CN114699930B - Polyazacyclic amide membrane for dye wastewater treatment and preparation method thereof - Google Patents
Polyazacyclic amide membrane for dye wastewater treatment and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of dye wastewater treatment by membrane separation, and particularly relates to a polyazacyclic amide membrane for dye wastewater treatment and a preparation method thereof. The method takes a cyclic monomer azacyclane as a water phase monomer, and adopts interfacial polymerization to prepare the polyazacyclic amide membrane. The invention adopts novel cyclic molecular azacycloalkane as a water phase monomer, loads the water phase monomer on the surface of a base membrane, and then reacts with trimesoyl chloride to carry out an interfacial polymerization process, thereby constructing the polyazacyclic amide membrane with stable structure and high selectivity. According to the polyazacyclic amide membrane prepared by the invention, the intra-ring pores of the nitrogen heterocycles are increased, and the characteristic of intercepting macromolecular dyes is kept, so that the dyes/salts are effectively separated.
Description
Technical Field
The invention belongs to the field of dye wastewater treatment through membrane separation, and particularly relates to a polyazacyclic amide membrane for dye wastewater treatment and a preparation method thereof.
Background
Due to the rapid growth of population, urbanization and industrialization, the discharge amount of textile dye wastewater is rapidly increasing. The dye pollutants can not only harm human health by polluting fresh water resources, but also have harmful effects on aquatic organisms. Therefore, how to remove the dye pollutants efficiently is urgent. Heretofore, conventional techniques such as adsorption, distillation, flocculation, biodegradation, advanced oxidation, and the like have been widely used for the treatment of dye wastewater. While these methods are effective in removing dyes, one major challenge is the low selectivity of the dye/salt mixture, which impacts dye purification and recovery as well as inorganic salt recycling. Compared with the above technology, the powder is looseThe filter membrane has the advantages of high separation coefficient, high flux, environmental friendliness and the like due to the fact that the molecular size of the filter membrane is similar to that of most dyes, and the filter membrane is widely applied to a dye wastewater treatment separation system. More importantly, unlike conventional dense nanofiltration membranes, loose nanofiltration membranes are primarily characterized by high divalent salts (e.g., na) 2 SO 4 ) Permeability, which makes it possible to separate the dye/salt mixture.
At present, the loose nanofiltration membrane construction method mainly comprises blending-phase conversion, surface chemical modification, bionic material deposition, interfacial polymerization and the like. The interfacial polymerization is a method for industrially synthesizing a large-area film, and the method mainly utilizes piperazine as a water-phase monomer and trimesoyl chloride as an oil-phase monomer to prepare the polypiperazine amide nanofiltration membrane. However, such polyamide membranes have high retention of both dyes and multivalent inorganic salts, making it difficult to effectively separate dye/salt mixtures. Therefore, the crosslinking degree of the film is finely adjusted and the pore diameter and porosity are increased by adopting or introducing long-chain branched monomers, multiple primary amine monomers and hydroxyl cyclic monomers, so that the separation selectivity of the dye/salt is improved. However, amine monomers have high reactivity, and are easy to form compact polyamide, so that through-channels are difficult to obtain, and the increase of membrane flux is not obvious. Compared with the hydroxyl cyclic monomer, the hydroxyl cyclic monomer has the following advantages: the polyester film with lower crosslinking degree is formed, and meanwhile, the free volume and the pore canal connectivity of the film can be increased by the pores in the ring, so that the improvement of the dye/salt separation selectivity is facilitated. However, the weak acid and alkali resistance of the membrane limits the application of the membrane in dye wastewater treatment.
Disclosure of Invention
The invention aims to provide a polyazacyclic amide membrane for dye wastewater treatment and a preparation method thereof, which can better solve the problems of acid and alkali resistance of the membrane and effectively separate a dye/salt mixture.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a polyazacyclic amide membrane for dye wastewater treatment is obtained by the following preparation method: the polyazacyclic amide membrane is prepared by using a cyclic monomer azacycloalkane as a water phase monomer and adopting interfacial polymerization.
The solvent of the azacycloalkane is aqueous solution, and the mass concentration of the aqueous solution is 0.05-0.2wt%.
The pH of the aqueous solution of the azacycloalkane is preferably 7 to 14, more preferably 12 to 14.
Taking a normal hexane solvent of trimesoyl chloride as an oil phase monomer, wherein the mass concentration is 0.05-0.2wt%; the mass ratio of the aqueous solution of the azacycloalkane to the n-hexane solution of trimesoyl chloride is as follows: 1:1-3.
Preferably, the azacycloalkane is 1,4, 7-triazacyclononane, 1,4,8, 11-tetraazacyclotetradecane or 1,4,7,10, 13-pentaazacyclopentadecane.
The molecular formula of the azacycloalkane is as follows:
firstly, soaking an aqueous solution of azacycloalkane on the surface of a base film for 3-10min; adding oil phase monomer solution, reacting for 0.5-2min, preferably 0.5-1min, and heat treating at 50-80 deg.C for 1-5min.
The basement membrane can be one of polysulfone, polyethersulfone, polyacrylonitrile or Kevlar basement membrane.
Specifically, the preparation method of the polyazacyclic amide membrane for dye wastewater treatment comprises the following steps:
(1) Fixing a base membrane in a membrane component, soaking an azacyclo-alkane aqueous solution with the mass fraction of 0.05-0.2wt% on the surface of the base membrane for 3-10 minutes, and removing the excessive azacyclo-alkane aqueous solution until no obvious water stain exists on the membrane;
(2) Pouring 0.05-0.2wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 0.5-2min;
(3) After the reaction is finished, washing the surface of the membrane for 10-30s by using a normal hexane solvent, and then carrying out heat treatment at 50-80 ℃ for 1-5min to obtain the polyazacyclic amide membrane.
The invention uses novel cyclic monomer azacyclane as water phase monomer to construct the polyazacyclic amide membrane with stable structure and high selectivity. The azacycloalkane is a piperazine cyclic compound with secondary amine groups, and the existence of a plurality of secondary amine groups enables the compound to be subjected to interfacial polymerization reaction with trimesoyl chloride to form a polyamide membrane with a stable structure, and the formed amido bond is more stable than an ester bond. In addition, azacycloalkanes and piperazines have unique advantages in the design and development of high dye/salt selective membranes: with the increase of the number of carbon or nitrogen atoms on the azacycloalkane ring, the internal pore of the nitrogen heterocycle per se is increased, so that the free volume in the film and the connectivity in the pore channel can be increased in principle, the permeability of the composite film is improved, meanwhile, the increased steric hindrance and the reduced solubility of the composite film can weaken the reaction activity of the azacycloalkane, the degree of crosslinking of the film is reduced to a certain extent to obtain more and larger-sized through nanopores, a microchannel which is beneficial to the permeation of hydrated ions is formed, and in addition, the characteristic of intercepting macromolecular dye is retained, so that the effective separation of dye/salt is realized. In addition, by changing the interfacial polymerization conditions, for example, as the pH of the aza-cyclic monomer-water phase increases, the degree of cross-linking of the polyazacyclic amide membrane decreases, thereby increasing the flux of the composite membrane. In addition, the invention controls the monomer concentration and the interfacial polymerization reaction time, and optimizes the interfacial reaction condition, thereby increasing the porosity of the membrane and further optimizing the separation performance of the composite membrane.
In the method for preparing the polyazacyclic amide membrane, azacycloalkane does not need to be pretreated, and different kinds of polyazacyclic aqueous solutions are directly loaded on the surface of a base membrane such as a polysulfone membrane, and then an oil phase solution is added to carry out interfacial polymerization reaction, so that the polyazacyclic amide membrane for treating dye wastewater can be prepared.
Compared with the prior art, the invention has the following advantages:
the invention adopts novel cyclic molecular azacycloalkane as a water phase monomer, loads the water phase monomer on the surface of a base membrane, and then reacts with trimesoyl chloride to carry out an interfacial polymerization process, thereby constructing the polyazacyclic amide membrane with stable structure and high selectivity. According to the polyazacyclic amide membrane prepared by the invention, the intra-ring pores of the nitrogen heterocycles are increased, and the characteristic of intercepting macromolecular dyes is kept, so that the dyes/salts are effectively separated.
Drawings
FIG. 1 is a schematic representation of the polyazacyclic amide membranes prepared in example 3, example 4, and example 7, respectively.
Detailed Description
The technical solution of the present invention is described below by using specific examples, but the scope of the present invention is not limited thereto: example 1
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) Fixing a polysulfone membrane in a membrane component, taking 0.18wt% of 1,4, 7-triazacyclononane aqueous solution, adjusting the pH to 12, soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing the excessive 1,4, 7-triazacyclononane aqueous solution until no obvious water stain exists on the membrane;
2) Pouring 0.1wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1min;
3) After the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment for 3min at 80 ℃ to obtain the polyazacyclic amide membrane which is marked as a TFC-1 membrane.
Example 2
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) Fixing a polysulfone membrane in a membrane component, taking 0.18wt% of 1,4, 7-triazacyclononane aqueous solution, adjusting the pH to 13, soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing the excessive 1,4, 7-triazacyclononane aqueous solution until no obvious water stain exists on the membrane;
2) Pouring 0.1wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1min;
3) After the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment for 3min at 80 ℃ to obtain the polyazacyclic amide membrane, which is marked as a TFC-2 membrane.
Example 3
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) Fixing a polysulfone membrane in a membrane component, taking 0.18wt% of 1,4, 7-triazacyclononane aqueous solution, adjusting the pH to 14, soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing the excessive 1,4, 7-triazacyclononane aqueous solution until no obvious water stain exists on the membrane;
2) Pouring 0.1wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1min;
3) After the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment at 80 ℃ for 3min to obtain the polyazacyclic amide membrane, which is marked as a TFC-3 membrane.
Example 4
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) Fixing a polysulfone membrane in a membrane component, taking 0.12wt% of 1,4,8, 11-tetraazacyclotetradecane aqueous solution, adjusting the pH to 12, soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing excessive aqueous phase solution until no obvious water stain exists on the membrane;
2) Pouring 0.1wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1min;
3) After the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment for 3min at 80 ℃ to obtain the polyazacyclic amide membrane which is marked as a TFC-4 membrane.
Example 5
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) Fixing a polysulfone membrane in a membrane component, taking 0.12wt% of 1,4,8, 11-tetraazacyclotetradecane aqueous solution, adjusting the pH to 13, soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing excessive aqueous phase solution until no obvious water stain exists on the membrane;
2) Pouring 0.1wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1min;
3) After the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment for 3min at 80 ℃ to obtain the polyazacyclic amide membrane which is marked as a TFC-5 membrane.
Example 6
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) Fixing a polysulfone membrane in a membrane component, taking 0.12wt% of 1,4,8, 11-tetraazacyclotetradecane aqueous solution, adjusting the pH to 14, soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing excessive aqueous phase solution until no obvious water stain exists on the membrane;
2) Pouring 0.1wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1min;
3) After the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment for 3min at 80 ℃ to obtain the polyazacyclic amide membrane which is marked as a TFC-6 membrane.
Example 7
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) Fixing a polysulfone membrane in a membrane component, taking 0.10wt% of 1,4,7,10, 13-pentaazacyclopentadecane aqueous solution, adjusting the pH to 13, soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing excessive aqueous phase solution until no obvious water stain exists on the membrane;
2) Pouring 0.1wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1min;
3) After the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment for 3min at 80 ℃ to obtain the polyazacyclic amide membrane, which is marked as a TFC-7 membrane.
Example 8
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) Fixing a polysulfone membrane in a membrane component, taking 0.10wt% of 1,4,7,10, 13-pentaazacyclopentadecane aqueous solution, adjusting the pH to 14, soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing excessive aqueous phase solution until no obvious water stain exists on the membrane;
2) Pouring 0.1wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1min;
3) After the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment for 3min at 80 ℃ to obtain the polyazacyclic amide membrane which is marked as a TFC-8 membrane.
Comparative example 1
Preparing a PIP-TMC polyamide nanofiltration membrane:
1) Fixing a polysulfone membrane in a membrane component, soaking 0.10wt% of piperazine aqueous solution on the surface of the polysulfone membrane, wherein the pH of the aqueous phase monomer solution is 11, and removing the excess piperazine aqueous solution after soaking for 5 minutes until no obvious water stain exists on the membrane;
2) Pouring 0.1wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1min;
3) After the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment at 80 ℃ for 3min to obtain the polypiperazine amide membrane, which is marked as PIP/TMC-TFC membrane.
Comparative example 2
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) Fixing a polysulfone membrane in a membrane component, taking 0.18wt% of 1,4, 7-triazacyclononane aqueous solution, wherein the pH of the aqueous phase monomer solution is 9, soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing the excessive 1,4, 7-triazacyclononane aqueous solution until no obvious water stain exists on the membrane;
2) Pouring 0.1wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1min;
3) After the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment for 3min at 80 ℃ to obtain a polyazacyclic amide membrane which is marked as a TFC membrane of comparative example 2;
comparative example 3
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) Fixing a polysulfone membrane in a membrane component, taking 0.12wt% of 1,4,8, 11-tetraazacyclotetradecane aqueous solution, wherein the pH of the aqueous phase monomer solution is 10, and soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing excessive aqueous phase solution until no obvious water stain exists on the membrane;
2) Pouring 0.1wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1min;
3) After the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment at 80 ℃ for 3min to obtain the polyazacyclic amide membrane which is marked as a comparative example 3TFC membrane.
Comparative example 4
A preparation method of a polyazacyclic amide membrane for dye wastewater treatment comprises the following specific steps:
1) Fixing a polysulfone membrane in a membrane component, taking 0.10wt% of 1,4,7,10, 13-pentaazacyclopentadecane aqueous solution, wherein the pH of the aqueous phase monomer solution is 12, soaking the aqueous solution on the surface of the polysulfone membrane for 5 minutes, and removing excessive aqueous phase solution until no obvious water stain exists on the membrane;
2) Pouring 0.1wt% of trimesoyl chloride-n-hexane solution onto the surface of the membrane, and reacting for 1min;
3) After the reaction is finished, washing the surface of the membrane for 30s by using a normal hexane solvent, and then carrying out heat treatment at 80 ℃ for 3min to obtain the polyazacyclic amide membrane which is marked as a TFC membrane of comparative example 4.
The water flux and the removal rate of dyes and inorganic salts from the dye wastewater of the polyazacyclic amide membranes prepared in examples 1 to 8 and the amide membranes prepared in comparative examples 1 to 4 were measured at room temperature, and the results are shown in tables 1 and 2. The test was carried out at normal temperature in a cross-flow apparatus at a pressure of 0.4MPa.
Table 1 shows that the water flux of the polyazeamide membranes prepared in examples 1-8 and the water flux of the polyazeamide membranes prepared in comparative examples 1-4 and the rejection rate of the nanofiltration membranes on the dye in the dye wastewater reported by the literature are within a reasonable error range, and the data error is within a reasonable error range.
TABLE 1
It can be seen from the table that compared with the traditional polypiperazine polyamide membrane and the nanofiltration membrane reported in the literature, the polyazacyclic amide membrane has the water flux 5-10 times that of the traditional polypiperazine polyamide membrane on the premise of keeping higher retention rate of the dye, and shows excellent dye removal capability.
Table 2 shows that the water flux of the polyazacyclic amide membranes prepared in examples 1-8 and the water flux of the amide membranes prepared in comparative examples 1-4 and the retention rate of inorganic salts in dye wastewater by the nanofiltration membranes reported in the literature are within reasonable error ranges.
TABLE 2
As can be seen from the table, compared with the conventional polypiperazine amide membrane and the nanofiltration membrane reported in the literature, the polyazacyclic amide membrane has a higher retention rate of divalent salt without adjusting the pH of the aqueous phase monomer, and thus the separation of the divalent salt from the dye molecule cannot be realized. After the pH of the aqueous phase monomer solution is adjusted, the retention rate of the polyazacyclic amide membrane on inorganic salt is greatly reduced, and excellent dye/salt separation capability is shown.
Claims (6)
1. A preparation method of a polyazacyclic amide membrane for dye wastewater treatment is characterized in that a cyclic monomer azacycloalkane is used as a water phase monomer, and interfacial polymerization is adopted to prepare the polyazacyclic amide membrane; the azacycloalkane is 1,4, 7-triazacyclononane, 1,4,8, 11-tetraazacyclotetradecane or 1,4,7,10, 13-pentaazacyclopentadecane; the aqueous solution of the azacycloalkane has a pH of 12 to 14.
2. The method for producing a polyazacyclic amide membrane for dye wastewater treatment according to claim 1, wherein the solvent of azacycloalkane is an aqueous solution having a mass concentration of 0.05 to 0.2wt%.
3. The method for preparing the polyazacyclic amide membrane for dye wastewater treatment according to claim 2, wherein the n-hexane solvent of trimesoyl chloride is used as an oil phase monomer, and the mass concentration is 0.05-0.2wt%; the mass ratio of the aqueous solution of the azacyclane to the n-hexane solution of trimesoyl chloride is as follows: 1:1-3.
4. The method for preparing polyazacyclic amide membrane for dye wastewater treatment according to claim 1, wherein the aqueous solution of azacycloalkane is first immersed for 3-10min on the surface of the base membrane; then adding oil phase monomer solution to react for 0.5-2min, and then carrying out heat treatment at 50-80 ℃ for 1-5min.
5. Polyazacyclic amide membranes obtainable by the process of any of claims 1-4.
6. Use of the polyazacyclic amide membrane obtained by the preparation method of claim 5 in dye wastewater treatment.
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