CN113041850A - Preparation method of porous cross-linked anion exchange membrane for diffusion dialysis - Google Patents
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Abstract
The invention discloses a preparation method of a porous cross-linked anion exchange membrane for diffusion dialysis, which is characterized in that chloromethylated polyether sulfone is dissolved in an organic solvent to form a membrane casting solution, then a matrix is coated with the membrane casting solution, then a phase inversion method is carried out to prepare a porous base membrane, and the porous base membrane is soaked in a pentamethyldiethylenetriamine solution to carry out synchronous cross-linking and quaternization modification, thereby preparing the porous cross-linked anion exchange membrane suitable for diffusion dialysis. The porous cross-linking anion exchange membrane with high acid dialysis coefficient and high acid/salt separation factor is prepared based on the special microstructure of the porous membrane, particularly the sufficient free space in the internal porous structure, so that the ion transmission rate is greatly improved, and the three tertiary amine groups contained in the pentamethyl diethylenetriamine are utilized to realize synchronous cross-linking and quaternization modification on the porous base membrane, thereby meeting the requirements of diffusion dialysis use.
Description
Technical Field
The invention belongs to the technical field of membranes, and particularly relates to a preparation method of a porous cross-linked anion exchange membrane for diffusion dialysis.
Background
Diffusion dialysis is currently recognized as the most economically promising method for waste acid recovery. The anion exchange membrane is the core component of diffusion dialysis, the performance of which directly determines the effectiveness of the diffusion dialysis acid recovery process, in particular, the acid dialysis coefficient (U) of the membraneAcid(s)) And acid/salt separation factor (S)Acid/salt) The rate and purity of acid recovery from the diffusion dialysis process is determined separately. To date, the performance of anion exchange membranes for diffusion dialysis has not been ideal enough, mainly its acid dialysis coefficient and acid/salt separation factor. Taking the TWDD series diffusion dialyzer which has been widely commercialized in China at present as an example, the production efficiency is low, and the treatment capacity per square meter per day is only 11.3L. This is mainly due to the low acid dialysis coefficient of the commercial DF-120 anion exchange membrane supported thereby, specifically, the use of DF-120 membrane for HCl (concentration of 1.0 mol/L)/FeCl at 25 deg.C2When the mixed waste acid simulation solution with the concentration of 0.2 mol/L is used for carrying out diffusion dialysis acid recovery, the acid dialysis coefficient is only 8.5 multiplied by 10-3m/h and at the same time its acid/salt separation factor is only 18.5. Therefore, the prepared anion exchange membrane with high acid dialysis coefficient and high acid/salt separation factor is used for diffusion dialysis and has important significance for promoting the development of the waste acid resource utilization industry in China.
Journal of Membrane Science in the Netherlands (Journal of Membrane Science, 2010, 347, 240-249) A process for preparing the anionic exchange membrane used for diffusion dialysis includes such steps as cutting the brominated polyphenylether (BPPO) film into pieces, immersing in 1mol/L KOH solution at 60 deg.C for 24 hr to obtain hydroxylated BPPO, dissolving in the mixture of chloroform and N, N-dimethyl formamide (DMF) to obtain uniform solution, adding the alcohol solution of Trimethylamine (TMA), quaternizing at room temp for 8 hr, adding gamma-aminopropyl triethoxy silane (EPH), tetraethoxy silane (TEOS) and water, sol-gel reaction at 40 deg.C for 24 hr, scraping the film on teflon plate, and heating at 130 deg.C to remove solvent. The diffusion dialysis experimental result shows that the compact anion exchange membrane is used for treating HCl (the concentration is 1.0 mol/L)/FeCl at the temperature of 25 DEG C2When the mixed waste acid simulation solution with the concentration of 0.2 mol/L is used for acid recovery, the acid dialysis coefficient of the membrane is 5.0 multiplied by 10-3~11.0×10-3m/h, and the acid/salt separation factor is 17.0-23.0.
The Netherlands Journal of Membrane Science 2015, 490, 29-37 discloses a preparation method of an anion exchange Membrane for diffusion dialysis, which comprises the steps of firstly reacting 4, 4' -bis (4-aminophenoxy) biphenyl (BABP) and glycidyl trimethyl ammonium chloride (EPTAC) in dimethyl sulfoxide (DMSO) at 85 ℃ overnight, then pouring the reaction solution into low-temperature acetone, filtering and cleaning to obtain quaternized BABP (QBABP), then dissolving the quaternized BABP and QBABP together with polyvinyl alcohol (PVA) and Tetraethoxysilane (TEOS) in DMSO, stirring uniformly, carrying out sol-gel reaction at 60 ℃ overnight to obtain a casting Membrane solution, coating the casting Membrane in a culture dish, and heating to remove the DMSO to obtain a compact anion exchange Membrane. The diffusion dialysis experimental result shows that the compact anion exchange membrane is used for treating HCl (the concentration is 1.0 mol/L)/FeCl at the temperature of 25 DEG C2(the concentration is 0.2 mol/L) mixed waste acid simulation solution is used for acid recovery, and the acid dialysis coefficient of the membrane is 17.2 multiplied by 10-3~25.2×10-3m/h, and an acid/salt separation factor of 14.0 to 21.0.
Despite the advances made in the above work, the anion exchange membranes prepared have unsatisfactory diffusion dialysis performance, particularly acid dialysis coefficient. According to the dissolution-diffusion model, when small molecules or ions pass through a dense or nano-porous polymer membrane, the diffusion rate of the small molecules or ions is in a positive relation with the volume of free space in the membrane. The compact anion exchange membrane has compact internal structure, small free space volume and slow dialysis speed of ions in the membrane. Therefore, the diffusion dialysis performance of the compact anion exchange membrane is difficult to be fundamentally improved by modifying the compact anion exchange membrane.
Chinese patent application No. 201910182068.9 discloses a method for preparing an anion exchange membrane for diffusion dialysis, which comprises dissolving chloromethylated polyethersulfone (CMPES) in an organic solvent to form a casting solution, scraping the casting solution on a substrate, controlling the concentration and the thickness of the casting solution, preparing a chloromethylated polyethersulfone (CMPES) porous base membrane by a solvent-free phase inversion method, and finally soaking the base membrane in a 1, 4-dimethylpiperazine solution with a certain concentration and a certain temperature for a certain time to obtain the porous anion exchange membrane. The diffusion dialysis experiment shows that the porous anion exchange membrane is used for the ion exchange membrane containing HCl (with the concentration of 0.1 mol/L)/FeCl at the temperature of 25 DEG C2When the mixed waste acid simulation solution with the concentration of 1.0 mol/L is used for acid recovery, the acid dialysis coefficient of the membrane is from 24.7 multiplied by 10-3The m/h is increased to 75.0X 10-3m/h, but the acid/salt separation factor of the membrane dropped from 35.8 to 18.2. Compared with compact anion exchange membranes, especially commercial DF-120 anion exchange membranes, the porous anion exchange membranes prepared by using 1, 4-dimethylpiperazine containing 2 tertiary amine groups and a cyclic structure as a modifying functional agent have greatly improved acid dialysis coefficients, but the acid/salt separation factors of the porous anion exchange membranes are still not ideal, and the acid dialysis coefficients and the acid/salt separation factors of the porous anion exchange membranes have the 'adverse effect' (Trade-Off). It can be seen that an anion exchange membrane having both a high acid dialysis coefficient and a high acid/salt separation factor for diffusion dialysis cannot be obtained by the above method.
It must be noted that the pore diameter of the nano-pores on the surface of the porous base membrane is far larger than the hydration radius of most ions, and the ions cannot be effectively trapped. In order to ensure the acid/salt separation effect of the porous anion exchange membrane, the porous base membrane must be effectively crosslinked. Meanwhile, the porous base membrane is not charged, and the porous anion-exchange membrane can have ion transmission capability only by positively charging modification on the base membrane. Although the tertiary amine group and chloromethyl group of chloromethyl polyether sulfone (CMPES) have higher nucleophilic substitution reactivity, the membrane preparation method of the above Chinese patent selects 1, 4-dimethylpiperazine containing 2 tertiary amine groups as the functional agent for modifying the porous basement membrane, and can realize quaternization modification (positive charge modification) of the basement membrane, however, after 1 tertiary amine group contained in 1, 4-dimethylpiperazine reacts with the CMPES basement membrane, the reaction of another tertiary amine and CMPES becomes difficult because of larger steric hindrance of the annular structure of 1, 4-dimethylpiperazine, that is, 1, 4-dimethylpiperazine can not realize effective crosslinking of the CMPES porous basement membrane, and thus a porous anion exchange membrane with high acid/salt separation performance can not be obtained. Further, the insufficient degree of crosslinking results in poor swelling resistance of the final porous anion-exchange membrane, and in particular, as the content of hydrophilic ion-exchange groups as ion transport sites increases, the pore size of the nanopores on the surface of the membrane becomes larger due to the increased swelling of the membrane, and the ion-rejection capacity of the membrane decreases, thereby further causing the "counter-effect" of the acid dialysis coefficient and the acid/salt separation factor of the above porous anion-exchange membrane.
The Netherlands Journal of Membrane Science (Journal of Membrane Science, 2017, 524, 557-. Diffusion dialysis experiments show that the porous cross-linked anion-exchange membrane contains HCl (with the concentration of 0.1 mol/L)/FeCl at the temperature of 25 DEG C2When the mixed waste acid simulation solution with the concentration of 1.0 mol/L is used for acid recovery, the acid dialysis coefficient of the membrane is 42.0 multiplied by 10-3m/h is increased to 65.0×10-3m/h, while the acid/salt separation factor of the membrane increased from 24.5 to 34.0. Compared with a compact anion exchange membrane, especially a commercial DF-120 anion exchange membrane, the porous anion exchange membrane prepared by adopting N, N, N ', N' -tetramethyl-1, 3-propane diamine containing 2 tertiary amine groups and a flexible fatty chain segment as a modifying functional agent has greatly improved acid dialysis coefficient. Compared with the porous anion exchange membrane prepared by taking 1, 4-dimethylpiperazine as a modifying functional agent, the porous anion exchange membrane prepared by taking N, N, N ', N' -tetramethyl-1, 3-propanediamine as the modifying functional agent can overcome the 'adverse effect' of an acid dialysis coefficient and an acid/salt separation factor, because the flexible fatty chain segment of the N, N, N ', N' -tetramethyl-1, 3-propanediamine has better mobility and smaller steric hindrance than that of the 1, 4-dimethylpiperazine, the porous base membrane is more fully crosslinked, and the synchronous crosslinking and quaternization modification of the porous base membrane can be realized. However, their acid/salt separation factor is still not ideal, which is mainly due to the insufficient degree of crosslinking.
In conclusion, the development of diffusion dialysis as an effective technique for waste acid recovery is limited by the technical bottleneck that the anion exchange membrane as a core component has poor diffusion dialysis performance. The traditional compact anion exchange membrane has compact internal structure and small free space volume, so that the ion transmission rate in the membrane is low, and the acid dialysis coefficient of the anion exchange membrane cannot be fundamentally improved. Although the existing porous anion exchange membrane can effectively improve the acid dialysis coefficient of the membrane, the acid/salt separation performance of the existing porous anion exchange membrane is poor, so that the purity of the recovered acid is poor. Therefore, it is very important to take a powerful measure to improve the acid/salt separation performance of the porous anion exchange membrane.
Disclosure of Invention
The invention aims to provide a preparation method of a porous cross-linked anion-exchange membrane for diffusion dialysis, which utilizes the chloromethyl reaction of 3 tertiary amines contained in pentamethyl diethylenetriamine and chloromethyl polyether sulfone (CMPES) porous basement membrane to carry out cross-linking and quaternization modification (positive charge modification) on the porous basement membrane so as to prepare the porous cross-linked anion-exchange membrane, so as to overcome the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention claims to protect a porous cross-linked anion exchange membrane for diffusion dialysis and a preparation method thereof, wherein chloromethylated polyethersulfone is dissolved in an organic solvent to form a membrane casting solution, then the membrane is coated on a substrate, and a chloromethylated polyethersulfone porous base membrane is prepared by a solvent-free phase-induced conversion method; and then soaking the obtained chloromethylated polyether sulfone porous base membrane in a pentamethyl diethylenetriamine solution for synchronous crosslinking and quaternization modification, thereby obtaining the porous crosslinking anion exchange membrane suitable for diffusion dialysis.
The structural formula of the chloromethylated polyether sulfone is as follows:
wherein, X =20% to 90%, which represents the chloromethylation degree of the chloromethylated polyethersulfone, i.e. the mole percentage of chloromethyl-containing repeating units in the chloromethylated polyethersulfone to all repeating units.
The organic solvent is selected from any one of N-methyl pyrrolidone, N-methyl formamide, N-methyl acetamide or dimethyl sulfoxide.
The concentration of the casting solution is 15-30 wt%.
The substrate is selected from any one of a polyethylene film, a polytetrafluoroethylene plate, a metal plate or a glass plate.
The coating method is scraping, spraying, dipping or coating.
The thickness of the film coating of the casting solution is 150-350 microns.
The concentration of the pentamethyl diethylenetriamine solution is 0.5-5 mol/L, the solvent is selected from any one of water, methanol, ethanol and acetone, and the structural formula of the pentamethyl diethylenetriamine is as follows:
。
the soaking temperature is 25-90 ℃, and the soaking time is 0.5-48 h.
The invention has the advantages that:
in the preparation of common anion exchange membranes for diffusion dialysis, an organic solvent is used as a reaction medium to synthesize a polymer containing quaternary ammonium groups, and then the reaction solution is used as a membrane casting solution to be coated and then heated to evaporate the solvent, so that the anion exchange membrane with a compact structure is finally obtained. Firstly, the preparation process is complicated and long-lasting, and the curing and forming of the anion exchange membrane needs heating to volatilize the organic solvent, so that the energy consumption is high and the pollution is serious; secondly, the microstructure of the anion exchange membrane is compact, the volume of the free space is small, and the resistance to ion transmission is large, so that the acid dialysis coefficient is low, and the efficiency of diffusion dialysis acid recovery is low. According to the porous anion-exchange membrane provided by the invention, after the porous base membrane is prepared by a solvent-free phase-induced conversion method in the membrane preparation process, the porous base membrane is soaked in a pentamethyldiethylenetriamine solution for modification, the process is simple, the time is short, and the solvent is not required to be heated, so that the energy consumption and the environmental pollution can be reduced; meanwhile, the porous anion exchange membrane prepared by the invention has sufficient free space in the internal microstructure, so that the transmission rate of ions can be increased, and the acid dialysis coefficient of the membrane can be improved.
The preparation method is characterized in that a chloromethylation polyether sulfone porous base membrane is prepared in Chinese patent with application number of 201910182068.9, and then the chloromethylation polyether sulfone porous base membrane is soaked in a 1, 4-dimethyl piperazine solution for modification, and the porous base membrane cannot be effectively crosslinked due to the fact that the steric hindrance of the 1, 4-dimethyl piperazine with an annular structure is large, so that the prepared porous anion exchange membrane is poor in acid/salt separation performance, and a 'counter effect' between an acid dialysis coefficient and an acid/salt separation factor exists.
A chloromethylation polysulfone porous basement Membrane is prepared in Journal of Membrane Science, 2017, 524, 557-containing 564 in the Netherlands, and is soaked in an N, N, N ', N' -tetramethyl-1, 3-propanediamine solution containing 2 tertiary amine groups for modification to obtain the porous cross-linked anion-exchange Membrane. Compared with the porous anion exchange membrane prepared by modifying 1, 4-dimethylpiperazine, the porous anion exchange membrane prepared by modifying N, N, N ', N' -tetramethyl-1, 3-propane diamine can overcome the 'paradox effect' between the acid dialysis coefficient and the acid/salt separation factor, this is because the structure of the soft aliphatic segment of N, N, N ', N' -tetramethyl-1, 3-propanediamine has better mobility and less steric hindrance than the cyclic structure of 1, 4-dimethylpiperazine, so that the N, N, N ', N' -tetramethyl-1, 3-propane diamine can perform two-dimensional crosslinking on the porous base membrane, and the acid/salt separation factor of the porous anion exchange membrane prepared by modifying the N, N, N ', N' -tetramethyl-1, 3-propane diamine is still not ideal.
The invention adopts pentamethyl diethylenetriamine containing 3 tertiary amine groups and a flexible fatty chain segment structure as a functional modifier, has stronger mobility and smaller steric hindrance than 1, 4-dimethyl piperazine and pentamethyl diethylenetriamine, and can perform effective synchronous crosslinking and quaternization modification on a base membrane; compared with N, N, N ', N' -tetramethyl-1, 3-propane diamine and pentamethyl diethylene triamine, the porous base membrane has equivalent mobility and steric hindrance, but 3 tertiary amine groups contained in the porous base membrane can perform three-dimensional crosslinking on the porous base membrane, so that the acid/salt selectivity of the prepared porous crosslinked anion exchange membrane is greatly improved. Therefore, the preparation method can prepare the porous cross-linked anion-exchange membrane with high acid dialysis coefficient and high acid/salt separation factor so as to promote the rapid development of the waste acid recycling industry in China.
Drawings
FIG. 1 is a schematic diagram of the reaction mechanism of the preparation process of the present invention for synchronously crosslinking and positively charging modification of a Chloromethylpolyethersulfone (CMPES) porous base membrane.
FIG. 2 is an XPS comparison spectrum of chloromethyl polyethersulfone (CMPES) porous base membrane and porous cross-linked anion exchange membrane prepared in example 1.
Detailed Description
The technical solution of the present invention is described in detail and completely by using the following embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The chemical reagents used in the examples of the present invention are all commercially available.
Comparative example 1
A porous anion exchange membrane was prepared with reference to the disclosure of chinese patent application No. 201910182068.9 (example 1). Specifically, chloromethylated polyethersulfone (CMPES) with the chloromethylation degree of 55% is dissolved in N-methylpyrrolidone to form casting solution with the concentration of 25wt%, a scraper is used for scraping the membrane on a glass plate, the thickness is controlled to be 250 micrometers, and then the glass plate is immersed in deionized water for phase conversion to obtain the chloromethylated polyethersulfone (CMPES) porous base membrane. The porous base membrane is soaked in 1, 4-dimethylpiperazine water solution with the concentration of 1mol/L and the temperature of 70 ℃ for 6h to obtain the 1, 4-dimethylpiperazine functionalized polyether sulfone porous anion exchange membrane. The Ion Exchange Capacity (IEC) of the membrane was measured to be 1.25 mmol/g.
Using the porous anion exchange membrane of comparative example 1, HCl (concentration 1.0 mol/L)/FeCl was treated at 25 ℃2(concentration is 0.2 mol/L) mixed waste acid simulation solution for acid recovery, and the acid dialysis coefficient of the membrane is measured to be 50.0 multiplied by 10-3m/h, the separation coefficient is 20.9.
Comparative example 2
Porous anion exchange membranes were prepared with reference to the disclosure (experimental part) of Journal of Membrane Science, 2017, 524, 557-564, the Netherlands. Specifically, chloromethylated polysulfone (CMPSF) with the chloromethylation degree of 129% is dissolved in N-methyl pyrrolidone to form casting solution with the concentration of 25wt%, a scraper is used for scraping the membrane on a glass plate, the thickness is controlled to be 250 micrometers, and then the glass plate is immersed in deionized water for phase conversion to obtain the chloromethylated polysulfone (CMPSF) porous base membrane. Soaking the porous base membrane in an N, N, N ', N' -tetramethyl-1, 3-propanediamine aqueous solution with the concentration of 1mol/L and the temperature of 60 ℃ for 5 hours to obtain the N, N, N ', N' -tetramethyl-1, 3-propanediamine functionalized polyether sulfone porous anion exchange membrane. The Ion Exchange Capacity (IEC) of the membrane was measured to be 1.18 mmol/g.
Using the porous anion exchange membrane of this comparative example 2, HCl (concentration 1.0 mol/L)/FeCl was treated at 25 ℃2(the concentration is 0.2 mol/L) mixed waste acid simulation solution is subjected to acid recoveryThe acid dialysis coefficient of the membrane was found to be 65.0X 10-3m/h, the separation coefficient is 30.4.
Example 1
Dissolving chloromethylated polyether sulfone (CMPES) with the chloromethylation degree of 60% in N-methylpyrrolidone to form casting solution with the concentration of 25wt%, scraping the film on a glass plate by using a scraper, controlling the thickness to be 250 micrometers, and then soaking the glass plate in deionized water for phase conversion to obtain the chloromethyl polyether sulfone (CMPES) porous basement membrane. Soaking the porous base membrane in a pentamethyl diethylenetriamine aqueous solution with the concentration of 2mol/L and the temperature of 60 ℃ for 12h to obtain the pentamethyl diethylenetriamine functionalized porous cross-linked anion exchange membrane. The ion exchange capacity (IEC, i.e., the content of quaternary ammonium groups) of the membrane was measured to be 1.28 mmol/g.
The CMPES porous base film and the porous crosslinked anion exchange membrane prepared in this example were subjected to X-ray photoelectron spectroscopy (XPS) analysis, and the results are shown in FIG. 2. As can be seen from FIG. 2, from the porous base membrane to the porous cross-linked anion exchange membrane, a high resolution XPS spectrum of the N region shows a quaternary ammonium group (N) at 402eV+R4) By reaction of pentamethyldiethylenetriamine with chloromethyl group of CMPES porous-based membrane. The results prove that the pentamethyldiethylenetriamine carries out successful quaternization modification on the porous base membrane.
Then the porous basement membrane and the porous cross-linked anion exchange membrane prepared by the embodiment are respectively soaked in HCl and H with the temperature of 80 ℃ and the concentration of 10mol/L2SO4And HNO3In the water solution for 7 days to research the acid resistance of the membrane, and then the membrane is respectively soaked in organic solvents of N-methylpyrrolidone, N-methylformamide, N-methylacetamide or dimethyl sulfoxide and the like at the temperature of 80 ℃ for 7 days to research the solvent resistance of the membrane. The result shows that the shape and the quality of the porous anion exchange membrane are kept stable after the porous anion exchange membrane is soaked in high-concentration high-temperature acid solution and high-temperature organic solvent for a long time, which indicates that the porous cross-linked anion exchange membrane prepared by the invention has good acid resistance and solvent resistance. In contrast, the porous base membrane, although stable in an acid solution, is soaked in an organic solventThe modified pentamethyl diethylenetriamine is completely dissolved after being soaked for a few minutes, so that the successful crosslinking modification of pentamethyl diethylenetriamine can realize great improvement on the organic solvent resistance of the film.
The porous cross-linked anion-exchange membrane of the present example was used for the treatment of HCl (concentration of 1.0 mol/L)/FeCl at 25 deg.C2(concentration is 0.2 mol/L) mixed waste acid simulation solution for acid recovery, and the acid dialysis coefficient of the membrane is measured to be 49.7 multiplied by 10-3m/h, acid/salt separation factor 3509.7, much higher than the diffusion dialysis performance of a commercial DF-120 anion exchange membrane with a compact microstructure (acid dialysis coefficient 8.5X 10)-3m/h, acid/salt separation factor of 18.5) because the porous membrane substrate employed in the present invention can facilitate the ion transport rate by increasing the free space volume within the membrane. The porous cross-linked anion exchange membrane prepared in this example has similar ion exchange capacity and acid dialysis coefficient compared to the porous anion exchange membrane prepared in comparative example 1, but the acid/salt separation factor is improved by 166.9 times (from 20.9 to 3509.7), which is mainly attributed to the use of pentamethyldiethylenetriamine. Compared with 1, 4-dimethylpiperazine containing a ring structure, the flexible fatty chain segment of pentamethyl diethylenetriamine has higher mobility and steric hindrance than 1, 4-dimethylpiperazine, so that the reaction degree with the porous base membrane is higher, and 3 tertiary amine groups contained in pentamethyl diethylenetriamine can perform three-dimensional crosslinking on the porous base membrane, thereby greatly improving the acid/salt separation factor. Due to the optimization of the microstructure of the membrane matrix and the chemical composition of the modifier, the porous cross-linked anion-exchange membrane prepared by the invention has excellent diffusion dialysis performance and meets the requirements of diffusion dialysis practical application.
Example 2
A porous cross-linked anion exchange membrane was prepared in a similar manner to example 1, except that the soaking time was changed to 48 h. The ion exchange capacity of the membrane was measured to be 1.56 mmol/g. The porous cross-linked anion-exchange membrane of the present example was used for the treatment of HCl (concentration of 1.0 mol/L)/FeCl at 25 deg.C2(concentration is 0.2 mol/L) mixed waste acid simulation solution for acid recovery, and the acid dialysis coefficient of the membrane is measured to be 75.3 multiplied by 10-3 m/h，The acid/salt separation factor was 4368.2.
Compared with the comparative example 2, the ion exchange capacity of the porous cross-linked anion-exchange membrane prepared in the example is improved by 32.2 percent (from 1.18mmol/g to 1.56 mmol/g), and the acid dialysis coefficient is improved by 15.8 percent (from 65.0 multiplied by 10)-3The m/h is increased to 75.3 multiplied by 10-3m/h), the acid/salt separation factor increased 142.7 fold (from 30.4 to 4368.2), which is mainly attributed to the use of pentamethyldiethylenetriamine. Compared with N, N, N ', N' -tetramethyl-1, 3-propane diamine containing 2 tertiary amine groups and pentamethyl diethylenetriamine, the mobility and the steric hindrance are equivalent to those of the N, N, N ', N' -tetramethyl-1, 3-propane diamine, but the 3 tertiary amine groups contained in the membrane not only can provide more chemical sites to perform quaternization modification on the porous base membrane, but also can perform three-dimensional stereo crosslinking on the porous base membrane, so that the porous crosslinked anion exchange membrane prepared by the invention has higher acid dialysis coefficient and acid/salt separation factor.
Example 3
A porous crosslinked anion exchange membrane was prepared in a similar manner to example 1 except that the soaking time was changed to 0.5h, and the ion exchange capacity of the membrane was measured to be 0.53 mmol/g. The porous cross-linked anion-exchange membrane of the present example was used for the treatment of HCl (concentration of 1.0 mol/L)/FeCl at 25 deg.C2(concentration is 0.2 mol/L) mixed waste acid simulation solution for acid recovery, and the acid dialysis coefficient of the membrane is measured to be 15.6 multiplied by 10-3m/h, acid/salt separation factor 58.5.
As can be seen by comparison of examples 1-3, the ion exchange capacity of the porous cross-linked anion exchange membrane increased with increasing soaking time (0.5 h to 48 h), from 0.53mmol/g to 1.56mmol/g, while the acid dialysis coefficient of the membrane increased from 15.6X 10-3The m/h is increased to 75.3 multiplied by 10-3m/h) and the acid/salt separation factor (from 58.5 to 4368.2). This is because the degree of crosslinking and quaternization modification of the porous base film by pentamethyldiethylenetriamine increases with the increase in the soaking time. The content of ion exchange groups in the membrane can be improved by improving the quaternization modification degree, so that more sites are provided for ion transmission, and the acid dialysis coefficient of the membrane is improved; improvement of the degree of crosslinkingThe high level can increase the ion retention capacity of the membrane, thereby increasing the acid/salt separation factor of the membrane. The above results demonstrate that the method can break the "paradox effect" between the acid dialysis coefficient and the acid/salt separation factor of the membrane, and achieve a simultaneous increase in both.
Example 4
A porous crosslinked anion-exchange membrane was prepared in a similar manner to example 2, except that the concentration of the membrane-casting solution was changed to 15wt%, and the ion-exchange capacity of the membrane was measured to be 1.78 mmol/g. The porous cross-linked anion-exchange membrane of the present example was used for the treatment of HCl (concentration of 1.0 mol/L)/FeCl at 25 deg.C2(concentration is 0.2 mol/L) mixed waste acid simulation solution for acid recovery, and the acid dialysis coefficient of the membrane is determined to be 80.7 multiplied by 10-3m/h, acid/salt separation factor 689.2.
Example 5
A porous crosslinked anion-exchange membrane was prepared in a similar manner to example 2, except that the concentration of the membrane-casting solution was changed to 30wt%, and the ion-exchange capacity of the membrane was measured to be 1.06 mmol/g. The porous cross-linked anion-exchange membrane of the present example was used for the treatment of HCl (concentration of 1.0 mol/L)/FeCl at 25 deg.C2(concentration is 0.2 mol/L) mixed waste acid simulation solution for acid recovery, and the acid dialysis coefficient of the membrane is measured to be 40.2 multiplied by 10-3m/h, acid/salt separation factor 6278.3.
As can be seen by comparing examples 2, 4 and 5, the density of the porous base membrane prepared increases as the concentration of the casting solution increases. The density is improved, so that ion interception is facilitated, and the acid/salt separation factor of the porous cross-linked anion exchange membrane is increased; however, too high density is not beneficial to quaternization modification of the porous base membrane, and the ion exchange group capacity and the acid dialysis coefficient of the final porous cross-linked anion exchange membrane are reduced.
Example 6
A porous crosslinked anion-exchange membrane was prepared in a similar manner to example 2 except that the coating thickness of the membrane casting solution was changed to 150 μm, and the ion exchange capacity of the membrane was measured to be 1.79 mmol/g. The porous cross-linked anion-exchange membrane of the present example was used for the treatment of HCl (concentration of 1.0 mol/L)/FeCl at 25 deg.C2(concentration 0.2 mol/L)The mixed waste acid simulated solution is subjected to acid recovery, and the acid dialysis coefficient of the membrane is measured to be 82.8 multiplied by 10-3m/h, acid/salt separation factor 871.9.
Example 7
A porous crosslinked anion-exchange membrane was prepared in a similar manner to example 2 except that the coating thickness of the membrane casting solution was changed to 350. mu.m, and the ion exchange capacity of the membrane was measured to be 0.95 mmol/g. The porous cross-linked anion-exchange membrane of the present example was used for the treatment of HCl (concentration of 1.0 mol/L)/FeCl at 25 deg.C2(concentration is 0.2 mol/L) mixed waste acid simulation solution for acid recovery, and the acid dialysis coefficient of the membrane is measured to be 43.5 multiplied by 10-3m/h, acid/salt separation factor 5214.2.
As can be seen from the comparison of examples 2, 6 and 7, the density of the prepared porous base membrane is increased along with the increase of the coating film thickness of the casting solution. The density is improved, so that ion interception is facilitated, and the acid/salt separation factor of the porous cross-linked anion exchange membrane is increased; however, too high density is not beneficial to quaternization modification of the porous base membrane, and the ion exchange group capacity and the acid dialysis coefficient of the final porous cross-linked anion exchange membrane are reduced.
Example 8
The porous cross-linked anion-exchange membrane was prepared by a method similar to that of example 2 except that the concentration of the pentamethyldiethylenetriamine aqueous solution was changed to 0.5mol/L, and the ion exchange capacity of the membrane was measured to be 0.45 mmol/g. The porous cross-linked anion-exchange membrane of the present example was used for the treatment of HCl (concentration of 1.0 mol/L)/FeCl at 25 deg.C2(concentration is 0.2 mol/L) mixed waste acid simulation solution for acid recovery, and the acid dialysis coefficient of the membrane is measured to be 23.8 multiplied by 10-3m/h, acid/salt separation factor 1258.1.
Example 9
A porous crosslinked anion-exchange membrane was prepared in a similar manner to example 2 except that the concentration of the aqueous solution of pentamethyldiethylenetriamine was changed to 5mol/L, and the ion-exchange capacity of the membrane was measured to be 1.83 mmol/g. The porous cross-linked anion-exchange membrane of the present example was used for the treatment of HCl (concentration of 1.0 mol/L)/FeCl at 25 deg.C2(concentration 0.2 mol/L) mixed waste acid simulation solutionAcid recovery, and the acid dialysis coefficient of the membrane is measured to be 82.1 multiplied by 10-3m/h, acid/salt separation factor 4968.2.
As can be seen by comparing examples 2, 8 and 9, as the concentration of the aqueous pentamethyldiethylenetriamine solution increases, the degree of crosslinking and modification of the pore-crosslinked anion exchange membrane increases, and the acid dialysis coefficient and the acid/salt separation factor of the membrane also increase.
Example 10
A porous crosslinked anion-exchange membrane was prepared in a similar manner to example 2 except that the temperature of the aqueous solution of pentamethyldiethylenetriamine was changed to 25 ℃ and the ion-exchange capacity of the membrane was measured to be 0.51 mmol/g. The porous cross-linked anion-exchange membrane of the present example was used for the treatment of HCl (concentration of 1.0 mol/L)/FeCl at 25 deg.C2(concentration is 0.2 mol/L) mixed waste acid simulation solution for acid recovery, and the acid dialysis coefficient of the membrane is measured to be 24.1 multiplied by 10-3m/h, acid/salt separation factor 1353.6.
Example 11
A porous crosslinked anion-exchange membrane was prepared in a similar manner to example 2 except that the temperature of the aqueous solution of pentamethyldiethylenetriamine was changed to 90 ℃ and the ion exchange capacity of the membrane was measured to be 1.92 mmol/g. The porous cross-linked anion-exchange membrane of the present example was used for the treatment of HCl (concentration of 1.0 mol/L)/FeCl at 25 deg.C2(the concentration is 0.2 mol/L) mixed waste acid simulation solution is used for acid recovery, and the acid dialysis coefficient of the membrane is measured to be 84.6 multiplied by 10-3m/h, acid/salt separation factor 5124.3.
As can be seen by comparing examples 2, 10 and 11, as the temperature of the pentamethyldiethylenetriamine solution is increased, the degree of crosslinking and modification of the pore-crosslinked anion exchange membrane is increased, and the acid dialysis coefficient and the acid/salt separation factor of the membrane are also increased.
Example 12
A porous crosslinked anion-exchange membrane was prepared in a similar manner to example 2 except that the chloromethylation substitution degree of chloromethyl polyethersulfone was changed to 20%, and the ion-exchange capacity of the membrane was measured to be 0.41 mmol/g. The porous cross-linked anion-exchange membrane of the present example was used for the treatment of HCl (concentration of 1.0 mol/L)/FeCl at 25 deg.C2(the concentration is 0.2 mol/L) mixed waste acid simulation solution is used for acid recovery, and the acid dialysis coefficient of the membrane is measured to be 21.1 multiplied by 10-3m/h, acid/salt separation factor 1029.3.
Example 13
A porous crosslinked anion-exchange membrane was prepared in a similar manner to example 2 except that the chloromethylation substitution degree of chloromethyl polyethersulfone was changed to 90%, and the ion-exchange capacity of the membrane was measured to be 2.01 mmol/g. The porous cross-linked anion-exchange membrane of the present example was used for the treatment of HCl (concentration of 1.0 mol/L)/FeCl at 25 deg.C2(the concentration is 0.2 mol/L) mixed waste acid simulation solution is used for acid recovery, and the acid dialysis coefficient of the membrane is measured to be 85.5 multiplied by 10-3m/h, acid/salt separation factor 6356.7.
As can be seen from the comparison of examples 2, 12 and 13, as the chloromethylation substitution degree of chloromethylated polyethersulfone is increased, the porous base membrane can provide more reaction sites to react with pentamethyldiethylenetriamine, thereby facilitating the crosslinking and quaternization modification of the porous base membrane, and simultaneously increasing the ion exchange capacity, acid dialysis coefficient and acid/salt separation factor of the final porous crosslinked anion-exchange membrane.
Example 14
The porous cross-linked anion-exchange membrane is prepared by a method similar to that in example 2, only the solvent of the membrane casting solution is changed into N-methylformamide, the matrix of the membrane coating is changed into a polyethylene membrane, the method of the membrane coating is changed into spraying, and the solvent of the pentamethyldiethylenetriamine solution is changed into methanol, so that the porous cross-linked anion-exchange membrane with similar properties is obtained.
Example 15
The porous cross-linked anion-exchange membrane is prepared by a method similar to that in example 2, only the solvent of the membrane casting solution is changed into N-methylacetamide, the matrix of the coating film is changed into a polytetrafluoroethylene plate, the coating method is changed into impregnation, and the solvent of the pentamethyldiethylenetriamine solution is changed into ethanol, so that the porous cross-linked anion-exchange membrane with similar properties is obtained.
Example 16
The porous cross-linked anion-exchange membrane prepared by the method similar to that in example 2 is obtained by changing the solvent of the casting solution into dimethyl sulfoxide, the matrix of the coating film into a metal plate, the method of the coating film into coating, and the solvent of the pentamethyldiethylenetriamine solution into acetone.
The results of the above examples show that the porous cross-linked anion exchange membrane with high acid dialysis coefficient and high acid/salt separation factor can be prepared by using the special microstructure of the porous membrane, especially sufficient free space in the internal microporous structure of the porous membrane and using pentamethyldiethylenetriamine as the cross-linking and quaternizing bifunctional agent, and the diffusion dialysis performance of the porous cross-linked anion exchange membrane is far higher than that of the existing anion exchange membrane, so that the porous cross-linked anion exchange membrane has a prospect of large-scale application.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a porous cross-linked anion exchange membrane for diffusion dialysis is characterized in that chloromethylated polyether sulfone is dissolved in an organic solvent to form a membrane casting solution, then coating is carried out on a substrate, and a chloromethylated polyether sulfone porous base membrane is prepared by a solvent-free phase-induced conversion method; and then soaking the obtained chloromethylated polyether sulfone porous base membrane in a pentamethyl diethylenetriamine solution for synchronous crosslinking and quaternization modification, thereby obtaining the porous crosslinking anion exchange membrane suitable for diffusion dialysis.
2. The method of preparing a porous cross-linked anion exchange membrane for diffusion dialysis as claimed in claim 1, wherein the structural formula of chloromethylated polyethersulfone is:
wherein, X =20% to 90%, which represents the chloromethylation degree of the chloromethylated polyethersulfone, i.e. the mole percentage of chloromethyl-containing repeating units in the chloromethylated polyethersulfone to all repeating units.
3. The method of preparing a porous cross-linked anion exchange membrane for diffusion dialysis as claimed in claim 1, wherein the organic solvent is selected from any one of N-methylpyrrolidone, N-methylformamide, N-methylacetamide or dimethylsulfoxide.
4. The method of preparing a porous cross-linked anion exchange membrane for diffusion dialysis as claimed in claim 1, wherein the concentration of the membrane casting solution is 15wt% to 30 wt%.
5. The method of preparing a porous cross-linked anion exchange membrane for diffusion dialysis as claimed in claim 1, wherein the substrate is selected from any one of polyethylene membrane, polytetrafluoroethylene sheet, metal sheet or glass sheet.
6. The method for preparing a porous cross-linked anion exchange membrane for diffusion dialysis as claimed in claim 1, wherein the coating is by scraping, spraying, dipping or coating.
7. The method for preparing a porous cross-linked anion exchange membrane for diffusion dialysis as claimed in claim 1, wherein the thickness of the coating film of the casting solution is 150 to 350 μm.
8. The method for preparing the porous cross-linked anion-exchange membrane for diffusion dialysis as claimed in claim 1, wherein the concentration of the pentamethyldiethylenetriamine solution is 0.5 to 5mol/L, and the solvent is selected from any one of water, methanol, ethanol or acetone.
9. The method for preparing a porous cross-linked anion exchange membrane for diffusion dialysis as claimed in claim 1, wherein the soaking temperature is 25-90 ℃ and the soaking time is 0.5-48 h.
10. A porous cross-linked anion exchange membrane prepared by the method of any of claims 1 to 9.
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