Acid-resistant nano-separation membrane having enhanced flow rate, and method for manufacturing same
The present invention relates to an acid-resistant nanomembrane with an improved flow rate and a method of producing the acid-resistant nanomembrane, and more particularly, to an acid-resistant nanomembrane with an improved flow rate, which can also be used under strong-acid and high-temperature conditions for the recovery of rare metals, valuable metals, and the like generated in a smelting process and which exhibits both excellent flow rate and excellent acid resistance, and a method of producing the acid-resistant nanomembrane.
1. A method of producing an acid-resistant nanomembrane with an improved flow rate, the method comprising:
immersing a porous support in a first solution, wherein the first solution contains a first amine-based compound represented by Chemical Formula 1, a second amine-based compound, and a phenol-based compound;
forming a polyamide layer on the surface of the immersed porous support by treating the porous support with a second solution containing an acid halide compound; and
subjecting the porous support, on which the polyamide layer has been formed, to hydrophilization:
wherein R 1 and R 2 are each independently a C 1 -C 10 alkylene group, and n is an integer of 1 to 100,
the first solution comprises the first amine-based compound and the second amine-based compound in a weight ratio of 1:0.04 to 1:2, and the first amine-based compound and the phenol-based compound in a weight ratio of 1:0.02 to 1:1,
the second amine-based compound includes one or more selected from the group consisting of m-phenylenediamine, and piperazine,
the phenol-based compound includes one or more selected from the group consisting of pyrocatechol, resorcinol, hydroquinone, pyrogallol, and phloroglucinol,
the acid-resistant nanomembrane has a flow rate of 25 GFD or more, and a salt removal rate of 90% or more at 25° C. and 75 psi, and
the acid-resistant nanomembrane has a flow rate of 30 GFD, or more and a salt removal rate of 85% or more at 25° C. and 75 psi when immersed in a 15 wt. % aqueous sulfuric acid solution for 30 days.
2. The method of claim 1 , wherein, in Chemical Formula 1, R 1 and R 2 are each independently a C 2 -C 6 linear alkylene group or a C 2 -C 6 branched alkylene group, and n is an integer of 1 to 10.
3. The method of claim 1 , wherein the first solution includes a hydrophilic polymer in an amount of 0.4 part by weight to 40 parts by weight based on 100 parts by weight of the first amine-based compound, wherein the hydrophilic polymer includes one or more selected from the group consisting of polyvinylpyrrolidone, polyethylene glycol, and polyvinyl alcohol.
4. The method of claim 1 , wherein the acid halide compound includes one or more selected from among isophthaloyl chloride, trimesoyl chloride, and terephthaloyl chloride.
5. The method of claim 1 , wherein the hydrophilization is carried out using a hydrophilization solution comprising an acid, base, salt or a combination thereof at a total concentration of 0.01 wt. % to 2 wt. %.
6. The method of claim 5 , wherein the acid, base, or salt is one or more selected from the group consisting of potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium hydroxide, sulfuric acid, sodium sulfate, sodium sulfite, and sodium bicarbonate.
7. The method of claim 1 , wherein the hydrophilization is carried out at 10° C. to 90° C. for 0.1 minute to 5 minutes.
8. The method of claim 1 , wherein the porous support includes a nonwoven fabric and a porous polymer layer, wherein the porous polymer layer has an average thickness of 10 μm to 200 μm and is formed to include one or more selected from the group consisting of polysulfone, polyethersulfone, polyimide, polypropylene, and polyvinylidene fluoride.
9. An acid-resistant nanomembrane with an improved flow rate, the acid-resistant nanomembrane comprising:
a porous support; and
a polyamide layer, which is provided on the surface of the porous support and formed by the interfacial polymerization between a first solution containing a first amine-based compound, a second amine-based compound, and a phenol-based compound and a second solution containing an acid halide compound, wherein the first amine-based compound includes a compound represented by Chemical Formula 1:
wherein R 1 and R 2 are each independently a C 1 -C 10 alkylene group, and n is an integer of 1 to 100,
wherein the polyamide layer has a hydrophilically modified surface
the first solution comprises the first amine-based compound and the second amine-based compound in a weight ratio of 1:0.04 to 1:2, and the first amine-based compound and the phenol-based compound in a weight ratio of 1:0.02 to 1:1,
the second amine-based compound includes one or more selected from the group consisting of m-phenylenediamine and piperazine,
the phenol-based compound includes one or more selected from the group consisting of pyrocatechol, resorcinol, hydroquinone, pyrogallol, and phloroglucinol,
the acid-resistant nanomembrane has a flow rate of 25 GFD or more, and a salt removal rate of 90% or more at 25° C. and 75 psi, and
the acid-resistant nanomembrane has a flow rate of 30 GFD, or more and a salt removal rate of 85% or more at 25° C. and 75 psi when immersed in a 15 wt. % aqueous sulfuric acid solution for 30 days.
10. The acid-resistant nanomembrane of claim 9 , wherein the polyamide layer has an average thickness of 0.05 μm to 1 μm, and the porous support includes a nonwoven fabric having an average thickness of 30 μm to 300 μm and a porous polymer layer having an average thickness of 10 μm to 200 μm,
wherein the porous polymer layer is formed to include one or more selected from the group consisting of polysulfone, polyethersulfone, polyimide, polypropylene, and polyvinylidene fluoride.
11. A membrane module, comprising the acid-resistant nanomembrane of claim 9 .