Elsevier

Journal of Membrane Science

Volume 640, 15 December 2021, 119833
Journal of Membrane Science

High performance polyamine-based acid-resistant nanofiltration membranes catalyzed with 1,4-benzenecarboxylic acid in interfacial cross-linking polymerization process

https://doi.org/10.1016/j.memsci.2021.119833Get rights and content

Highlights

  • Successful formation of polyamine-based acid-resistant NF membrane by BPEI with TPA and CC in IP.

  • Formation of a moderately dense PA layer network via heat post-treatment to improve performance.

  • SDS surfactant (SDS) was effective in PSf wettability and aided the dispersal of BPEI/TPA solution.

  • TPA-BPEI1.00/CC NF membrane shows excellent acid stability even at 55 ± 1°C.

  • TPA-BPEI1.00/CC NF membrane have 12.8 LMHbar−1 water flux and 94.7% of MgCl2 rejection.

Abstract

Acid-resistant nanofiltration (NF) membranes with both improved permeability and acid stability are in desperate demand for acidic wastewater treatment. Herein, we report a novel polyamine-based nanofiltration membrane with improved flux and excellent acid stability prepared via interfacial cross-linking polymerization reaction of branched polyethyleneimine (BPEI) and 1,4-benzenecarboxylic acid (TPA) with cyanuric chloride (CC) on porous polysulfone support. Evaluated using various characterization techniques, the optimized NF membrane achieved at 1.0% (w/v) BPEI, 0.10% (w/v) CC and 0.15 g/L TPA at 90 °C for 10 min exhibited high rejection of different model salt solutions in the order MgCl2 > Na2SO4 > NaCl, with excellent permeation flux up to 12.8 LMHbar−1. Furthermore, membrane exhibited good acid stability even at extreme conditions. After exposure to 25% (w/w) H2SO4 and 5% (w/w) HNO3 acid solutions at 25 °C, 55 °C and 80 °C for 720 h, 72 h and 24 h respectively, the fluxes increased with a slight decline in their rejection levels. Meanwhile, a long hour stability test slightly dropped the MgCl2 rejection level by ∼10%. The dynamic CuSO4/H2SO4 mixed solution acid test of the membrane also revealed good permselectivity. This fabricated membrane thus provides a prospect of good application in acidic wastewater treatment and acid recovery process.

Introduction

Nanofiltration (NF) is a proven and excellent pressure-driven separation process with a semi-permeable membrane having its separation characteristics between RO and UF membrane [1]. When compared with UF, NF membranes possess smaller pore size for molecules separation of <1000 g/mol, thus retaining organic molecules with molecular weight larger than 200 g/mol but when placed aside RO membrane, it is designed to have a higher molecular weight cut-off (MWCO) (usually within 200–2000 Da) and resultantly a higher water permeability obtained at lower operating pressure [2]. NF has been widely applied in water softening, drinking water purification and wastewater reclamation. It has also found its place in the treatment of effluents from pulp and paper [3], mining and extraction [4], steel and metal [5,6] and so on, which usually has a large volume of acids such as hydrochloric acid, nitric acid and sulfuric acid in them [7,8]. However, these strong acids usually degrade membrane components by altering their morphology and physicochemical properties, thus resulting in performance declination [9].

Generally, commercial NF membranes are thin-film composite (TFC) polyamides, but these membranes are unstable in extreme conditions such as very low pH and high temperature. The amide bonds present in the membrane are intrinsically susceptible to hydrolysis at harsh conditions resulting in an intense reduction in membrane performance [10]. Nevertheless, recently some acid-resistant NF membranes such as Nanopro A series from AMS Technologies, Duracid Series from GE, NP010 and NP030 membranes from Microdyn-Nadir's, Hydranautics-Nitto Denko's NTR-7400 series and MPF series from Koch membrane systems are commercially available for extreme condition applications. However, all these membranes have shortcomings of comparative low flux below 10 LMH under very high-pressure operation up to 40 bar or having high water flux with low rejection, which renders them less commercially attractive [6,11]. Although polysulfonamide-based TFC membranes have shown better stability in acidic condition because of their less tendency of hydrolysis, their fabrication processes are usually burdensome and the formation of active layer is usually complicated with the resulting membranes mostly suffering from low permeability [12]. Therefore, new membranes with high flux and good rejection performance, coupled with excellent acid stability are being investigated.

Recently, polyamine-based TFC membranes formed using polymeric amine reactants and having a tight network with triazine ring moieties have been reported [13]. The uniqueness of this membrane network is the absence of carbonyl groups that are susceptible to nucleophilic attack thus providing superior chemical stability of the membrane at high pH conditions [8,14]. The most commonly adopted method in the fabrication of this polyamine membrane network is interfacial polymerization (IP) [15]. Other methods used include chemical cross-linking, electrostatic assembly and surface modification [[16], [17], [18]]. Lately, polyethyleneimine (PEI) has begun to gain popularity in the formation of tight polyamine network, showing excellent durability and chemical stability in extremely acidic conditions, especially when they are synthesized with appropriate crosslinkers and precursors [19]. PEI is a multifunctional amine having linear or branched topology forms with a unique hydrophilic cationic polymeric structure. Branched PEI (BPEI) contains primary, secondary and tertiary amine groups while linear PEI (LPEI) includes secondary amines only. Their structure has one positively charged nitrogen atom in every three atoms with amorphous net structures which function actively in membrane-enclosed organelles [20]. These active amino groups, especially the primary and secondary amines in BPEI, provide several prospects for reactivity and structural modifications and have been linked to their toxicity [21]. PEI has widely been adopted in the preparation of positively charged NF membranes [[22], [23], [24]]. On the other hand, cyanuric chloride (CC) is a chloro-1,3,5-triazine and is been employed as an organochloride cross-linking reagent to react with PEI and some other amines via IP process to form stable acid-resistant polyamine TFC NF membranes and this is currently receiving attention [25].

Lee et al. prepared acid-resistant NF membranes via the IP of PEI and CC on porous polyethersulfone (PESU) support by suction filtration. The resulting polyamine membranes at extreme pH conditions, displayed a strong resistance towards nucleophilic attack, which was due to the stable C–N bond in polyamine and triazine ring in CC but with average rejection performance and low flux [26]. Jiang et al. fabricated a pH-stable positively charged NF membrane with a mixture of PEI and PIP (as aqueous phase) and CC (as organic phase) via IP on polysulfone (PSf). No visible change was observed in the chemical and separation performance of the fabricated membrane after immersion in aqueous solutions of HNO3 and NaOH for 30 days with a considerable rejection performance achieved but with very low permeance [27]. Yun et al. prepared a NF membrane having an acid resistive ability, by thermally cross-linking BPEI with Poly(ethylene glycol) diglycidyl ether on loose PES. The resulting membrane exhibited excellent stability by maintaining selective separation performance and flow rate for about 720 h and also shows good rejection for MgCl2 and MgSO4 but poor rejection of monovalent salts [28]. Janus acid-resistant NF membranes were fabricated by Ref. [25] via IP of BPEI and CC. The prepared membrane showed better acid stability than commercial polyamide membranes with higher MgCl2 rejection and considerable higher flux compared to previously reported polyamine acid-resistant NF membrane in literature, but the condition of extremity adopted is low and thus does not represent or match the acid concentration in real-life situations and applications. Hence, the need for the fabrication of acid-resistant NF membrane with improved structural stability in more intense and harsh conditions in terms of higher acid concentration and temperature, while still minimizing the flux and selectivity trade-off phenomenon.

Apart from conditions surrounding polymerization reactions such as monomer concentration, curing temperature, curing time and choice of solvents [29] which can influence the morphology and chemical structure of the active layer, the introduction of hydrophilic monomers such as carboxylic acid monomers or sulfonic acid acting as catalysts or additives [[30], [31], [32]], can also enhance water flux and salt rejection of TFC NF membranes by tuning the active layer thus forming a roughness surface structure. In addition, these catalysts or additives could also enhance the structural stability of the membrane in extreme conditions while still ameliorating their permeability and separation performance [33]. 1,4-benzenecarboxylic acid (also known as terephthalic acid, TPA) is a carboxylic acid monomer and catalyst with promising potentials [34]. It is a vital antepenultimate unit, chiefly used in the production of various polyesters as raw material [35,36]. It has found application in the conversion process of bio-based materials and the synthesis of linear and cross-linked polymers (particularly polyesters and polyamides). It is also recently been used for various purposes in the non-fiber field [37]. Although partially soluble in water at room temperature, it displays a unique solubility property at high temperature and its aqueous solutions are stable even at temperatures about 270°C. Some previous studies reported its vast application, even in critical conditions [34,36].

Inspired by the catalytic reactivity of TPA and its superb stability even at high temperature and putting into consideration the high prospect of reactivity and structural modifications possessed by BPEI in membrane polymer formations, we prepared a potential acid-resistant NF membrane by polymerizing BPEI catalyzed with TPA solution (in the aqueous phase) with CC (in the organic phase) to form a tailored selective layer with improved structural stability in intense and harsh conditions, for high acid concentration and temperature, without significantly sacrificing permeability and selectivity. Moreover, the influence of the TPA–BPEI mixture on the intrinsic properties of the polyamine layer such as pore size, surface wettability and thickness were also investigated. The process of fabrication was optimized systematically to achieve the best flux and separation performance. The condition for evaluating acid stability of the membrane was made more intense than previous works to match or at least get close to real-life situation. This was thus accomplished by immersing the optimized membrane in 25 wt% H2SO4 and 5 wt% HNO3 under different immersion temperatures and time duration. Their separation performance and any morphological and chemical structure changes were further investigated.

Section snippets

Materials and chemicals

Polysulfone (PSf) pellets (Udel P-1700) was purchased from Solvay Advanced Polymers, Shanghai, China. Analytical grade of 1-Methyl-2-pyrrolidinone (NMP, anhydrous, greater than 99.5%) used as solvent to dissolve PSf pellets, sodium dodecyl sulfate (SDS) used as a surfactant, ethanol (moisture ≤0.3%) used as solvent to aid TPA dissolution, concentrated sulfuric acid H2SO4, with 98% purity) and nitric acid (HNO3, with 70% purity) used for membrane acid stability test were all supplied by

Surface morphology of BPEI/TPA-CC NF membrane

Morphology of the prepared NF membranes was obtained at high magnifications. Fig. 2 illustrated the SEM images of membrane surfaces and cross-section for the PSf support and prepared BPEI/TPA-CC NF membrane at different concentrations of BPEI molecules. The PSf typically displayed a porous and rough surface (Fig. 2a1), which disappeared after the polymerization reaction of the active layer occurred. As the concentration of BPEI increases from 0.50% to 1.00% in the aqueous phase, a clean surface

Conclusion

The preparation and performance of a novel polyamine-based thin film composite nanofiltration membrane, with improved flux and excellent acid stability has been reported in this study. This was achieved by a catalyzed interfacial cross-linking polymerization reaction of BPEI and TPA with CC on porous PSf support. By adjusting the concentrations of BPEI and TPA, an optimal interfacial polymerization condition was obtained at 0.15 g/L TPA and 1.0% (w/v) BPEI at curing temperature of 90 °C for

CRediT authorship contribution statement

Kayode Hassan Lasisi: Conceptualization, Investigation, Methodology, Writing – original draft, Writing – review & editing. Weihao Yao: Data curation, Software. Qiang Xue: Methodology, Data curation. Qin Liu: Formal analysis, Writing – review & editing. Kaisong Zhang: Conceptualization, Funding acquisition, Formal analysis, Investigation, 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.

Acknowledgement

This work was supported by grants from the National Key R&D Program of China (2018YFC1903205), Ministry of Science and Technology; the Bureau of Frontier Sciences and Education (QYZDB-SSW-DQC044), the Bureau of International Cooperation (132C35KYSB20160018), the Chinese Academy of Sciences and the Joint Project between CAS-CSIRO (132C35KYSB20170051) and FJIRSM & IUE Joint Research Fund (No. RHZX-2019-002). K. H. Lasisi appreciates Chinese Academy of Sciences-The World Academy of Sciences

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