Next Article in Journal
Screening the Lipid Production Potential of Oleaginous Yeast Yarrowia lipolytica under Wood Hydrolysates
Previous Article in Journal
Rhaphiolepis indica Fruit Extracts for Control Fusarium solani and Rhizoctonia solani, the Causal Agents of Bean Root Rot
 
 
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Preparation of a Cation Exchange Membrane by a Sol-Gel Method-Based Polyvinyl Alcohol to Improve Alkali Recovery via Diffusion Dialysis in the Textile Industry

1
Department of Modern Garment Engineering, Anhui Vocational and Technical College, Hefei 230011, China
2
School of Materials & Chemical Engineering, Anhui Jianzhu University, Hefei 230022, China
*
Author to whom correspondence should be addressed.
Separations 2023, 10(7), 370; https://doi.org/10.3390/separations10070370
Submission received: 8 June 2023 / Revised: 20 June 2023 / Accepted: 21 June 2023 / Published: 23 June 2023
(This article belongs to the Section Materials in Separation Science)

Abstract

:
In this work, a novel silane coupled cationic precursor (SAGS) was synthesized by 3-glycidyloxypropyltrimethoxysilane and sodium 2-((2-aminorthyl)amino) ethanesulfonate. A series of cation exchange membranes were prepared with poly(vinyl alcohol) (PVA) and SAGS by a sol-gel-based process. The structure of the prepared membranes were characterized by Fourier transform infrared spectrum (FTIR) and scanning electron microscopy (SEM), and its properties were studied by water uptake (WR), cation exchange capacity (CEC), linear expansion ratio (LER), alkali stability, thermogravimetric analysis (TGA), mechanical properties, and diffusion dialysis performance. FTIR and X-ray photoelectron spectroscopy (XPS) confirmed the successful preparation of SAGS membranes, and SEM images showed that the prepared membranes were dense and uniform. The WR values of the SAGS membranes were in the range of 91.49–122.39%, and the LER values were 17.65–28.21%. In addition, the SAGS membranes had suitable CEC value, good alkali resistance, and thermal stability which ensured the application of membranes in the field of diffusion dialysis (DD) for alkali recovery. In the DD test, the dialysis coefficients of NaOH (UOH) ranged from 0.012 mm/h to 0.023 mm/h, and the separation factors (S) was in the range of 30.77–16.43. In conclusion, the prepared CEM containing silicon oxygen bonds by PVA and SAGS reaction has the advantages of low price, friendly environment, good alkali resistance, simple preparation process, and great application potential in the textile manufacturing wastewater recovery.

1. Introduction

In the textile industry, sodium tungstate (Na2WO4) is commonly used as fabric weighting agent in the production process of fireproof artificial silk [1] and waterproof artificial cotton [2], which can effectively improve the waterproof and fireproof performance of artificial silk or cotton [3,4,5]; however, it is accompanied by the production of a large amount of Na2WO4 and sodium hydroxide (NaOH) wastewater [6,7,8]. Due to massive NaOH in the wastewater, the recovery and reuse of NaOH have significant economic and social significance [9,10,11,12]. Diffusion dialysis is one of the most effective ways to treat the wastewater, which contains Na2WO4 and NaOH [13,14,15,16]. Diffusion dialysis has the advantages of low energy consumption, good separation effect, and a simple process [15,16,17]. The key core of recovery NaOH via diffusion dialysis is to prepare high-performance cation exchange membranes (CEM) [18,19,20,21,22,23]. The cation exchange membrane (CEM) consists mainly of fixed groups (such as sulfonate or carboxyl groups) and and dissociable ions, which can be used for the transport of cations [20,21,22,23]. The preparation of high-performance cation exchange membranes has been the unremitting pursuit of many scholars [21,22,23,24,25,26].
CEM can be divided into two main types, the heterogeneous ion exchange membrane, such as the semi-interpenetrating network structure of the cation exchange membrane and the blending polymer cation exchange membrane [27,28,29,30]; and the homogeneous ion exchange membrane, such as sulfonated polyether ether ketone [31,32], sulfonated polyphenyl ether [33,34], and perfluorosulfonic acid membrane (Nafion) [35,36]. The performance requirements of CEM should contain the following three characteristics. 1. High ion permeability flux and selectivity. This requires that the membrane not only has appropriate water content, but also has good barrier properties to anion [26,37,38]. 2. Outstanding thermal stability, mechanical stability, and low swelling degree. The performance of membrane decreased in the long-time application process, so it was necessary to maintain the performance stability of the separation process over a long period of time [27,39]. 3. Good alkali resistance. For diffusion dialysis, cation exchange membranes adopting traditional polymers as the backbone can no longer meet the requirement of long-term stability under strong alkaline condition, which was also difficult for commercialization of recovery alkaline via diffusion dialysis [40]. High-performance cation exchange membranes had many problems, such as cumbersome preparation methods, unfriendly environment, high price and limited application environment [23,24,25,26]. Hence, it was the pursuit of the majority of ion exchange membrane researchers to prepare cation exchange membranes with simple preparation, environmentally friendly process, and excellent performance.
At present, CEMs based on polyvinyl alcohol (PVA) are studied intensively [41,42]. For example, Y H. Wu et al. prepared cation exchange hybrid membranes with blending sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (SPPO) in PVA/SiO2 matrix [43], the PVA improved the hydrophilicity of the hybrid membrane, and the ion flux of CEM increased. Chunhua Dai et al. prepared hybrid cation exchange membrane by combining benzaldehyde disulfonic acid disodium salt with PVA [44], the results showed that the prepared cation exchange membranes had good performance [11]. There is also a lot of literature on the preparation of CEMs with PVA. The main reason for this is that polyvinyl alcohol is a new green material with a low price, environmental friendliness, wide compatibility, and good alkali resistance, which have attracted the interest of many researchers. Therefore, PVA has often been used to prepare CEM.
In this paper, a silane coupling agent containing an epoxy group was used to react with an amino-containing sulfonate to synthesize a silane coupling agent with sulfonate group (SAGS) [45], and then the cation exchange membrane was prepared with PVA and SAGS by sol-gel reaction. The preparation process was carried out in the aqueous phase, which was environmentally friendly. The preparation process of the membrane uses silane coupling agents to connect the corresponding polymer main chains, making the prepared cation exchange membrane environmentally friendly, cost-effective, and suitable for sustainable industrial development. At the same time, the performance of the prepared membrane was comprehensively studied, which provided technical support for recovery NaOH via diffusion dialysis in the recycling wastewater in the textile industry.

2. Materials and Methods

2.1. Materials

Polyvinyl alcohol (PVA) and dimethyl sulfoxide (DMSO) were purchased from Sinopharm Chemical Reagent (Shanghai, China), and the average degree of PVA was 1750 ± 50. 3-glycidyloxypropyltrimethoxysilane (97%) and sodium 2-((2-aminorthyl)amino)ethanesulfonate (50% in H2O) were supplied by Shanghai Macklin Biochemical Technology Co., Ltd. (Shanghai, China).

2.2. Methods

2.2.1. Synthesis of SAGS

First, 1.36 g (0.005 mol) 3-glycidyloxypropyltrimethoxy-silane and 16.64 g DMSO were loaded in a dried 50 mL round-bottomed flask with adequately stirring at 80 °C in order to completely mix. After 30 min, 2.00 g 2-((2-aminorthyl)amino)-ethanesulfonate was slowly added dropwise into the mixed solution and then the mixture was continually stirred at 80 °C for 6 h to fully react. The product was a colorless transparent viscous solution in DMSO. The reaction synthesis process of SAGS is shown in Figure 1.

2.2.2. Preparation of SAGS-X Cation Exchange Membrane

First, PVA was completely dissolved using DMSO at 90 °C to prepare 5 wt% PVA solution. Second, the SAGS solution was added into the PVA solution to according to different mass ratios (SAGS to PVA: 16%, 32%, 48%, 64% and 80%). The sol-gel reaction lasted for 24 h at 60 °C. The solution after the sol-gel reaction was cast on a clean glass plate and dried in a vacuum oven at 60 °C to form membrane. After the solvent had fully evaporated, the membrane was detached from the plate and then the membrane was heated in vacuum oven at 110 °C for 4 h to completely cross-link the membrane. Finally, the membrane was stored in deionized water for further testing. The prepared membranes were named SAGS-X, where X represented the mass percentage of SAGS in PVA. The preparation process of SAGS-X cation exchange membrane is shown in Figure 2.

2.3. SEM, TGA, FTIR, XPS

The chemical functional groups information of the SAGS-X cation exchange membranes was obtained by Fourier transform infrared spectroscopy (FTIR, Nicolet 6700, MA, Thermo Fisher Scientific of American). FTIR condition was set with a resolution of 0.1 cm−1 and a wavenumber range of 4000–400 cm−1. The surface elemental compositions of prepared membranes were analyzed by X-ray photoelectron spectroscopy (XPS, Escalab 250Xi, Waltham, MA, USA, Thermo Fisher Scientific) measurements. The cross-section microstructure analysis of the SAGS-X cation exchange membranes was performed by scanning electron microscopy (SEM, JSM-7500F, Tokyo, JEOL of Japan). Thermal stability of the SAGS-X cation exchange membranes was obtained by thermogravimetric analysis (TGA, TGA-50H, Tokyo, Shimadzu of Japan). TGA condition was set with a constant heating ratio of 10 °C per minute from room temperature to 600 °C under N2 atmosphere.

2.4. Water Uptake (WR)

Water uptake (WR) was measured by the standard method described below. Primarily, the SAGS-X CEM was dried to a constant weight, and we recorded the weight in the dry state (Wdry) by analytical balance, and then the membrane was completely immersed in deionized water for 48 h at room temperature. After wiping off the surface moisture, the membrane was weighed again and recorded the weight (Wwet) of in a fully absorbed moisture state. Water uptake (WR) that was based on the data obtained above was calculated, and the formula is as follows:
W R = W w e t W d r y W d r y × 100

2.5. Cation Exchange Capacity (CEC) and the Thickness of the Membrane

The cation exchange capacity (CEC) of the SAGS-X CEM was determined by studying the content of -SO3H groups in membrane under dry weight conditions. The theoretical value of CEC (CECT) was obtained through theoretical simulation calculation. The experimental value of CEC (CECE) was characterized by a titration method. First, the dried SAGS-X CEM was accurately weighed by analytical balance (WDry). Then the membrane was equilibrated with 1 M HCl aqueous solution for 48 h to convert to H+ form. Afterwards the membrane was washed with DI water three times in order to completely remove the residual acid, and finally put into 0.04 M NaCl aqueous solution for 48 h. The content of H+ which was released by the membrane was tested through titration with 0.04 M NaOH aqueous solution to determine cation exchange capacity. The CEC (mmol·g−1) was calculated as follows,
C E C = C N a O H V N a O H W D r y
where CNaOH was the concentration of the NaOH aqueous solution, and VNaOH was the volume of the NaOH aqueous solution.
The thickness of the membrane used spiral micrometer to measure.

2.6. Linear Expansion Ratio (LER) and Alkali Stability

Linear expansion ratio (LER) was important properties to evaluate dimensional stability of cation exchange membrane. The membrane in the dry state was cut into a rectangular shape with a length of 5 cm and a width of 1 cm. LER test was similar to the WR test, the membrane lengths in both dry and wet states were recorded before and after the test. LER was calculated as follows:
L E R = L w e t L d r y L d r y × 100
Alkali stability was a key property of CEM to estimate membrane application performance. The weight of the membrane in the dry state was recorded. After that, the membrane was immersed into 2 M NaOH aqueous solution for 7 days at room temperature. Finally, the membrane was washed, dried, and weighed again. The weight maintenance rate was calculated as the ratio of the mass of the membrane before and after the acid resistance test which was a main indicator to evaluate the alkali stability of the membrane.

2.7. Diffusion Dialysis (DD)

At first, the prepared SAGS-X CEM was immersed in feed solution (1 M NaOH + 0.1 M Na2WO4), which was used to simulate wastewater, for 2 h. Next, the membrane needed to be washed carefully several times with the use of DI water. Then, the membrane was placed in the experimental device, which was the combination of two compartments. These two compartments were separated by the prepared membrane, and the effect area between the two parts was 5.5 cm2. Based on the work above, 100 mL DI water was poured into one compartment and 100 mL feed solution was put into the other compartment. After that, in order to minimize concentration polarization, both compartments needed to be strongly stirred for 60 min. Later, 10 mL solution from each compartment of the experimental device was removed. OH concentration in the solution was determined by titration with HCl solution, while WO42− concentration was determined by thiocyanate spectro photometric method. The calculation of dialysis coefficients (U) and separation factors (S) was calculated as follows,
U = M A t C
where M was the amount of component transported in moles, A was the effective area in square meters, t was the time in hours, and ∆C was the logarithmic mean of the concentration difference between the two chambers. ∆C can be calculated as below,
C = C f 0 C f t C d t ln C f 0 C f t C d t
where  C f 0  and  C f t  were the feed concentrations at time 0 and t, respectively, and  C d t  was the dialysate concentration at time t.
The separation factor (S) of membrane was calculated using the ratio of dialysis coefficients (U) of the two species (WO42− and OH) presented in the solution. S can be calculated as follows:
S = U O H U W O 4 2
The data obtained from WR, LER, CEC, DD performance, and film thickness had been tested for an average of three times.

3. Results and Discussion

3.1. FT-IR

The chemical structure information of membranes SAGS-16, SAGS-32, SAGS-48, SAGS-64, and SAGS-80, which was studied by FT-IR (Figure 3). The large and wide bands at 3600–3200 cm−1 was the tensile vibration peaks of hydroxyl in PVA and SAGS [45]. The peaks that appeared at 2937 cm−1 and 2907 cm−1 were due to the symmetric and asymmetric stretching vibration peaks of methylene [46]. The absorption peak at 1646 cm−1 was ascribed to the bending vibration peak of the hydroxyl groups on the sulfonic groups [44]. The uptake peaks at 1420 cm−1 and 1323 cm−1 were due to the bending vibration peaks of methylene and the rocking vibration peaks of hydroxyl groups, respectively [44]. The absorption peak at 1191 cm−1 was assigned to the S=O asymmetric vibration peak of -SO3H groups [46]. The S-O stretching vibration peak of -SO3H groups was also clearly observed at 1041 cm−1 [46]. The presence of -SO3H groups in the membranes could be fully confirmed by the characteristic absorption peaks of -SO3H groups which appeared at 1191 cm−1 and 1041 cm−1. The stretching vibration of Si-O-Si and Si-O-C appears at 1018 cm−1, and these groups mainly formed by the sol-gel process.

3.2. Thermal Stability

Thermal stability of the SAGS-X CEMs was evaluated using TGA and DTG. According to Figure 4, the weight loss process of the SAGS-X CEM was divided into three decomposition stages. In the first decomposition stage, the main loss of membranes was the free water and bound water in the membrane in the temperature range of 80–120 °C [13]. The second decomposition stage occurring from 280 °C to 310 °C was mainly the degradation of grafted side chain functional groups, such as -SO3H groups [47]. The mass loss in the last decomposition temperature which was from 370–480 °C was mainly due to the degradation of the polymer backbone [48]. According to the TGA curve, the residual mass of the prepared membranes gradually increased from SAGS-16 to SAGS-80. Therefore, the addition of SAGS which could increase the overall crosslinking degree of the membrane significantly improved the thermal stability of the prepared membranes. The initial decomposition temperature (IDT) of the SAGS membranes was 266.6–282.5 °C, and thermal degradation temperature (Td) was in the range of 278.5 °C to 283.9 °C from Table 1. So that the IDT and Td values of the SAGS-X CEMs were completely higher than the operating temperature of the CEM.

3.3. XPS Spectra of Membranes

In order to obtain more comprehensive structural information of prepared membrane, the surface chemical component of the membrane was determined by XPS. The test results of membranes are shown in Figure 5.
The peak at 537–526 eV is O 1s. The peak in this region is related to -OH on the PVA chain and -O- in the silane coupling agent [49]. For O 1 s, it was divided into two subspecies, including -OH (located at ca. 536 eV) and O-Si (located at ca. 528 eV). This indicated the presence of hydroxyl and silicon oxygen bonds in the membrane, which was also confirmed by infrared detection. The peak at 102 eV was Si 2p, which confirmed the presence of the Si bond in the membrane [49]. The tensile vibration of Si-O-Si and Si-O-C at 1018 cm−1 in FTIR spectra also confirmed the existence of Si.
In addition, the success synthesized of membrane can be supported by the high-resolution spectra of S 2p. taking membrane SAGS-16 as an example, the XPS signal can be clearly deconvolved into two peaks in Figure 5B. The two peaks detected at 168.2 eV and 163.5 eV in Figure 5B were related to the S atom in the sulphonic group [50]. The characteristic absorption peaks at 1191 cm−1 and 1041 cm−1 in FTIR spectra also confirmed the presence of sulfonic acid groups.

3.4. Water Uptake (WR), Linear Expansion Ratio (LER) and Cation Exchange Capacity (CEC)

The water uptake of the SAGS CEM was tested to collect data, which is shown in Table 2. The WR value of the membrane was 91.49–122.39%. The increased WR value was due to the strong hydrophilicity of the sulfonic acid group. The content of SAGS in the membrane increased, the number of sulfonic acid groups also enhanced, which resulted in an increase in the water uptake of the membrane. The increased content of SAGS made polar groups increase, and resulted in the formation of larger ion clusters, which would cause the membrane to absorb more water and increased the WR value. The LER value of the membrane was 17.65–28.21% (Table 2). The enhanced LER was due to the SAGS content increase, which improved the crosslinking degree of the membrane and enhanced the dimensional stability [46]. The number of ion exchange groups of the prepared membrane was determined by the CEC value. The CEC of the prepared membrane was estimated by using the titration method, and the results were shown in Table 2. The CEC value was 0.25–0.84 mmol/g. The CEC value mainly depends on the number of sulfonic acid groups present in the membrane. With the increased content of SAGS, the number of sulfonic acid groups increased, and the CEC value of the membrane increased. The thickness of the SAGS cation membrane was 91–112 μm. Compared with other membranes, as shown in Table 3, the experimental membrane had good CEC value and lower LER value.

3.5. Mechanical Properties and Alkali Resistance

Mechanical properties were the material properties of CEMs. The TS and Eb values were shown in Figure 6. The tensile strength (TS) of the membrane was 20.1–30.8 MPa, and elongation at break (Eb) value was 92.3–107.2%. Due to the stronger molecular force caused by the cross-linking of the polymer chains, which improved the mechanical properties of the membrane, enhanced the value of TS and Eb of the membrane [53,54]. For SAGS-80, TS and Eb values of the membrane decreased attribute to excessive crosslinking of the membrane, which lead to uneven stress distribution of the membrane and excessive hardness of the local membrane, thereby affecting the TS and Eb values of the membrane [54,55]. Compared with other reported membranes, the prepared membranes had good TS and Eb values. The relevant data were shown in Table 4.

3.6. Alkali Resistance

The alkali resistance of the membrane reflected its potential application in the field of diffusion dialysis for alkali recovery. The membrane was immersed in a 2 M NaOH environment at 25 °C for 7 days [58], and weight maintenance of the membrane was tested. The relevant data were shown in Table 5, and it can be observed clearly that the weight maintenance of SAGS-X CEM was above 88%. The data showed that the SAGS-X CEM had good alkali resistance that was suitable for application in the field of diffusion dialysis for alkali recovery.

3.7. Membrane Morphologies

With the use of SEM, the homogeneity and uniformity of five prepared membranes could be researched in detail. The cross-sectional morphologies of obtained membranes were presented in Figure 7. According to the SEM images, it was not difficult to observe that the membranes were dense and compact without any holes and cracks, which was mainly attributed to the cross-linking between PVA and SAGS. With the increase in SAGS content in the membrane, the degree of crosslinking between SAGS and PVA also increased, which resulted in an increased compactness of the membrane. In addition, the phenomenon of particle aggregation was also observed in Figure 7. The white dots that appear in the images are the silica particles in the membrane [54]. Taking SAGS-80 as an example, the membrane with highest SAGS content, showed the most obvious aggregation due to the accelerated hydrolysis of silica precursor. In addition, the SAGS-64 and SAGS-80 showed the slight phase separation, which was of great help to improve the diffusion dialysis performance for alkali recovery [45].

3.8. Diffusion Dialysis (DD)

The performance of diffusion dialysis was vital for anion exchange membranes, which was about whether the prepared membranes could be used in industrial production and daily life. Thus the diffusion dialysis experiment was carried out by taking NaOH/Na2WO4 mixture (1.0 M NaOH/0.1 M Na2WO4) as the feed solution, and relevant experimental results were shown in Figure 8.
From the collected data, UOH value was increased from 0.012 mm/h to 0.023 mm/h with the increase in SAGS content. That was mainly due to the fact that -SO3H groups carried the negative charge, so OH and WO42− groups which carried the same charge were hardly able to pass through the cation exchange membranes [52]. On the contrary, those cations in the feed solution can be easily transported to the side. For the sake of meeting the requirement of electric neutrality, anions also must be migrated. Compared with WO42−, OH had less charge and the size of OH was smaller, which resulted in the gradual increase of the UOH value. Secondly, the increased CEC and WR had an effect on the performance of diffusion dialysis [45]. Both of these showed an upward trend, which had a positive effect on ion migration, hence the increase in UOH values.
The UWO42− value ranged from 0.39 × 10−3 mm/h to 1.40 × 10−3 mm/h. Under the condition that the membrane structure became more and more dense, the reason for the increase in UWO42− value was phase separation [55]. Based on the previous discussion, larger ion channels appeared on the membrane because of phase separation, which indicated that WO42− groups could pass through the membrane easily. The increased IEC and WR also promoted the migration of WO42− same as OH groups; however, this migration of WO42− was not conducive to membrane selectivity, which caused the decrease in S value.
The S value was the ratio of UOH and UWO42−, and the value was in the range of 30.77–16.43. Compared with some membranes previously reported, the prepared membranes showed the higher separation factor (13.6–18.1) [53], (16.9–18.5) [57]. In order to better prove the changes in different ion transport properties caused by the changes in the internal structure of the membrane, the internal transport mechanism diagram based on the corresponding data was drawn and shown in Figure 9 [54,58,59]. Compared with other membranes, the prepared membrane had good S value. The relevant data were shown in Table 6.

4. Conclusions

A series of long chain PVA-based cation exchange membranes had been successfully prepared by sol-gel process. The CEM containing silicon oxygen bonds prepared by reaction of PVA and SAGS had the advantages of low price, environmentally friendly, and simple preparation process. The SAGS membrane had moderate WR and LER, suitable CEC value, and excellent alkali stability. Moreover, the SAGS membrane had extremely high thermal stability and a microstructure conducive for diffusion dialysis. In the DD test, the UOH and S value of the SAGS membrane were in the range of 0.012–0.023 mm/h and 16.43–30.77, respectively. When the content of SAGS reached 80%, the membrane had a maximum UOH value (0.023 mm/h) and a minimum S value (16.34). Hence, these good properties indicated that the membrane had certain application potential in the field of DD for alkali recovery.

Author Contributions

Software and Formal analysis, H.S.; Resources, Y.G. and H.S.; Writing—original draft, J.Y.; Writing—review & editing, C.C. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by Natural Science Foundation of Anhui Provincial, China (1908085MB55), Natural Science Foundation of Anhui Provincial Education, China (KJ2020ZD44), Science and Technology Projects of Anhui Province, China (202103c08020001).

Data Availability Statement

Not Applicable.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Liu, L.; Ma, Z.; Zhu, M.; Liu, L.; Dai, J.; Shi, Y.; Gao, J.; Dinh, T.; Nguyen, T.; Tang, L.-C.; et al. Superhydrophobic self-extinguishing cotton fabrics for electromagnetic interference shielding and human motion detection. J. Mater. Sci. Technol. 2023, 132, 59–68. [Google Scholar] [CrossRef]
  2. Wang, S.; Du, X.; Luo, Y.; Lin, S.; Zhou, M.; Du, Z.; Cheng, X.; Wang, H. Hierarchical design of waterproof, highly sensitive, and wearable sensing electronics based on MXene-reinforced durable cotton fabrics. Chem. Eng. J. 2021, 408, 127363. [Google Scholar] [CrossRef]
  3. Krishnan, S.A.G.; Gumpu, M.B.; Arthanareeswaran, G.; Goh, P.S.; Aziz, F.; Ismail, A.F. Electrochemical quantification of atrazine-fulvic acid and removal through bismuth tungstate photocatalytic hybrid membranes. Chemosphere 2023, 311, 137016. [Google Scholar] [CrossRef] [PubMed]
  4. Krishnan, S.A.G.; Sasikumar, B.; Arthanareeswaran, G.; László, Z.; Nascimben Santos, E.; Veréb, G.; Kertész, S. Surface-initiated polymerization of PVDF membrane using amine and bismuth tungstate (BWO) modified MIL-100(Fe) nanofillers for pesticide photodegradation. Chemosphere 2022, 304, 135286. [Google Scholar] [CrossRef]
  5. Yang, Y.; Fan, H.; Wu, T.; Yang, G.; Han, B. Complete degradation of high-loaded phenol using tungstate-based ionic liquids with long chain substituent at mild conditions. Green Energy Environ. 2023, 8, 452–458. [Google Scholar] [CrossRef]
  6. Li, B.; Shu, J.; Wu, Y.; Su, P.; Yang, Y.; Chen, M.; Liu, R.; Liu, Z. Enhanced removal of Mn2+ and NH4+-N in electrolytic manganese residue leachate by electrochemical and modified phosphate ore flotation tailings. Sep. Purif. Technol. 2022, 291, 120959. [Google Scholar] [CrossRef]
  7. Li, X.; Miao, J.; Xia, R.; Yang, B.; Chen, P.; Cao, M.; Qian, J. Preparation and properties of sulfonated poly (2, 6-dimethyl-1, 4-phenyleneoxide)/mesoporous silica hybrid membranes for alkali recovery. Microporous Mesoporous Mater. 2016, 236, 48–53. [Google Scholar] [CrossRef]
  8. Zhang, X.; Zhang, X.; An, C.; Wang, S. Electrochemistry-enhanced peroxymonosulfate activation by CoAl-LDH@biochar for simultaneous treatment of heavy metals and PAHs. Sep. Purif. Technol. 2023, 311, 123341. [Google Scholar] [CrossRef]
  9. Zhang, X.; Niu, J.; Hao, X.; Wang, Z.; Guan, G.; Abudula, A. A novel electrochemically switched ion exchange system for phenol recovery and regeneration of NaOH from sodium phenolate wastewater. Sep. Purif. Technol. 2020, 248, 117125. [Google Scholar] [CrossRef]
  10. Zhao, Y.; Wang, X.; Yuan, J.; Ji, Z.; Liu, J.; Wang, S.; Guo, X.; Li, F.; Wang, J.; Bi, J. An efficient electrodialysis metathesis route to recover concentrated NaOH-NH4Cl products from simulated ammonia and saline wastewater in coal chemical industry. Sep. Purif. Technol. 2022, 301, 122042. [Google Scholar] [CrossRef]
  11. Chen, T.; Bi, J.; Ji, Z.; Yuan, J.; Zhao, Y. Application of bipolar membrane electrodialysis for simultaneous recovery of high-value acid/alkali from saline wastewater: An in-depth review. Water Res. 2022, 226, 119274. [Google Scholar] [CrossRef]
  12. Deng, S.; Wang, C.; Ngo, H.H.; Guo, W.; You, N.; Tang, H.; Yu, H.; Tang, L.; Han, J. Comparative review on microbial electrochemical technologies for resource recovery from wastewater towards circular economy and carbon neutrality. Bioresour. Technol. 2023, 376, 128906. [Google Scholar] [CrossRef] [PubMed]
  13. Chen, W.; Shen, H.; Gong, Y.; Li, P.; Cheng, C. Anion exchange membranes with efficient acid recovery obtained by quaternized poly epichlorohydrin and polyvinyl alcohol during diffusion dialysis. J. Membr. Sci. 2023, 674, 121514. [Google Scholar] [CrossRef]
  14. You, X.; Chen, J.; Pan, S.; Lu, G.; Teng, L.; Lin, X.; Zhao, S.; Lin, J. Piperazine-functionalized porous anion exchange membranes for efficient acid recovery by diffusion dialysis. J. Membr. Sci. 2022, 654, 120560. [Google Scholar] [CrossRef]
  15. Liu, B.; Duan, Y.; Li, T.; Li, J.; Zhang, H.; Zhao, C. Nanostructured anion exchange membranes based on poly(arylene piperidinium) with bis-cation strings for diffusion dialysis in acid recovery. Sep. Purif. Technol. 2022, 282, 120032. [Google Scholar] [CrossRef]
  16. Yan, J.; Wang, H.; Fu, R.; Fu, R.; Li, R.; Chen, B.; Jiang, C.; Ge, L.; Liu, Z.; Wang, Y.; et al. Ion exchange membranes for acid recovery: Diffusion Dialysis (DD) or Selective Electrodialysis (SED)? Desalination 2022, 531, 115690. [Google Scholar] [CrossRef]
  17. Lin, J.; Huang, J.; Wang, J.; Yu, J.; You, X.; Lin, X.; Van der Bruggen, B.; Zhao, S. High-performance porous anion exchange membranes for efficient acid recovery from acidic wastewater by diffusion dialysis. J. Membr. Sci. 2021, 624, 119116. [Google Scholar] [CrossRef]
  18. Park, J.; Ko, Y.-j.; Lim, C.; Kim, H.; Min, B.K.; Lee, K.-Y.; Koh, J.H.; Oh, H.-S.; Lee, W.H. Strategies for CO2 electroreduction in cation exchange membrane electrode assembly. Chem. Eng. J. 2023, 453, 139826. [Google Scholar] [CrossRef]
  19. Fujimura, Y.; Kawakatsu, T.; Morimoto, M.; Asakawa, H.; Nakagawa, K.; Yoshioka, T. Study for removing of silica nanoparticle in pure isopropyl alcohol with a cation exchange membrane. J. Mol. Liq. 2022, 367, 120441. [Google Scholar] [CrossRef]
  20. Nazif, A.; Saljoughi, E.; Mousavi, S.M.; Karkhanechi, H. Improved permselectivity and mechanical properties of sulfonated poly dimethyl phenylene oxide cation exchange membrane using MXene nanosheets. Desalination 2023, 549, 116329. [Google Scholar] [CrossRef]
  21. Pahnavar, Z.; Ghaemy, M.; Naji, L.; Hasantabar, V. Self-extinguished and flexible cation exchange membranes based on modified K-Carrageenan/PVA double network hydrogels for electrochemical applications. Int. J. Biol. Macromol. 2023, 231, 123253. [Google Scholar] [CrossRef] [PubMed]
  22. Li, C.; Song, K.; Hao, C.; Liang, W.; Li, X.; Zhang, W.; Wang, Y.; Song, Y. Fabrication of S-PBI cation exchange membrane with excellent anti-fouling property for enhanced performance in electrodialysis. Colloids Surf. A 2023, 661, 130910. [Google Scholar] [CrossRef]
  23. Zheng, Y.; Jin, Y.; Zhang, N.; Wang, D.; Yang, Y.; Zhang, M.; Wang, G.; Qu, W.; Wu, Y. Preparation and characterization of Ti3C2TX MXene/PVDF cation exchange membrane for electrodialysis. Colloids Surf. A 2022, 650, 129556. [Google Scholar] [CrossRef]
  24. Xue, J.; Liu, X.; Zhang, J.; Yin, Y.; Guiver, M. Poly(phenylene oxide)s incorporating N-spirocyclic quaternary ammonium cation/cation strings for anion exchange membranes. J. Membr. Sci. 2020, 595, 117507. [Google Scholar] [CrossRef]
  25. Swanckaert, B.; Loccufier, E.; Geltmeyer, J.; Rabaey, K.; De Buysser, K.; Bonin, L.; De Clerck, K. Sulfonated silica-based cation-exchange nanofiber membranes with superior self-cleaning abilities for electrochemical water treatment applications. Sep. Purif. Technol. 2023, 309, 123001. [Google Scholar] [CrossRef]
  26. Thakur, A.K.; Malmali, M. Advances in polymeric cation exchange membranes for electrodialysis: An overview. J. Environ. Chem. Eng. 2022, 10, 108295. [Google Scholar] [CrossRef]
  27. Kozmai, A.E.; Mareev, S.A.; Butylskii, D.Y.; Ruleva, V.D.; Pismenskaya, N.D.; Nikonenko, V.V. Low-frequency impedance of ion-exchange membrane with electrically heterogeneous surface. Electrochim. Acta 2023, 451, 142285. [Google Scholar] [CrossRef]
  28. Szakács, S.; Koók, L.; Nemestóthy, N.; Bélafi-Bakó, K.; Bakonyi, P. Studying microbial fuel cells equipped with heterogeneous ion exchange membranes: Electrochemical performance and microbial community assessment of anodic and membrane-surface biofilms. Bioresour. Technol. 2022, 360, 127628. [Google Scholar] [CrossRef]
  29. Lee, S.; Meng, W.; Wang, Y.; Wang, D.; Zhang, M.; Wang, G.; Cheng, J.; Zhou, Y.; Qu, W. Comparison of the property of homogeneous and heterogeneous ion exchange membranes during electrodialysis process. Ain Shams Eng. J. 2021, 12, 159–166. [Google Scholar] [CrossRef]
  30. İpekçi, D.; Kabay, N.; Bunani, S.; Altıok, E.; Arda, M.; Yoshizuka, K.; Nishihama, S. Application of heterogeneous ion exchange membranes for simultaneous separation and recovery of lithium and boron from aqueous solution with bipolar membrane electrodialysis (EDBM). Desalination 2020, 479, 114313. [Google Scholar] [CrossRef]
  31. Chikumba, F.T.; Tamer, M.; Akyalçın, L.; Kaytakoğlu, S. The development of sulfonated polyether ether ketone (sPEEK) and titanium silicon oxide (TiSiO4) composite membranes for DMFC applications. Int. J. Hydrogen Energy 2023, 48, 14038–14052. [Google Scholar] [CrossRef]
  32. Lou, X.; Lu, B.; He, M.; Yu, Y.; Zhu, X.; Peng, F.; Qin, C.; Ding, M.; Jia, C. Functionalized carbon black modified sulfonated polyether ether ketone membrane for highly stable vanadium redox flow battery. J. Membr. Sci. 2022, 643, 120015. [Google Scholar] [CrossRef]
  33. Haragirimana, A.; Li, N.; Hu, Z.; Chen, S. A facile, effective thermal crosslinking to balance stability and proton conduction for proton exchange membranes based on blend sulfonated poly(ether ether ketone)/sulfonated poly(arylene ether sulfone). Int. J. Hydrogen Energy 2021, 46, 15866–15877. [Google Scholar] [CrossRef]
  34. Devrim, Y. Fabrication and Performance Evaluation of Hybrid Membrane based on a Sulfonated Polyphenyl Sulfone/Phosphotungstic acid/Silica for Proton Exchange Membrane Fuel Cell at Low Humidity Conditions. Electrochim. Acta 2014, 146, 741–751. [Google Scholar] [CrossRef]
  35. Vrána, J.; Charvát, J.; Mazúr, P.; Bělský, P.; Dundálek, J.; Pocedič, J.; Kosek, J. Commercial perfluorosulfonic acid membranes for vanadium redox flow battery: Effect of ion-exchange capacity and membrane internal structure. J. Membr. Sci. 2018, 552, 202–212. [Google Scholar] [CrossRef]
  36. Jung, B.; Moon, H.-M.; Baroña, G.N.B. Effect of methanol on plasticization and transport properties of a perfluorosulfonic ion-exchange membrane. J. Power Sources 2011, 196, 1880–1885. [Google Scholar] [CrossRef]
  37. Pan, J.; Zhao, L.; Yu, X.; Dong, J.; Liu, L.; Zhao, X.; Liu, L. Optimizing functional layer of cation exchange membrane by three-dimensional cross-linking quaternization for enhancing monovalent selectivity. Chin. Chem. Lett. 2022, 33, 2757–2762. [Google Scholar] [CrossRef]
  38. Jalal, N.M.; Jabur, A.R.; Hamza, M.S.; Allami, S. Sulfonated electrospun polystyrene as cation exchange membranes for fuel cells. Energy Rep. 2020, 6, 287–298. [Google Scholar] [CrossRef]
  39. Salma, U.; Shalahin, N. A mini-review on alkaline stability of imidazolium cations and imidazolium-based anion exchange membranes. Results Mater. 2023, 17, 100366. [Google Scholar] [CrossRef]
  40. Zhao, X.; Cheng, X.; Sun, J.; Liu, J.; Liu, Z.; Wang, Y.; Pan, J. Zero Liquid Discharge and Resource Treatment of Low-Salinity Mineralized Wastewater Based on Combing Selectrodialysis with Bipolar Membrane Electrodialysis. Separations 2023, 10, 269. [Google Scholar] [CrossRef]
  41. Dong, F.; Xu, S.; Wu, X.; Jin, D.; Wang, P.; Wu, D.; Leng, Q. Cross-linked poly(vinyl alcohol)/sulfosuccinic acid (PVA/SSA) as cation exchange membranes for reverse electrodialysis. Sep. Purif. Technol. 2021, 267, 118629. [Google Scholar] [CrossRef]
  42. Hao, J.; Wu, Y.; Xu, T. Cation exchange hybrid membranes prepared from PVA and multisilicon copolymer for application in alkali recovery. J. Membr. Sci. 2013, 425–426, 156–162. [Google Scholar] [CrossRef]
  43. Wu, Y.; Hao, J.; Wu, C.; Mao, F.; Xu, T. Cation exchange PVA/SPPO/SiO2 membranes with double organic phases for alkali recovery. J. Membr. Sci. 2012, 423–424, 383–391. [Google Scholar] [CrossRef]
  44. Dai, C.; Mondal, A.N.; Wu, L.; Wu, Y.; Xu, T. Crosslinked PVA-based hybrid membranes containing di-sulfonic acid groups for alkali recovery. Sep. Purif. Technol. 2017, 184, 1–11. [Google Scholar] [CrossRef]
  45. Mondal, A.N.; Zheng, C.; Cheng, C.; Miao, J.; Hossain, M.M.; Emmanuel, K.; Khan, M.I.; Afsar, N.U.; Ge, L.; Wu, L.; et al. Novel silica-functionalized aminoisophthalic acid-based membranes for base recovery via diffusion dialysis. J. Membr. Sci. 2016, 507, 90–98. [Google Scholar] [CrossRef]
  46. Liu, C.-P.; Dai, C.-A.; Chao, C.-Y.; Chang, S.-J. Novel proton exchange membrane based on crosslinked poly(vinyl alcohol) for direct methanol fuel cells. J. Power Sources 2014, 249, 285–298. [Google Scholar] [CrossRef]
  47. Gouda, M.H.; Elessawy, N.A.; Toghan, A. Development of effectively costed and performant novel cation exchange ceramic nanocomposite membrane based sulfonated PVA for direct borohydride fuel cells. J. Ind. Eng. Chem. 2021, 100, 212–219. [Google Scholar] [CrossRef]
  48. Yang, C.-C. Alkaline direct methanol fuel cell based on a novel anion-exchange composite polymer membrane. J. Appl. Electrochem. 2012, 42, 305–317. [Google Scholar] [CrossRef]
  49. Gong, Y.F.; Chen, W.; Shen, H.Y.; Cheng, C.L. Semi-interpenetrating Polymer-Network Anion Exchange Membrane Based on Quaternized Polyepichlorohydrin and Polyvinyl Alcohol for Acid Recovery by Diffusion Dialysis. Ind. Eng. Chem. Res. 2023, 62, 5624–5634. [Google Scholar] [CrossRef]
  50. Mosa, J.; Duran, A.; Aparicio, M. Sulfonic acid-functionalized hybrid organic-inorganic proton exchange membranes synthesized by sol-gel using 3-mercaptopropyl trimethoxysilane (MPTMS). J. Power Sources 2015, 297, 208–216. [Google Scholar] [CrossRef]
  51. Liang, Y.; Huang, X.; Yao, L.; Xia, R.; Cao, M.; Ge, Q.; Zhou, W.; Qian, J.; Miao, J.; Wu, B. Regulation of Polyvinyl Alcohol/Sulfonated Nano-TiO2 Hybrid Membranes Interface Promotes Diffusion Dialysis. Polymers 2021, 13, 14. [Google Scholar] [CrossRef]
  52. Peng, L.; Huang, X.; Liu, D.; Miao, J.; Wu, B.; Cao, M.; Ge, Q.; Yang, B.; Su, L.; Xia, R.; et al. Preparation of Polyvinyl Alcohol (PVA)-Based Composite Membranes Using Carboxyl-Type Boronic Acid Copolymers for Alkaline Diffusion Dialysis. Polymers 2020, 12, 2360. [Google Scholar] [CrossRef] [PubMed]
  53. Wu, Y.; Gu, J.; Wu, C.; Xu, T. PVA-based cation exchange hybrid membranes with multifunctional groups prepared from ternary multisilicon copolymer. Sep. Purif. Technol. 2013, 104, 45–54. [Google Scholar] [CrossRef]
  54. Ashraf, M.A.; Islam, A.; Butt, M.A. Novel Silica Functionalized Monosodium Glutamate/PVA Cross-Linked Membranes for Alkali Recovery by Diffusion Dialysis. J. Polym. Environ. 2022, 30, 516–527. [Google Scholar] [CrossRef]
  55. Cui, M.B.; Wu, Y.H.; Ran, J.; Xu, T.W. Preparation of cation-exchange hybrid membranes with multi-functional groups and their performance on alkali recovery. Desalin. Water Treat. 2015, 54, 2627–2637. [Google Scholar] [CrossRef]
  56. Ji, W.; Afsar, N.U.; Wu, B.; Sheng, F.; Shehzad, M.A.; Ge, L.; Xu, T. In-situ crosslinked SPPO/PVA composite membranes for alkali recovery via diffusion dialysis. J. Membr. Sci. 2019, 590, 117267. [Google Scholar] [CrossRef]
  57. Gu, J.; Wu, C.; Wu, Y.; Luo, J.; Xu, T. PVA-based hybrid membranes from cation exchange multisilicon copolymer for alkali recovery. Desalination 2012, 304, 25–32. [Google Scholar] [CrossRef]
  58. Shen, H.Y.; Gong, Y.F.; Chen, W.; Wei, X.B.; Li, P.; Cheng, C.L. Anion Exchange Membrane Based on BPPO/PECH with Net Structure for Acid Recovery via Diffusion Dialysis. Int. J. Mol. Sci. 2023, 24, 8596. [Google Scholar] [CrossRef]
  59. Hao, J.W.; Wu, Y.H.; Ran, J.; Wu, B.; Xu, T.W. A simple and green preparation of PVA-based cation exchange hybrid membranes for alkali recovery. J. Membr. Sci. 2013, 433, 10–16. [Google Scholar] [CrossRef]
Figure 1. Synthesis scheme of the silane coupling agent with sulfonate group (SAGS).
Figure 1. Synthesis scheme of the silane coupling agent with sulfonate group (SAGS).
Separations 10 00370 g001
Figure 2. Synthesis scheme of the SAGS-X cation exchange membranes.
Figure 2. Synthesis scheme of the SAGS-X cation exchange membranes.
Separations 10 00370 g002
Figure 3. FTIR spectra of the SAGS-X cation exchange membranes.
Figure 3. FTIR spectra of the SAGS-X cation exchange membranes.
Separations 10 00370 g003
Figure 4. TGA and DTG curves of the SAGS-X cation exchange membranes.
Figure 4. TGA and DTG curves of the SAGS-X cation exchange membranes.
Separations 10 00370 g004
Figure 5. (A) XPS spectra of prepared membranes; (B) high-resolution S 2p spectra of prepared membranes.
Figure 5. (A) XPS spectra of prepared membranes; (B) high-resolution S 2p spectra of prepared membranes.
Separations 10 00370 g005
Figure 6. Tensile strength (TS) and elongation at break (Eb) of the SAGS-X cation exchange membranes.
Figure 6. Tensile strength (TS) and elongation at break (Eb) of the SAGS-X cation exchange membranes.
Separations 10 00370 g006
Figure 7. The morphology of the SAGS-X cation exchange membranes by SEM.
Figure 7. The morphology of the SAGS-X cation exchange membranes by SEM.
Separations 10 00370 g007
Figure 8. UOH and S of membrane SAGS-X cation exchange membranes.
Figure 8. UOH and S of membrane SAGS-X cation exchange membranes.
Separations 10 00370 g008
Figure 9. The internal transport mechanism diagram of the SAGS-X cation exchange membranes.
Figure 9. The internal transport mechanism diagram of the SAGS-X cation exchange membranes.
Separations 10 00370 g009
Table 1. IDT and Td values of the SAGS-X cation exchange membranes.
Table 1. IDT and Td values of the SAGS-X cation exchange membranes.
MembraneSAGS-16SAGS-32SAGS-48SAGS-64SAGS-80
IDT (°C) a266.6268.4271.5266.8282.5
Td (°C) b283.9278.5280.3278.7282.5
a IDT is the initial decomposition temperature determined from TGA thermograms. b Thermal degradation temperature (Td) is defined as the temperature at which the weight loss becomes 5% in TGA thermograms.
Table 2. WR, LER and CEC of the SAGS-X cation exchange membranes.
Table 2. WR, LER and CEC of the SAGS-X cation exchange membranes.
MembraneSAGS-16SAGS-32SAGS-48SAGS-64SAGS-80
WR91.4994.3496.67112.31122.39
LER17.6524.4226.5127.3228.21
CECT0.360.640.851.031.17
CECE0.250.420.570.720.84
Thickness (μm)9991103112107
Table 3. Ion exchange capacity (CEC), water uptake (WR), and linear expansion ratio (LER) values of different membranes.
Table 3. Ion exchange capacity (CEC), water uptake (WR), and linear expansion ratio (LER) values of different membranes.
MembraneCEC (mmol/g)WR (%)LER (%)Ref.
SAGS-X0.25–0.8491.49–122.3917.65–28.21This work
PVA/TiO20–0.015790.9–101.7187.2–206.5[51]
PVA/CBACS0.0147–0.0518122.6–150222.6–241.9[52]
Table 4. TS and Eb values of different membranes.
Table 4. TS and Eb values of different membranes.
MembraneTS (MPa)Eb (%)Ref.
SAGS-X20.1–30.892.3–107.2This work
PVA/SSS/γ-MPS9.1–26.012.4–21.1[56]
PVA/SPPO12–1327–49[54]
PVA/MA/γ-MPS14.2–28.318.8–67.3[57]
Table 5. Weight maintenance of the SAGS-X cation exchange membranes.
Table 5. Weight maintenance of the SAGS-X cation exchange membranes.
MembraneSAGS-16SAGS-32SAGS-48SAGS-64SAGS-80
Weight maintenance (%)91.494.388.390.291.9
Table 6. The UOH and S values of different membranes.
Table 6. The UOH and S values of different membranes.
MembraneUOH (10−3 m/h)SRef.
SAGS-X12–2316.43–30.77This work
PVA/SSS11–1913.6–18.1[53]
PVA/γ-MPS/SSS10.2–11.116.9–18.5[57]
PVA/THOPS11–2211.6–20.6[59]
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Yao, J.; Shen, H.; Gong, Y.; Cheng, C. Preparation of a Cation Exchange Membrane by a Sol-Gel Method-Based Polyvinyl Alcohol to Improve Alkali Recovery via Diffusion Dialysis in the Textile Industry. Separations 2023, 10, 370. https://doi.org/10.3390/separations10070370

AMA Style

Yao J, Shen H, Gong Y, Cheng C. Preparation of a Cation Exchange Membrane by a Sol-Gel Method-Based Polyvinyl Alcohol to Improve Alkali Recovery via Diffusion Dialysis in the Textile Industry. Separations. 2023; 10(7):370. https://doi.org/10.3390/separations10070370

Chicago/Turabian Style

Yao, Jun, Haiyang Shen, Yifei Gong, and Congliang Cheng. 2023. "Preparation of a Cation Exchange Membrane by a Sol-Gel Method-Based Polyvinyl Alcohol to Improve Alkali Recovery via Diffusion Dialysis in the Textile Industry" Separations 10, no. 7: 370. https://doi.org/10.3390/separations10070370

APA Style

Yao, J., Shen, H., Gong, Y., & Cheng, C. (2023). Preparation of a Cation Exchange Membrane by a Sol-Gel Method-Based Polyvinyl Alcohol to Improve Alkali Recovery via Diffusion Dialysis in the Textile Industry. Separations, 10(7), 370. https://doi.org/10.3390/separations10070370

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop