KR101737092B1 - Polyamide nanofiltration composite membrane having improved acid resistance and manfacturing method thereof - Google Patents
Polyamide nanofiltration composite membrane having improved acid resistance and manfacturing method thereof Download PDFInfo
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- KR101737092B1 KR101737092B1 KR1020160023420A KR20160023420A KR101737092B1 KR 101737092 B1 KR101737092 B1 KR 101737092B1 KR 1020160023420 A KR1020160023420 A KR 1020160023420A KR 20160023420 A KR20160023420 A KR 20160023420A KR 101737092 B1 KR101737092 B1 KR 101737092B1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/00—Details relating to properties of membranes
- B01D2325/22—Thermal or heat-resistance properties
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
One embodiment of the present invention relates to a porous support; And a piperazine-based polyamide active layer formed on the porous support and having a structure crosslinked by a triazine-based compound, and a process for producing the polyamide-based nano-separation membrane.
Description
The present invention relates to a polyamide-based nano-separator excellent in acid resistance and a method for producing the same.
The nano-separator is a composite membrane prepared by coating an active layer of a thin film on the surface of a porous support, and is known as a separator having high permeability and high removal rate.
In general, the polyamide-based separator has a structure in which an amine-containing aqueous solution is mixed with a polyfunctional acyl halide-based compound on a microporous support, and the polyamine- And an organic solution. The polyvinyl alcohol separation membrane is prepared by coating polyvinyl alcohol on a microporous support and crosslinking.
Polyamide based membranes are more economical than other membranes and are superior in water quality and can be applied to a wide range regardless of the quality of raw water. Particularly, the polyamide-based separator can be produced by a method of controlling the electrostatic property using the negative charge property of the membrane surface caused by unreacted monomers existing on the surface, controlling the pore size of the membrane surface, or controlling the hydrophobicity of the membrane, The removal efficiency of the separation membrane can be increased.
On the other hand, acid wastewater discharged in a large amount in the acid cleaning process of the smelting process contains oil and rare metals such as copper, lead, iron and chromium, and it is necessary to recover it efficiently and economically. However, there is no technology to directly recover oil and rare metals from acidic wastewater solutions, and in the actual process, neutralization, coagulation sedimentation, adsorption, ion exchange, etc. are used to neutralize and then dispose acidic wastewater.
These processes are mostly costly, have a large amount of waste and secondary pollution and are not environmentally friendly. In addition, when the conventional polyamide-based separation membrane is introduced into the treatment process of acid wastewater, the active layer of the separation membrane is exposed to a high concentration of acid for a long time, so that the ion removal rate of the separation membrane is remarkably deteriorated.
On the other hand, there is a growing demand for nano-separators that enable technically and economically recyclable acid wastewater containing oil and rare metals.
Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above problems occurring in the prior art, and an object of the present invention is to provide a polyamide resin composition which is excellent in acid resistance and can maintain water permeability and ion removal rate at the initial stage of the process even when exposed to high- And a method of manufacturing the same.
An aspect of the present invention relates to a porous support; And a piperazine-based polyamide active layer formed on the porous support and having a structure crosslinked by a triazine-based compound.
In one embodiment, the porous support comprises a polymeric material selected from the group consisting of polysulfone, polyethersulfone, polyimide, polyamide, polyetherimide, polyacrylonitrile, poly (methyl methacrylate), polyethylene, And at least one polymer selected from the group consisting of halogenated polymers.
In one embodiment, the triazine-based compound may be selected from the group consisting of 1,2,3-triazine, 1,2,4-triazine, and 1,3,5-triazine.
In one embodiment, the triazine-based compound may be 1,3,5-triazine.
In one embodiment, the 1,3,5-triazine can be a melamine.
In one embodiment, the piperazine-based polyamide active layer may satisfy the following equations (1) and (2).
&Quot; (1) "
&Quot; (2) "
Where N and O are the weight percentages of nitrogen and oxygen, respectively, relative to the total weight of the piperazine-based polyamide active layer, and m and n are the fraction of the crosslinked and linear portions of the piperazine-based polyamide active layer, respectively , 0.45? M? 0.55.
In one embodiment, the water permeability of the nano-separator may be greater than 15GFD.
According to another aspect of the present invention, there is also provided a method for preparing an amine aqueous solution, comprising: (a) preparing an aqueous amine solution containing a piperazine and a triazine-based compound; (b) applying a porous support to the aqueous amine solution; And (c) applying the porous support to an organic solution containing an amine-reactive compound. The present invention also provides a method for producing a polyamide-based nano-separator.
In one embodiment, the content of piperazine in the amine aqueous solution may be 0.5 to 10% by weight.
In one embodiment, the content of the triazine-based compound in the amine aqueous solution may be 0.3 to 5.0% by weight.
In one embodiment, the amine-reactive compound may be selected from the group consisting of trimesoyl chloride (TMC), isophthaloyl chloride (IPC), terephthaloyl chloride (TPC), and mixtures of two or more thereof.
In one embodiment, the content of the amine-reactive compound in the organic solution may be 0.01 to 0.5 wt%.
According to one aspect of the present invention, by adding a certain amount of a triazine-based compound to an active layer of a polyamide-based nano-separator, a copolymer formed by the interfacial polymerization of piperazine and an amine-reactive monomer has a cross- , The acid resistance, heat resistance, and durability of the polyamide-based nano-separator can be improved.
It should be understood that the effects of the present invention are not limited to the effects described above, but include all effects that can be deduced from the description of the invention or the composition of the invention set forth in the claims.
1 shows FT-IR analysis results of active layers according to Examples and Comparative Examples of the present invention.
2 is an FE-SEM image of the surface of the active layer before and after sulfuric acid exposure according to the comparative example of the present invention.
3 is an FE-SEM image of the surface of the active layer before and after sulfuric acid exposure according to Examples and Comparative Examples of the present invention.
4 is a schematic view of an apparatus for evaluating the performance of a nanofiber separator according to an embodiment of the present invention.
FIGS. 5 and 6 show the measurement results of the water permeability and the ion removal rate of the nanofiber separator according to the examples and the comparative examples of the present invention, respectively.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.
Throughout the specification, when a part is referred to as being "connected" to another part, it includes not only "directly connected" but also "indirectly connected" . Also, when an element is referred to as "comprising ", it means that it can include other elements, not excluding other elements unless specifically stated otherwise.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
An aspect of the present invention relates to a porous support; And a piperazine-based polyamide active layer formed on the porous support and having a structure crosslinked by a triazine-based compound.
The porous support is a typical microporous support and is not particularly limited as long as the pore size is not large enough to interfere with the formation of a thin film on the porous support, but is sufficiently large to allow penetration of permeated water.
If the size of the pores is more than 500 nm, the thin film formed on the upper part can not be formed in the pores so that a flat sheet structure can not be formed.
The porous support may be a member selected from the group consisting of polysulfone, polyether sulfone, polyimide, polyamide, polyetherimide, polyacrylonitrile, poly (methyl methacrylate), polyethylene, polypropylene, And may be formed by knife casting with one or more selected polymers.
The thickness of the porous support may be 25 to 125 탆, preferably 40 to 75 탆, but is not limited thereto.
The polyamide active layer may be composed of a copolymer formed by the interfacial polymerization of piperazine and an amine reactive compound. That is, the piperazine and amine-reactive compounds may be involved in the interfacial polymerization as monomers.
The amine-reactive compound may be at least one member selected from the group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide, and a polyfunctional isocyanate, and may preferably be an aromatic, polyfunctional acyl halide. The polyfunctional acyl halide can be, for example, one selected from the group consisting of trimesoyl chloride (TMC), isophthaloyl chloride (IPC), terephthaloyl chloride (TPC) But is not limited thereto.
The triazine-based compound participates in the interfacial polymerization of the piperazine and the amine-reactive compound to change the structure of the active layer (copolymer). The triazine-based compound does not directly participate as a monomer in the interfacial polymerization of the piperazine and the amine-reactive compound but participates as an additive, specifically, as a crosslinking agent, and adjusts the fraction of the cross-linked portion of the linear portion of the copolymer to a predetermined range .
Thus, the piperazine-based polyamide active layer may have a structure that satisfies the following equations (1) and (2) as a certain amount of triazine-based compound is added.
&Quot; (1) "
&Quot; (2) "
Where N and O are the weight percentages of nitrogen and oxygen, respectively, relative to the total weight of the piperazine-based polyamide active layer, and m and n are the fraction of the crosslinked and linear portions of the piperazine-based polyamide active layer, respectively , 0.45? M? 0.55.
The piperazine-based polyamide active layer to which the triazine-based compound is added may have at least one amide bond, and may be divided into a linear portion having a crosslinked portion and a pendant carboxyl group. The carboxyl group contained in the linear portion can improve the permeability of the separation membrane through hydrogen bonding, which is more stable and stronger in water than the hydrophilic amide group.
The crosslinked part and the linear part are expressed by the molecular formula (empirical formula) as C 18 H 22 N 3 O 3 and C 13 H 12 N 2 O 4 , respectively. Therefore, the number or ratio of N and O among them . Theoretically, when the ratio of O / N is 1.0, a fully crosslinked polyamide containing an amide bond in which an oxygen ion is bonded to a nitrogen ion can be formed, and when an O / N ratio is 2.0, an oxygen ion is bonded to a carboxyl group A fully linear polyamide can be formed.
Therefore, when the ratio of O / N is about 1.5, that is, when m satisfies the range of 0.45? M? 0.55 and the ratio of m and n is about 1: 1, the transmission performance by the linear structure and the cross- Acid resistance and durability can be balanced.
The triazine-based compound may be selected from the group consisting of 1,2,3-triazine, 1,2,4-triazine, and 1,3,5-triazine, preferably 1,3,5 - triazine, more preferably melamine.
Since the melamine has a conjugated bond with the triazine ring in the molecule, the fraction of the linear portion and the crosslinked portion of the copolymer is adjusted to a predetermined range to impart the necessary level of permeability and acid resistance to the nanofiber can do. This effect can also be understood to be due to the increase in the thickness of the active layer due to addition of the triazine-based compound.
The water permeability of the nano-separator may be 15GFD or more. Specifically, the initial water permeability of the nanofiber separator may be 15 GFD or more, and the water permeability after exposure to a high concentration of acid solution (sulfuric acid, 15 wt%) for 10 days or more may be maintained at 15 GFD or more. The acid resistance and durability as well as the permeation performance can be greatly improved.
Another aspect of the present invention is a method for preparing a polyamide resin composition comprising the steps of: (a) preparing an aqueous amine solution comprising a piperazine and a triazine-based compound; (b) applying a porous support to the aqueous amine solution; And (c) applying the porous support to an organic solution containing an amine-reactive compound. The present invention also provides a method for producing a polyamide-based nano-separator.
In the step (a), the content of the piperazine in the amine aqueous solution may be 0.5 to 10% by weight. If the content of piperazine is less than 0.5% by weight, the active layer may become unstable. If the content of piperazine is more than 10% by weight, the active layer may be excessively thickened and the water permeability may be significantly reduced.
The content of the triazine-based compound in the amine aqueous solution may be 0.3 to 5.0% by weight. If the content of the triazine compound is less than 0.3% by weight, the active layer may be exposed to a high concentration of acid for a long time, resulting in etching and breakage, and the ion removal rate may be significantly deteriorated. And the acid resistance of the separator may be lowered. The nature, kind, action, effect and the like of the triazine-based compound are as described above.
In the step (b), the amine aqueous solution may be applied to the porous support by various methods such as impregnation and coating for 10 seconds to 10 minutes, preferably 1 minute to 5 minutes. After the application, Sponge, air knife, or any other suitable means. The nature, kind, action, effect, etc. of the porous support are as described above.
In the step (c), the amine-reactive compound can be generally dissolved in an organic solvent, and the organic solvent includes, for example, hexane, cyclohexane, heptane, an alkane having 8 to 12 carbon atoms, And mixtures thereof. However, the present invention is not limited thereto.
The content of the amine-reactive compound in the organic solution may be 0.01 to 0.5 wt%. If the content of the amine-reactive compound is less than 0.01% by weight, interfacial polymerization with piperazine can not be performed smoothly. If the content of the amine-reactive compound exceeds 0.5% by weight, excess amine-reactive compound may remain after the reaction, .
In step (c), the organic solution may be applied to the porous support by various methods such as impregnation and coating for 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes, The reaction of the compound can be induced. The nature, kind, action, effect and the like of the amine-reactive compound are as described above.
Hereinafter, embodiments of the present invention will be described in detail.
Example
A polysulfone support was applied for 2 minutes to an aqueous solution containing 1.0% by weight of piperazine and 0.3% by weight of melamine. The excess solution existing on the surface of the support was removed using a roller, and then the solution was applied to a solution containing 0.1% by weight of trimethoyl chloride and a remaining amount of n-hexane for 1 minute and dried in an oven to prepare a nanofiber separator.
Comparative Example One
A nano-separator was prepared in the same manner as in the above example, except that the aqueous solution did not contain melamine.
Comparative Example 2
A nano separator was prepared in the same manner as in the above example except that the content of melamine in the aqueous solution was adjusted to 0.05 wt%.
Comparative Example 3
A nano-separator was prepared in the same manner as in the above example except that the content of melamine in the aqueous solution was adjusted to 0.1 wt%.
Experimental Example 1: Structural Characteristics of Nano Membrane 1
The chemical structure of the nanoparticle active layer was analyzed by XPS element composition analysis. The active layers of the nanocomposite membranes according to Examples and Comparative Examples contained oxygen, nitrogen, and carbon, and their contents were measured based on the peak intensities of O (1s), N (1s), and C (1s), respectively.
As described above, the active layer is formed of a polyamide structure having at least one amide bond, and can be divided into a linear portion having a crosslinked portion and a pendant carboxyl group. M and n were calculated by the following equations (1) and (2) in which the contents of the nitrogen element and the oxygen element in the cross-linked portion and the linear portion were respectively m and n, respectively, by NPS and XPS analysis.
&Quot; (1) "
&Quot; (2) "
The results of the XPS element composition analysis and m and n thus calculated are shown in Table 1 below.
(Full bridge)
(Fully linear)
Theoretically, a completely crosslinked active layer containing an amide bond in which an oxygen ion is bonded to a nitrogen ion is formed at an O / N ratio of 1.0, and a completely linear active layer in which oxygen ions are bonded to a carboxyl group at a time of 2.0.
Referring to Table 1, the nanofiber separator of Comparative Example 2 can be regarded as a nanofiber separator having a completely crosslinked structure with an O / N ratio of 1.23, and the nanofiber separator of Comparative Example 3 has a larger O / N ratio m is small, it can be regarded as a nanostructured membrane having a linear structure. Assuming an ideal nano-separator with a ratio of cross-linked to linear of about 1: 1, the nano-separator of the example is analyzed to have a ratio of m to n that is closest to 1: 1.1.
In addition, the structure of the active layer of the nano separator was analyzed by FT-IR analysis, and the results are shown in Table 2 and FIG.
Table 2 and Fig. Referring to 1, 3,600cm -1 and may determine the NH, C = N bond of the melamine in 1,529cm -1, CO-NH, that is from 1,547, 1,630 ~ 1,640cm -1, amide bond Structure can be confirmed. Peaks of the same pattern appearing in the range of 450 to 2,000 cm < -1 > represent typical polysulfone peaks.
Comparing the results of Examples and Comparative Example 1, it was found that the primary amine peaks of piperazine were reduced at 1,630-1,640 cm -1 , indicating that the trimethoyl chloride was converted by the melamine to the amine of the piperazine as well as to the amine of the melamine And the NH bond formed by the interfacial polymerization of piperazine / trimethoyl chloride was reduced in the reaction.
Experimental Example 2: Structural features of nano-separator 2
FE-SEM analysis was performed to confirm the surface changes before and after the 15 wt% sulfuric acid exposure of the nanocomposite membrane. FIG. 2 is an FE-SEM image of the nanoparticles of Comparative Example 1 before and after exposure to sulfuric acid, and FIG. 3 is a graph showing FE-SEM images of the nanoparticles before and after sulfuric acid exposure in Examples and Comparative Examples 2 and 3 Image.
2, the active layer formed by the interfacial polymerization before the sulfuric acid covers the polysulfone support (Fig. 2 (a)), whereas the nanoparticle applied for 15 days on 15 wt% sulfuric acid has a polyamide active layer It can be confirmed that polysulfone pores are clearly exposed by etching with sulfuric acid (Fig. 2 (b)).
On the other hand, referring to FIG. 3, when a melamine is added, a melamine layer having a nodular structure is formed on the surface of the separation membrane. Even if the separation membrane is applied to sulfuric acid for 10 days or longer, the melamine layer remains unetched, It is understood that the acid resistance is improved. Particularly, in the case of the nano-separator having a relatively large content of melamine, the melamine is uniformly applied on the surface of the separator, and the acid-resistance-improving effect is expected to be the most excellent.
This phenomenon can also be understood to be due to the fact that the etching of the active layer is inhibited as the melamine layer of the projecting structure covers the polyamide active layer to thicken the separating film.
Experimental Example 3: Performance of nano separator
4 is a schematic diagram of a performance evaluation apparatus for a nano separator. The nanocomposite membranes according to the Examples and Comparative Examples were mounted on a flat-plate cell to evaluate the permeation performance by a cross-flow method. Other evaluation conditions are shown in Table 3 below.
MgSO 4 solution (2,000 ppm)
The water flux (GFD) of the nanofiber separator was calculated by using the following equation (3) after measuring the weight of the permeate in a beaker. The ion rejection (%) was measured using a conductivity meter The electric conductivity of the water was measured and then calculated using the following equation (4).
&Quot; (3) "
&Quot; (4) "
The initial performance evaluation of the nanocomposite membranes according to the Examples and Comparative Examples was carried out. The results are shown in Table 4 below.
Referring to Table 4, the initial water permeability and removal rate of the nanoparticles of Example 1 and Comparative Examples 2 and 3 to which melamine was added were similar.
However, in order to evaluate the acid resistance of the nano-separator, the water permeability and the removal rate were measured by application of a nano-separator in a 15 wt% sulfuric acid solution. The results are shown in FIGS. 5 and 6.
Referring to FIG. 5, the water permeability and removal ratio of Examples, Comparative Examples 2 and 3 were measured to be higher than those of Comparative Example 1, and the acid resistance was relatively improved when melamine was added. Particularly, the nanoparticle membrane of the example in which 0.3% by weight of melamine was added had a divalent ion removal rate and water permeability of 96% and 17GFD or more, respectively, even after 10 days, and was superior to those of Comparative Examples 2 and 3 in acid resistance.
Referring to FIG. 6, the nanoparticle membrane of the Example had a lower unidimoride ion removal rate than that of Comparative Example 1 before 6 days, whereas the unidirectional ion removal rate of Comparative Example 1 then decreased sharply, After 7 days, the unidirectional ion removal rate of the Example was higher. In addition, the water permeability of the example was measured to be higher than that of Comparative Example 1 during the entire period, and it was analyzed that the acid resistance of Example 1 was relatively excellent.
In addition, the nanofiber separator according to the embodiment exhibits excellent permeation performance even under a low pressure of about 75 psi (about 5 bar), which is expected to be usefully applied to a system design for improving the recovery rate of crude oil and rare metals .
It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.
The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.
Claims (12)
And a piperazine-based polyamide active layer formed on the porous support and having a structure crosslinked by a triazine-based compound,
Wherein the piperazine-based polyamide active layer satisfies the following equations (1) and (2): < EMI ID =
&Quot; (1) "
&Quot; (2) "
In this formula,
N and O are the weight percentages of nitrogen and oxygen with respect to the total weight of the piperazine-based polyamide active layer,
m and n are fractions of a cross-linked portion and a linear portion in the above-mentioned piperazine-based polyamide active layer, respectively, and 0.45? m?
The porous support may be a member selected from the group consisting of polysulfone, polyether sulfone, polyimide, polyamide, polyetherimide, polyacrylonitrile, poly (methyl methacrylate), polyethylene, polypropylene, Wherein the polyamide-based nanofibers are formed by casting one or more selected polymers.
Wherein the triazine-based compound is one selected from the group consisting of 1,2,3-triazine, 1,2,4-triazine, and 1,3,5-triazine.
Wherein the triazine-based compound is 1,3,5-triazine.
Wherein the 1,3,5-triazine is melamine.
Wherein the nanofiber separator has a water permeability of 15 GFD or more.
(b) applying a porous support to the aqueous amine solution; And
(c) applying the porous support to an organic solution containing an amine-reactive compound to form a piperazine-based polyamide active layer having a structure crosslinked by the triazine-based compound on the porous support,
Wherein the piperazine-based polyamide active layer satisfies the following equations (1) and (2): < EMI ID =
&Quot; (1) "
&Quot; (2) "
In this formula,
N and O are the weight percentages of nitrogen and oxygen, respectively, relative to the total weight of the piperazine-based polyamide active layer,
m and n are fractions of a cross-linked portion and a linear portion in the above-mentioned piperazine-based polyamide active layer, respectively, and 0.45? m?
Wherein the content of the piperazine in the amine aqueous solution is 0.5 to 10% by weight.
Wherein the content of the triazine compound in the amine aqueous solution is 0.3 to 5.0% by weight.
Wherein the amine-reactive compound is selected from the group consisting of trimesoyl chloride (TMC), isophthaloyl chloride (IPC), terephthaloyl chloride (TPC), and mixtures of two or more thereof. ≪ / RTI >
Wherein the content of the amine-reactive compound in the organic solution is 0.01 to 0.5 wt%.
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| WO2019212707A1 (en) * | 2018-04-30 | 2019-11-07 | Entegris, Inc. | Polyamide coated filter membrane, filters, and methods |
| KR20200127265A (en) * | 2018-04-30 | 2020-11-10 | 엔테그리스, 아이엔씨. | Polyamide coated filter membrane, filter, and method |
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| TWI775337B (en) * | 2018-04-30 | 2022-08-21 | 美商恩特葛瑞斯股份有限公司 | Polyamide coated filter membrane, filters, and methods |
| KR102511437B1 (en) * | 2018-04-30 | 2023-03-17 | 엔테그리스, 아이엔씨. | Polyamide coated filter membranes, filters, and methods |
| CN111298663A (en) * | 2020-02-21 | 2020-06-19 | 郑州大学 | Photocatalytic self-cleaning loose nanofiltration membrane as well as preparation method and application thereof |
| CN112755806A (en) * | 2020-12-29 | 2021-05-07 | 湖南沁森高科新材料有限公司 | Chlorine-resistant reverse osmosis membrane and preparation method thereof |
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