Nanofiltration composite membranes

Abstract

Provided is a nanofiltration composite membrane, comprising: a supporting layer comprising a polyethylene terephthalate, a polymeric porous layer formed on the supporting layer, the polymeric porous layer comprising a polysulfone and an amphiphilic polymer represented by the formula below: ##STR00001##
and an interfacial polymerization layer formed on the polymeric porous layer and the interfacial polymerization layer comprising polyamide which is synthesized by polymerizing piperazine with 1,3,5-benzenetricarbonyl trichloride; wherein, n1, n2, n3, x, and y are integers greater than 0, the molecular weight of the amphiphilic polymer ranges from 90,000 to 200,000, and a weight ratio of the polysulfone to the amphiphilic polymer ranges from 2 to 20. The nanofiltration composite membrane can increase the removal rate of divalent ions and separate substances of specific molecular weights in solutions.

Claims

1. A nanofiltration composite membrane, comprising: a supporting layer comprising a polyester; a polymeric porous layer formed on the supporting layer, the polymeric porous layer comprising a polysulfone and an amphiphilic polymer represented by the formula below: ##STR00005## and an interfacial polymerization layer formed on the polymeric porous layer and comprising polyamide; wherein n1, n2, n3, x, and y are integers greater than 0, the molecular weight of the amphiphilic polymer ranges from 90,000 to 200,000, and a weight ratio of the polysulfone to the amphiphilic polymer is greater than or equal to 2 and less than or equal to 20.

2. The nanofiltration composite membrane of claim 1, wherein the weight ratio of the polysulfone to the amphiphilic polymer in the polymeric porous layer is greater than or equal to 2 and less than or equal to 10.

3. The nanofiltration composite membrane of claim 1, wherein the thickness of the supporting layer ranges from 0.09 millimeters (mm) to 0.1 mm, the thickness of the polymeric porous layer ranges from 0.02 mm to 0.06 mm, and the thickness of the interfacial polymerization layer ranges from 50 nanometers (nm) to 200 nm.

4. The nanofiltration composite membrane of claim 1, wherein the polyester is polyethylene terephthalate.

5. The nanofiltration composite membrane of claim 1, wherein the polyimide is synthesized by polymerizing piperazine with 1,3,5-benzenetricarbonyl trichloride.

6. The nanofiltration composite membrane of claim 1, wherein a removal rate of divalent ions of the nanofiltration composite membrane is greater than or equal to 96%.

7. The nanofiltration composite membrane of claim 2, wherein a removal rate of divalent ions of the nanofiltration composite membrane is greater than or equal to 96%.

8. The nanofiltration composite membrane of claim 3, wherein a removal rate of divalent ions of the nanofiltration composite membrane is greater than or equal to 96%.

9. The nanofiltration composite membrane of claim 4, wherein a removal rate of divalent ions of the nanofiltration composite membrane is greater than or equal to 96%.

10. The nanofiltration composite membrane of claim 5, wherein a removal rate of divalent ions of the nanofiltration composite membrane is greater than or equal to 96%.

11. The nanofiltration composite membrane of claim 1, wherein a molecular weight cutoff of the nanofiltration composite membrane ranges from 200 Dalton (Da) to 400 Da.

12. The nanofiltration composite membrane of claim 2, wherein a molecular weight cutoff of the nanofiltration composite membrane ranges from 200 Da to 400 Da.

13. The nanofiltration composite membrane of claim 3, wherein a molecular weight cutoff of the nanofiltration composite membrane ranges from 200 Da to 400 Da.

14. The nanofiltration composite membrane of claim 4, wherein a molecular weight cutoff of the nanofiltration composite membrane ranges from 200 Da to 400 Da.

15. The nanofiltration composite membrane of claim 5, wherein a molecular weight cutoff of the nanofiltration composite membrane ranges from 200 Da to 400 Da.

16. The nanofiltration composite membrane of claim 1, wherein the nanofiltration composite membrane has a permeate flux of divalent ion solution ranging from 40 L/m.sup.2/hr to 95 L/m.sup.2/hr.

17. The nanofiltration composite membrane of claim 2, wherein the nanofiltration composite membrane has a permeate flux of divalent ion solution ranging from 40 L/m.sup.2/hr to 95 L/m.sup.2/hr.

18. The nanofiltration composite membrane of claim 3, wherein the nanofiltration composite membrane has a permeate flux of divalent ion solution ranging from 40 L/m.sup.2/hr to 95 L/m.sup.2/hr.

19. The nanofiltration composite membrane of claim 4, wherein the nanofiltration composite membrane has a permeate flux of divalent ion solution ranging from 40 L/m.sup.2/hr to 95 L/m.sup.2/hr.

20. The nanofiltration composite membrane of claim 5, wherein the nanofiltration composite membrane has a permeate flux of divalent ion solution ranging from 40 L/m.sup.2/hr to 95 L/m.sup.2/hr.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) Sole FIGURE is a sectional view of the nanofiltration composite membrane of the instant disclosure.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(2) Hereinafter, one skilled in the art can easily realize the advantages and effects of the instant disclosure from the following examples. Therefore, it should be understood that the descriptions proposed herein are just preferable examples for the purpose of illustrations only, not intended to limit the scope of the disclosure. Various modifications and variations could be made in order to practice or apply the instant disclosure without departing from the spirit and scope of the disclosure.

(3) Please refer to the sole FIGURE. The nanofiltration composite membrane 1 was made of polymer. The nanofiltration composite membrane 1 comprised a supporting layer 11, a polymeric porous layer 12 formed on the supporting layer 11, and an interfacial polymerization layer 13 formed on the polymeric porous layer 12.

Ultrafiltration Membrane

Examples 1 to 4

(4) Polysulfone, amphiphilic polymer, lithium chloride, and N-methyl-2-pyrrolidone in Examples 1 to 4 were weighed according to Table 1 below and were stirred smoothly. After that, the mixture was agitated under a speed of 300 revolutions per minute (rpm) and at a temperature over 80° C. for 6 hours, and then degassed under vacuum for 3 hours to render a homogeneous pale yellow coating solution without bubbles. The structural formula of aforesaid polymer is showed below.

(5) ##STR00004##

(6) Nonwoven polyester fabric (as a supporting layer) was coated with a coating solution of 25° C. to 26° C. by using a slot-die head with adjustable thickness. The thickness was set as 0.2 mm and the width was set as 1040 mm. Wherein, the thickness of the nonwoven polyester fabric was 0.12 mm, the width of the nonwoven polyester fabric was 1070 mm, and the coating speed was around 3 meters per minute (m/min).

(7) Then the freshly coated nonwoven polyester fabric was immersed in the cosolvent comprising water and organic solvent (N-methyl-2-pyrrolidone) at a ratio of 2:1 to undergo phase inversion, and thus a membrane was formed. At last, the membrane was washed in a pure water tank, and the polymeric porous layer was formed on the nonwoven polyester fabric. The obtained bilayer structure was called ultrafiltration membrane. The ultrafiltration membrane comprised nonwoven polyester fabric and polymeric porous layer formed on the nonwoven polyester fabric.

Comparative Example 1

(8) The production procedure of Comparative Example 1 was almost the same as the production procedure of Examples 1 to 4 except that the amphiphilic polymer was not used or contained in the ultrafiltration membrane of Comparative Example 1.

Analysis 1: Permeate Flux of Pure Water Through Ultrafiltration Membrane

(9) The ultrafiltration membranes of Examples 1 to 4 (E1 to E4) and Comparative Example 1 (C1) were tested under the condition of 25° C. and the pressure of 2 kilograms per square centimeter (kg/cm.sup.2) to measure the amounts of pure water passing through the ultrafiltration membranes. The unit of permeate flux is LMH. Results were recorded in Table 1.

Analysis 2: Molecular Weight Cutoff of Ultrafiltration Membrane

(10) 1 wt % polyethylene glycol solution was filtered by ultrafiltration membranes of E1 to E4 and C1 respectively. The polyethylene glycol solution filtered by each of the ultrafiltration membranes was collected and tested by liquid chromatograph mass spectrometer to analyze the molecular weight distribution of polyethylene glycol. The results of molecular weight cutoff (MWCO) were showed in Table 1. The unit of molecular weight is Da. Table 1: Weight percentages of starting materials for preparation of the ultrafiltration membranes of E1 to E4 and C1 and test results of the properties of the ultrafiltration membranes of E1 to E4 and C1

(11) TABLE-US-00001 Ultrafiltration membrane E1 E2 E3 E4 C1 Polysulfone 20 20 20 20 20 (wt %) Amphiphilic 8.5 5 2.2 1.1 0 polymer (wt %) Lithium 1.2 1.2 1.2 1.2 1.2 chloride (wt %) N-methyl-2- 70.3 73.8 76.6 77.7 78.8 pyrrolidone (wt %) Weight ratio 2.4 4 9.1 18.2 — of the poly- sulfone to the amphiphilic polymer Permeate flux 137 177 261 312 426 of pure water (LMH) Molecular 6K-10K 20K-23K 30K-32K 50K-52K 70K-80K weight cutoff (Da)

Nanofiltration Composite Membrane

Examples 1A to 4A

(12) Interfacial polymerization layers were formed on each polymeric porous layer of E1 to E4 by surface condensation. The obtained three-layer structure was called nanofiltration composite membrane. In other words, the nanofiltration composite membrane comprised a supporting layer, a polymeric porous layer, and an interfacial polymerization layer. The procedures of formation of the interfacial polymerization layer on the polymeric porous layer were described below.

(13) The solutions with pH values ranging from 8 to 9 comprising piperazine and 3,5-diaminobenzoic acid were prepared according to Table 2 to render interfacial polymerization layers of Examples 1A to 4A (E1A to E4A). Specifically, piperazine and 3,5-diaminobenzoic acid were weighed according to Table 2 and dissolved in water to obtain the solutions with pH values ranging from 8 to 9. Consequently, the ultrafiltration membranes of E1 to E4 were immersed in aforesaid solutions for 2 minutes respectively. Afterwards, the residual water phase liquid on the surface of the ultrafiltration membranes was removed. The ultrafiltration membranes with water phase were contacted to an organic solution comprising 1,3,5-benzenetricarbonyl trichloride and n-hexane for 45 seconds to 50 seconds. The ultrafiltration membranes were washed by water for 2 minutes after the reaction ended. The nanofiltration composite membranes of E1A to E4A were formed subsequently.

Comparative Example 1A

(14) The production procedures of a nanofiltration composite layer of Comparative Example 1A (C1A) were the same as the production procedures of the nanofiltration composite layers of E1A to E4A.

Analysis 3: Permeate Flux Through Nanofiltration Composite Membrane and Removal Rate of Divalent Ions of Nanofiltration Composite Membrane

(15) The nanofiltration composite membranes of E1A to E4A and C1A were tested under pressure of 100 pounds per square inch (psi) and 2000 parts per million (ppm) magnesium sulfate solutions (MgSO.sub.4(aq)) were filtered by aforesaid nanofiltration composite membranes respectively to render the removal rates of divalent ions and permeate fluxes at 25° C. Herein, the removal rates of divalent ions were calculated by measuring each conductivity (conductivity.sub.(before)) of the magnesium sulfate solutions before filtration and each conductivity (conductivity.sub.(after)) of the magnesium sulfate solutions after filtered with the nanofiltration composite membranes. According to the formula of [(conductivity.sub.(before)−conductivity.sub.(after))/conductivity.sub.(before)×100%], the results were showed in Table 2 The unit of permeate flux is LMH.

Analysis 4: Removal Rate of Univalent Ions of Nanofiltration Composite Membrane

(16) The nanofiltration composite membranes of E1A to E4A and C1A were tested under pressure of 100 psi and 2000 ppm sodium chloride solutions (NaCl.sub.(aq)) were filtered by aforesaid nanofiltration composite membranes respectively to render the removal rates of univalent ions. Herein, the removal rates of univalent ions were calculated by measuring each conductivity (conductivity.sub.(before)) of the sodium chloride solutions before filtration and each conductivity conductivity.sub.(after)) of the sodium chloride solutions after filtered with the nanofiltration composite membranes. According to the formula of [(conductivity.sub.(before)−conductivity.sub.(after))/conductivity.sub.(before)×100%], the results were showed in Table 2.

Analysis 5: Molecular Weight Cutoff of Nanofiltration Composite Membrane

(17) 1 wt % polyethylene glycol solution was filtered by the nanofiltration composite membranes of E1A to E4A and C1A respectively. The polyethylene glycol solution filtered by each of the nanofiltration composite membranes was collected and tested by liquid chromatograph mass spectrometer to analyze the molecular weight distribution of polyethylene glycol. The results of molecular weight cutoff were showed in Table 2. The unit of molecular weight is Da. Table 2: Weight percentages of starting materials for preparation of the nanofiltration composite membranes of E1A to E4A and C1A and test results of the properties of the nanofiltration composite membranes of E1A to E4A and C1A

(18) TABLE-US-00002 Ultrafiltration membrane E1 E2 E3 E4 C1 Weight ratio 2.4 4 9.1 18.2 — of the poly- sulfone to the amphiphilic polymer Nanofiltration composite membrane E1A E2A E3A E4A C1A Piperazine 2 2 2 2 2 (wt %) 3,5-Diamino- 0.05 0.05 0.05 0.05 0.05 benzoic acid (wt %) 1,3,5-benzene- 0.2 0.2 0.2 0.15 0.1 tricarbonyl trichloride (wt %) Water (wt %) 97.75 97.75 97.75 97.80 97.85 Permeate flux of magnesium sulfate 46 65 74 94 97 solution (LMH) Removal rate 99.67 99.42 99.41 96.32 94.65 of divalent ions (%) Removal rate 37.26 35.72 32.65 29.32 — of univalent ions (%) Molecular 200-240 200-240 200-240 300-400 420-500 weight cutoff (Da)

Results and Discussion

(19) According to Table 2. due to the weight ratio of the polysulfone to the amphiphilic polymer in the polymeric porous layer of the nanofiltration composite membrane ranging from 2 to 20, the removal rates of divalent ions of the nanofiltration composite membranes of E1A to E4A of the instant disclosure were all greater than 96%. Therefore, aforesaid nanofiltration composite membranes could remove high concentration of divalent ions from hard water, and thus were suitable for applying to water softening.

(20) Regarding Table 1 and Table 2, as the amounts of the amphiphilic polymer in the polymeric porous layer increased, the removal rates of divalent ions of the nanofiltration composite membranes of E1A to E4A could be increased to be greater than 96%. The removal rates of divalent ions of the nanofiltration composite membranes of E1A to E3A were greater than 99%. Furthermore, the removal rate of divalent ions of the nanofiltration composite membranes of E1A was greater than 99.5%. In the contrast, in the absence of the amphiphilic polymer of the instant disclosure, the removal rate of divalent ions of the polymeric porous layer of C1A was less than 95%. According to the results above, the nanofiltration composite membrane of the instant disclosure has better efficiency of water softening.

(21) Regarding the nanofiltration composite membranes of E1A to E4A, the permeate flux of the magnesium sulfate solution ranged from 40 LMH to 95 LMH. These results all fell within the acceptable ranges. If only 96% of the removal rate of divalent ions is needed, the nanofiltration composite membrane of E4A can be used. The permeate flux of E4A could reach 94 LMH, which could accelerate the separation of divalent ions in water.

(22) Besides, regarding Table 2, the pores of nanofiltration composite membranes of E1A to E4A could retain substances with molecular weights ranging from 200 Da to 240 Da or from 300 Da to 400 Da. They could apply to separation of substances with molecular weights ranging from 200 Da to 240 Da or from 300 Da to 400 Da.

(23) In conclusion, the nanofiltration composite membrane of the instant disclosure can increase the removal rate of divalent ions and have appropriate permeate flux of divalent ion solution and removal rate of univalent ions. Moreover, the nanofiltration composite membrane of the instant disclosure can separate substances of specific molecular weights in solutions.

(24) Even though numerous characteristics and advantages of the instant disclosure have been set forth in the foregoing description, together with details of the structure and features of the invention, the disclosure is illustrative only. Changes may be made in the details, especially in matters of shape, size, and arrangement of parts within the principles of the invention to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed.