Membrane surface functionalization by the deposition of polyvinyl alcohol and graphene oxide for dyes removal and treatment of a simulated wastewater

https://doi.org/10.1016/j.cep.2021.108725Get rights and content

Highlights

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    A simple method was explored to modify the membrane's surface with PVA and GO.

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    High removal (>99%) of sunset yellow, tartrazine yellow and amaranth.

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    The removal efficiency remained above 94% after the fifth filtration cycle.

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    The effect of ionic strength simulating a real effluent was investigated.

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    Proposed modification on membrane surface showed antifouling potential.

ABSTRACT

The wide use of dyes has been arousing global concern due to the amount of wastewater improperly discharged into water resources, damaging the environment and human health. In this study, microfiltration polyethersulfone membranes were modified with polyvinyl alcohol (PVA) and graphene oxide (GO) by layer-by-layer self-assembly method and subsequently used for sunset yellow (SY) dye removal. Different masses of PVA (0, 30 and 60 g) and GO (0.5, 1 and 1.5 g) were deposited on the membrane surface, in which the MF/PVA60+GO1+PVA30 achieved the best performance among all modifications, with removal greater than 99.90%, ∼80% flux recovery rate and good regeneration ability (>94% removal after 5 reuse cycles). Moreover, BSA filtration confirmed its antifouling properties. In order to simulate a real wastewater, the SY dye filtration in the presence of dissolved salts was investigated, wherein a satisfactory removal rate (86.17%) was found for MF/PVA60+GO1+PVA30. Filtration tests were also performed with tartrazine yellow and amaranth dyes, which removal outcomes (>99%) confirm the versatility and efficiency of this membrane. The characterization by physical-chemical and spectroscopic techniques indicated that the membrane was successfully modified. Therefore, the proposed modification demonstrated a significant improvement in dyes removal, which allows its application for wastewater treatment purposes.

Introduction

The increasing contamination of water resources by wastewater with toxic and hazardous organic compounds has been considered a global concern [1,2]. Dyes as sunset yellow (SY), tartrazine yellow (TY), and amaranth (AM) are commonly found in surface water due to their widespread use in various industrial sectors (e.g., food, cosmetics and pharmaceuticals). The presence of these dyes in water bodies, even in small concentrations, is highly visible and results in serious impacts. The major impact is the reduction of sunlight infiltration, which affects the photosynthesis of living beings, and consequently the rate of dissolved oxygen [3]. In addition, excessive direct contact with this class of contaminant can be harmful to humans. Research suggests that the implications can range from skin diseases, cancer, and other consequences [4].

In this scenario, physicochemical techniques are proposed as treatment alternatives, since conventional water and effluent treatments are not able to completely remove dyes [5]. The membrane separation process (MSP) offers advantages over other technologies since they operate in different settings, have a high capacity to respond to adverse conditions, low energy consumption characteristics, ease of application, selective separation, and environmental sustainability [6,7].

However, fouling is the main issue associated with MSP, since this phenomenon is responsible for reducing the permeate flux and membrane performance, providing a reduction in its lifespan [8]. The modification of the membrane surface, in turn, presents itself as an efficient solution, once it acts directly on fouling-related factors, such as hydrophilicity, roughness and surface charges of the membrane [9]. The layer-by-layer (LbL) self-assembly modification technique has been highlighted in the literature due to the simplicity of the process, which consists in the deposition of thin polymers films or nanoparticles on the membrane surface according to its application [10,11].

Among all hydrophilic polymers, polyvinyl alcohol (PVA) is the most used, in view of its low cost and good chemical and thermal resistance [12,13]. According to Bagheripour et al. [14], PVA is a cationic, nontoxic and biocompatible polymer. When applied for modifying the membranes surface, it can influence their performance, particularly regarding membrane rejection and antifouling behavior.

Graphene oxide (GO) stands out among carbon-based nanomaterials, in which it has been considered a popular material for environmental remediation. Its unique properties are able to improve fouling, and increase permeate flux and selectivity in MSP [15,16]. According to Beluci et al. [17], this material has a single-atom, thick and two-dimensional structure, which in general increases the negative charge density. It occurs by the presence of functional groups in its structure (e.g., hydroxyl, epoxy and carboxyl). Furthermore, it has an excellent performance in removing pollutants, due to its large surface area.

Some papers have already proposed the combination of graphene oxide and other polymers for membrane surface modification, reporting good results on filtration performance and dyes removal [9,18]. Therefore, the aim of the present study was to investigate the surface modification of polyethersulfone (PES) sulfonated microfiltration (MF) membranes, using the LbL method through electrostatic deposition of PVA solution together with GO nanosheets. The performance of the modified membranes was evaluated in the SY dye removal. The membrane that obtained the best results was submitted to reuse cycles and filtration with TY and AM dyes, in order to verify its versatility and efficiency in the treatment of effluents. This study also evaluated the removal of SY in the presence of dissolved salts, aiming to determine the real applicability of the membrane since dyes are not individually found in water resources and wastewater, and this can cause synergistic effects which can hinder the membrane separation process.

Section snippets

Materials

Graphene oxide (GO) nanosheets were produced from graphite powder (Sigma Aldrich, particle size < 20 μm), phosphoric oxide (P2O5, Sigma Aldrich), potassium persulfate (K2S2O8, Sigma Aldrich), sulfuric acid (H2SO4, Anidrol) potassium permanganate (KMnO4, Sigma Aldrich), hydrogen peroxide (H2O2, 30 wt.% in H2O, Sigma Aldrich) and hydrochloric acid (HCl, 37 wt.% in H2O, Merck). All the above reagents were of analytical grade (purity ≥ 98%). Polyvinyl alcohol (PVA, M.W. 146,000 - 186,000, 87–89%

Membrane performance

The membrane filtration parameters were investigated, in which the results are shown in Table 1. For that reason, the effects of the PVA deposited mass in the first and last layer (0, 30 and 60 mg) of the membrane modification and GO were analyzed in the intermediate layer (0.5, 1.0 and 1.5 g).

According to the manufacturer of this commercial membrane, its permeability is about 15,000 L m−2 h−1 bar−1. Thus, the modification significantly altered the PWP, which varied according to the quantity of

Conclusion

The present study evaluated the behavior of the surface of microfiltration membranes modified by intercalated deposition of PVA-GO-PVA based on electrostatic interaction, through the LbL method and using a pressurized filtration system. The membrane labeled MF/PVA60+GO1+PVA30 showed a better performance compared to the other membranes tested, since the synergistic effect of PVA and GO resulted in >99.90% removal of the SY dye and a low fouling rate (∼20%). This membrane presented high

CRediT authorship contribution statement

Eduarda Freitas Diogo Januário: Conceptualization, Methodology, Formal analysis, Investigation, Writing – review & editing, Project administration. Taynara Basso Vidovix: Formal analysis, Writing – original draft, Investigation, Validation, Project administration, Visualization. Mariana Antonio Calsavara: Conceptualization, Methodology, Formal analysis, Investigation. Rosângela Bergamasco: Resources, Formal analysis. Angélica Marquetotti Salcedo Vieira: Resources, Supervision.

CRediT authorship contribution statement

Eduarda Freitas Diogo Januário: Conceptualization, Methodology, Formal analysis, Investigation, Writing – review & editing, Project administration. Taynara Basso Vidovix: Formal analysis, Writing – original draft, Investigation, Validation, Project administration, Visualization. Mariana Antonio Calsavara: Conceptualization, Methodology, Formal analysis, Investigation. Rosângela Bergamasco: Resources, Formal analysis. Angélica Marquetotti Salcedo Vieira: Resources, Supervision.

Declaration of Competing Interest

None.

Acknowledgements

This work was supported by the National Council for Scientific and Technological Development (CNPq) and Higher Education Personnel Improvement Coordination (CAPES) Financing Code 001. The authors also thank the Complex of Research Support Center (COMCAP) of the State University of Maringá (UEM) for the characterization analysis.

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