 98%, and the process reaches equilibrium at 5 hr. PAN beads were regenerated and reused, and 91% percentage removal was achieved. The equilibrium data are fitted to the pseudo-second-order kinetic model and Langmuir isotherm. Also, the adsorption is

CRediT authorship contribution statement

Ola Abd Al-Qader Mahmood: Investigation, Resources, Writing - original draft. Basma I. Waisi: Supervision, Formal analysis, Writing - review & editing.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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