WATER SEPARATION COMPOSITE MEMBRANE
20170113191 ยท 2017-04-27
Assignee
Inventors
- Yu-Lun LAI (Tainan City, TW)
- Chih-Chang CHANG (Taichung City, TW)
- Shao-I Yen (Zhudong Township, TW)
- Jung-Nan HSU (Taichung City, TW)
- Chun-Nan KUO (Taichung City, TW)
Cpc classification
B01D67/00046
PERFORMING OPERATIONS; TRANSPORTING
B01D2259/4508
PERFORMING OPERATIONS; TRANSPORTING
B01D67/0009
PERFORMING OPERATIONS; TRANSPORTING
B01D71/0211
PERFORMING OPERATIONS; TRANSPORTING
B01D2325/20
PERFORMING OPERATIONS; TRANSPORTING
B01D71/56
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01D69/12
PERFORMING OPERATIONS; TRANSPORTING
B01D71/56
PERFORMING OPERATIONS; TRANSPORTING
B01D69/10
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A water separation composite membrane is provided. The water separation composite membrane includes a carrier with a plurality of pores, wherein the carrier is made of a polymer having a repeat unit of
##STR00001##
and a selective layer disposed on the porous carrier, wherein the selective layer consists of a plurality of graphene oxide layers.
Claims
1. A water separation composite membrane, comprising: a carrier with a plurality of pores, wherein the carrier is made of a polymer having a repeat unit of ##STR00018## and a selective layer disposed on the porous carrier, wherein the selective layer consists of a plurality of graphene oxide layers.
2. The water separation composite membrane as claimed in claim 1, wherein the pores of the carrier have a diameter between 100 nm and 300 nm.
3. The water separation composite membrane as claimed in claim 1, wherein the polymer is polyamide or polycarbonate.
4. The water separation composite membrane as claimed in claim 1, wherein the selective layer has a thickness between 200 nm and 3000 nm.
5. The water separation composite membrane as claimed in claim 1, wherein the selective layer has a thickness between 400 nm and 2000 nm.
6. The water separation composite membrane as claimed in claim 1, wherein the water separation composite membrane has a water vapor permeance rate between 110.sup.6 mol/m.sup.2sPa and 110.sup.5mol/m.sup.2sPa.
7. The water separation composite membrane as claimed in claim 1, wherein the dehumidifying composite membrane has a water/air separation factor between 200 and 3000.
8. A water separation composite membrane, comprising: a carrier with a plurality of pores; and a selective layer disposed on the porous carrier, wherein the selective layer consists of a plurality of graphene oxide layers and an organic compound distributed between any two adjacent graphene oxide layers, wherein the organic compound has a structure represented by Formula (I) or Formula (II) ##STR00019## wherein X is independent OH, NH.sub.2, SH, ##STR00020## R.sup.1 and R.sup.2 are independent hydrogen, C.sub.1-12 alkyl; A is ##STR00021## and, n is 2-3 when X is OH, NH.sub.2, or SH, and n is 0-1 when X is ##STR00022##
9. The water separation composite membrane as claimed in claim 8, wherein the carrier has a plurality of pores, and the carrier is made of a polymer having a repeat unit of ##STR00023##
10. The water separation composite membrane as claimed in claim 9, wherein the pores of the carrier have a diameter between 100 nm and 300 nm.
11. The water separation composite membrane as claimed in claim 8, wherein the polymer is polycarbonate or polyamide.
12. The water separation composite membrane as claimed in claim 8, wherein the selective layer has a thickness between 200 nm and 4000 nm.
13. The water separation composite membrane as claimed in claim 8, wherein the selective layer has a thickness between 800 nm and 3000 nm.
14. The water separation composite membrane as claimed in claim 8, wherein the organic compound is ##STR00024##
15. The water separation composite membrane as claimed in claim 8, wherein the organic compound further reacts with the graphene oxide layer.
16. The water separation composite membrane as claimed in claim 8, wherein there is covalent bond, hydrogen bond, or ionic bond between the organic compound and the graphene oxide layer.
17. The water separation composite membrane as claimed in claim 8, wherein there is an interval between any two adjacent graphene oxide layers, and a swelling degree of the interval is between 0.1% and 20.0%.
18. The water separation composite membrane as claimed in claim 8, wherein the weight ratio of the organic compound to the graphene oxide layer is from 0.1 to 80.
19. The water separation composite membrane as claimed in claim 8, wherein the water separation composite membrane has a water vapor transmission rate between 510.sup.6 mol/m.sup.2sPa and 510.sup.5 mol/m.sup.2sPa.
20. The water separation composite membrane as claimed in claim 8, wherein the water separation composite membrane has a water/air separation factor between 1000 and 110.sup.7.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The disclosure can be more fully understood by reading the subsequent detailed description and examples with references made to the accompanying drawings, wherein:
[0012]
[0013]
[0014]
[0015]
[0016]
[0017]
DETAILED DESCRIPTION
[0018] This description is made for the purpose of illustrating the general principles of the disclosure and should not be taken in a limiting sense. The scope of the disclosure is determined by reference to the appended claims.
[0019] The disclosure provides a water separation composite membrane, which can serve as a water vapor/air separation component of a membrane dehumidification device. The water separation composite membrane of the disclosure includes a selective layer and a carrier, wherein the adhesion between the selective layer and the carrier is improved due to the chemical bonds (such as covalent bonds or hydrogen bonds) formed therebetween. Further, due to the multi-layer structure, thickness, and characteristic of the selective layer, the water separation composite membrane of the disclosure exhibits high water vapor permeance and high water/air separation factor when removing moisture from air. According to another embodiments of the disclosure, the selective layer further includes an organic compound distributed between any two adjacent graphene oxide layers, and the organic compound is bonded to the graphene oxide layer by means of chemical bonds to form a bridge between any two adjacent graphene oxide layers and to force any two adjacent graphene oxide layers separated from each other by an interval. Since the organic compound bridges between any two adjacent graphene oxide layers can control the distance between any two adjacent graphene oxide to form a passageway through which water molecules pass, resulting in improving the water vapor permeance and water/air separation factor of the water separation composite membrane. On the other hand, the moisture removed by the water separation composite membrane can be removed by applying a water vapor pressure difference across the water separation composite membrane. Therefore, the water separation composite membrane of the disclosure can be reusable.
[0020] According to embodiments of the disclosure, as shown in
##STR00007##
or made of a polymer having a repeat unit having a moiety of
##STR00008##
For example, the polymer having a repeat unit of
##STR00009##
or a repeat unit having a moiety of
##STR00010##
can be polyamide or polycarbonate. The pores of the carrier can have a diameter between 100 nm and 300 nm, in order to promote the moisture freely passing through. Further, the selective layer can have a thickness between 200 nm and 3000 nm, such as 400 nm and 2000 nm, in order to ensure that the water separation composite membrane employing the selective layer can have a water vapor permeance between 110.sup.6 mol/m.sup.2sPa and 110.sup.5 mol/m.sup.2sPa and a water/air separation factor between 200 and 3000 (measured at 20-35 C. and 60-80% RH). The selective layer can have a larger thickness when the specific graphene oxide deposition (g/cm.sup.2) is increased.
[0021] According to embodiments of the disclosure, as shown in
##STR00011##
[0022] wherein, X is independent OH, NH.sub.2, SH,
##STR00012##
R.sup.1 and R.sup.2 are independent hydrogen, C.sub.1-12 alkyl; A is
##STR00013##
and, n is 0-3. The organic compound can be bonded to the graphene oxide layer by means of hydrogen bonds or ionic bonds, or further react with the graphene oxide layer via nucleophilic substitution reaction or condensation to form covalent bonds therebetween, resulting in that the organic compound or the moiety derived from the organic compound serves as bridge between any two adjacent graphene oxide layers. Namely, please referring to
[0023] According to embodiments of the disclosure, regarding to the organic compound having the structure represented by Formula (I), n can be from 0 to 1, when X is
##STR00014##
For example, the organic compound having the structure represented by Formula (I) can be
##STR00015##
Further, n can be from 2 to 3, when X is OH, NH.sub.2, or SH. For example, the organic compound having the structure represented by Formula (I) can be
##STR00016##
Further, the organic compound having the structure represented by Formula (II) can be
##STR00017##
[0024] The carrier can have a plurality of pores, and the carrier can be polyamide, polycarbonate, polyvinylidene difluoride (PVDF), polyether sulfone (PES), polytetrafluoroethene (PTFE), or cellulose acetate (CA). The pores of the carrier can have a diameter between 100 nm and 300 nm, in order to promote the moisture freely passing through. Further, the selective layer can have a thickness between 200 nm and 4000 nm, such as 400 nm and 3000 nm.
[0025] According to embodiments of the disclosure, the selective layer of the water separation composite membrane can be prepared by coating a composition on a substrate, or subjecting a composition to a suction deposition. The composition includes a graphene oxide powder and the organic compound, wherein the weight ratio of the organic compound to the graphene oxide powder can be from about 0.1 to 80, such as from 1 to 0.1, from 1 to 80, from 5 to 60, or from 5 to 40. Namely, in the selective layer, the weight ratio of the organic compound to the graphene oxide layer can be from about 0.1 to 80, such as from 1 to 0.1, from 1 to 80, from 5 to 60, or from 5 to 40.
[0026] Below, exemplary embodiments will be described in detail so as to be easily realized by a person having ordinary knowledge in the art. The disclosure concept may be embodied in various forms without being limited to the exemplary embodiments set forth herein. Descriptions of well-known parts are omitted for clarity.
EXAMPLE 1
Water Separation Composite Membrane (I)
[0027] 1 part by weight of graphene oxide powder (synthesized using modified Hummer's method) was mixed with DI water, obtaining a solution with a solid content of 0.05 wt %. Next, a selective layer with a thickness of about 400 nm was formed by subjecting the composition to a suction deposition. Next, the selective layer was disposed on a porous hydrophilic nylon carrier (having pores with an average diameter of 200 nm) and baked at 50 C. for 60 minutes, obtaining the water separation composite membrane (I).
EXAMPLE 2
Water Separation Composite Membrane (II)
[0028] Example 2 was performed in the same manner as Example 1 except that the thickness of the selective layer was increased from about 400 nm to 800 nm, obtaining the water separation composite membrane (II).
EXAMPLE 3
Water Separation Composite Membrane (III)
[0029] Example 3 was performed in the same manner as Example 1 except that the thickness of the selective layer was increased from about 400 nm to 2000 nm, obtaining the water separation composite membrane (III).
EXAMPLE 4
Dehumidification Performance Test
[0030] The water vapor permeance between and the water/air separation factor of the water separation composite membranes (I)-(III) of Examples 1-3 were evaluated by a dehumidification device 100, and the results are shown in Table 1. As shown in
TABLE-US-00001 TABLE 1 membrane (I) membrane (II) membrane (III) thickness of the ~400 nm ~800 nm ~2000 nm selective layer water vapor permeance 1 10.sup.5 8 10.sup.6 6 10.sup.6 (mol/m.sup.2sPa) water/air separation ~200 ~1000 ~1000 factor
[0031] As shown in Table 1, with the increase of the thickness of the selective layer, the water separation composite membrane exhibits an improved water/air separation factor.
EXAMPLE 5
Water Separation Composite Membrane (IV)
[0032] 1 part by weight of graphene oxide powder (synthesized using modified Hummer's method) was mixed with DI water, obtaining a first solution with a solid content of 0.05wt %. Next, 0.1 parts by weight of ethanedial was mixed with DI water, obtaining a second solution with a solid content of 1.0 wt %. Next, the first solution and the second solution were mixed and stood at 50 C. for 60 minutes, obtaining a third solution (the weight ratio of the graphene oxide powder to the ethanedial was 1:0.1). Next, a selective layer was formed by subjecting the third composition to a suction deposition. Next, the selective layer was disposed on a porous hydrophilic nylon carrier (having pores with an average diameter of 200 nm) and baked at 50 C. for 60 minutes, obtaining the water separation composite membrane (IV). The average interval width of the graphene oxide layers of the water separation composite membrane (IV) at dry membrane state was measured by using X-ray diffraction measurement. Next, average interval width of the graphene oxide layers of the water separation composite membrane (IV) was measured again by using X-ray diffraction measurement, after placing the water separation composite membrane (IV) in water for 60 minutes. The results are shown in Table 2.
EXAMPLE 6
Water Separation Composite Membrane (V)
[0033] Example 6 was performed in the same manner as Example 5 except that the weight of ethanedial was increased from 0.1 parts by weight to 5 parts by weight, resulting that the third composition has the weight ratio of the graphene oxide powder to the ethanedial of 1:5 and obtaining the water separation composite membrane (V) (with a thickness of 800 nm). The average interval width of the graphene oxide layers of the water separation composite membrane (V) at dry membrane state was measured by using X-ray diffraction measurement. Next, average interval width of the graphene oxide layers of the water separation composite membrane (V) was measured again by using X-ray diffraction measurement, after placing the water separation composite membrane (V) in water for 60 minutes. The results are shown in Table 2.
EXAMPLE 7
Water Separation Composite Membrane (VI)
[0034] Example 7 was performed in the same manner as Example 5 except that the weight of ethanedial was increased from 0.1 parts by weight to 10 parts by weight, resulting that the third composition has the weight ratio of the graphene oxide powder to the ethanedial of 1:10 and obtaining the water separation composite membrane (VI). The average interval width of the graphene oxide layers of the water separation composite membrane (VI) at dry membrane state was measured by using X-ray diffraction measurement. Next, average interval width of the graphene oxide layers of the water separation composite membrane (VI) was measured again by using X-ray diffraction measurement, after placing the water separation composite membrane (VI) in water for 60 minutes. The results are shown in Table 2.
EXAMPLE 8
Water Separation Composite Membrane (VII)
[0035] Example 8 was performed in the same manner as Example 5 except that the weight of ethanedial was increased from 0.1 parts by weight to 15 parts by weight, resulting that the third composition has the weight ratio of the graphene oxide powder to the ethanedial of 1:15 and obtaining the water separation composite membrane (VII). The average interval width of the graphene oxide layers of the water separation composite membrane (VII) at dry membrane state was measured by using X-ray diffraction measurement. Next, average interval width of the graphene oxide layers of the water separation composite membrane (VII) was measured again by using X-ray diffraction measurement, after placing the dehumidifying composite membrane (VII) in water for 60 minutes. The results are shown in Table 2.
EXAMPLE 9
Water Separation Composite Membrane (VIII)
[0036] Example 9 was performed in the same manner as Example 5 except that the weight of ethanedial was increased from 0.1 parts by weight to 20 parts by weight, resulting that the third composition has the weight ratio of the graphene oxide powder to the ethanedial of 1:20 and obtaining the water separation composite membrane (VIII). The average interval width of the graphene oxide layers of the water separation composite membrane (VIII) at dry membrane state was measured by using X-ray diffraction measurement. Next, average interval width of the graphene oxide layers of the water separation composite membrane (VIII) was measured again by using X-ray diffraction measurement, after placing the dehumidifying composite membrane (VIII) in water for 60 minutes. The results are shown in Table 2.
EXAMPLE 10
Water Separation Composite Membrane (IX)
[0037] Example 10 was performed in the same manner as Example 5 except that the weight of ethanedial was increased from 0.1 parts by weight to 80 parts by weight, resulting that the third composition has the weight ratio of the graphene oxide powder to the ethanedial of 1:80 and obtaining the water separation membrane (IX). The average interval width of the graphene oxide layers of the water separation composite membrane (IX) at dry membrane state was measured by using X-ray diffraction measurement. Next, average interval width of the graphene oxide layers of the water separation composite membrane (IX) was measured again by using X-ray diffraction measurement, after placing the water separation composite membrane (IX) in water for 60 minutes. The results are shown in Table 2.
TABLE-US-00002 TABLE 2 weight ratio of the interval interval swelling graphene oxide width width degree powder to the (nm)(dry (nm)(wet of the ethanedial membrane) membrane) interval water 1:0 0.86 1.15 33.7% separation composite membrane (I) water 1:0.1 0.92 1.02 10.8% separation composite membrane (IV) water 1:5 0.98 1.07 9.2% separation composite membrane (V) water 1:10 0.91 1.05 15.4% separation composite membrane (VI) water 1:15 0.93 1.05 12.9% separation composite membrane (VII) water 1:20 0.94 0.99 5.3% separation composite membrane (VIII) water 1:80 1.15 1.16 0.8% separation composite membrane (IX)
EXAMPLE 11
Water Separation Composite Membrane (X)
[0038] Example 11 was performed in the same manner as Example 5 except that the third composition was directly coated on the porous hydrophilic nylon carrier, obtaining the water separation composite membrane (X).
EXAMPLE 12
Water Separation Composite Membrane (XI)
[0039] 1 part by weight of graphene oxide powder was mixed with DI water, obtaining a first solution with a solid content of 0.5 wt %. Next, 5 parts by weight of 1,2-ethanediamine was mixed with DI water, obtaining a second solution with a solid content of 1.0 wt %. Next, the first solution and the second solution were mixed and stood at 50 C. for 60 minutes, obtaining a third solution (the weight ratio of the graphene oxide powder to the 1,2-ethanediamine was 1:5). Next, a selective layer was formed by subjecting the third composition to a suction deposition. Next, the selective layer was disposed on a porous hydrophilic nylon carrier (having pores with an average diameter of 200 nm) and baked at 50 C. for 60 minutes, obtaining the water separation composite membrane (XI).
EXAMPLE 13
Water Separation Composite Membrane (XII)
[0040] Example 13 was performed in the same manner as Example 12 except that the weight of 1,2-ethanediamine was increased from 5 parts by weight to 10 parts by weight, resulting that the third composition has the weight ratio of the graphene oxide powder to the 1,2-Ethanediamine of 1:10 and obtaining the water separation composite membrane (XII).
EXAMPLE 14
Water Separation Composite Membrane (XIII)
[0041] 1 part by weight of graphene oxide powder was mixed with DI water, obtaining a first solution with a solid content of 0.5 wt %. Next, 10 parts by weight of 1,3-propanediamine was mixed with DI water, obtaining a second solution with a solid content of 1.0 wt %. Next, the first solution and the second solution were mixed and stood at 50 C. for 60 minutes, obtaining a third solution (the weight ratio of the graphene oxide powder to the 1,3-propanediamine was 1:10). Next, a selective layer was formed by subjecting the third composition to a suction deposition. Next, the selective layer was disposed on a porous hydrophilic nylon carrier (having pores with an average diameter of 200 nm) and baked at 50 C. for 60 minutes, obtaining the water separation composite membrane (XIII) The average interval width of the graphene oxide layers of the water separation composite membrane (XIII) at dry membrane state was measured by using X-ray diffraction measurement. Next, average interval width of the graphene oxide layers of the water separation composite membrane (XIII) was measured again by using X-ray diffraction measurement, after placing the water separation membrane (XIII) in water for 60 minutes. The results are shown in Table 3.
EXAMPLE 15
Water Separation Composite Membrane (XIV)
[0042] Example 15 was performed in the same manner as Example 14 except that the weight of 1,3-propanediamine was increased from 10 parts by weight to 20 parts by weight, resulting that the third composition has the weight ratio of the graphene oxide powder to the 1,3-propanediamine of 1:20 and obtaining the water separation composite membrane (XIV).
EXAMPLE 16
Water Separation Composite Membrane (XV)
[0043] Example 16 was performed in the same manner as Example 14 except that the weight of 1,3-propanediamine was increased from 10 parts by weight to 40 parts by weight, resulting that the third composition has the weight ratio of the graphene oxide powder to the 1,3-propanediamine of 1:40 and obtaining the water separation composite membrane (XV). The average interval width of the graphene oxide layers of the water separation composite membrane (XV) at dry membrane state was measured by using X-ray diffraction measurement. Next, average interval width of the graphene oxide layers of the water separation composite membrane (XV) was measured again by using X-ray diffraction measurement, after placing the water separation composite membrane (XV) in water for 60 minutes. The results are shown in Table 3.
EXAMPLE 17
Water Separation Composite Membrane (XVI)
[0044] Example 17 was performed in the same manner as Example 14 except that the weight of 1,3-propanediamine was increased from 10 parts by weight to 80 parts by weight, resulting that the third composition has the weight ratio of the graphene oxide powder to the 1,3-propanediamine of 1:80 and obtaining the water separation composite membrane (XVI). The average interval width of the graphene oxide layers of the water separation composite membrane (XVI) at dry membrane state was measured by using X-ray diffraction measurement. Next, average interval width of the graphene oxide layers of the water separation composite membrane (XVI) was measured again by using X-ray diffraction measurement, after placing the water separation composite membrane (XVI) in water for 60 minutes. The results are shown in Table 3.
TABLE-US-00003 TABLE 3 weight ratio of the graphene interval interval swelling oxide powder width width degree to the 1,3- (nm)(dry (nm)(wet of the propanediamine membrane) membrane) interval water 1:0 0.86 1.15 33.7% separation composite membrane (I) water 1:10 1.00 1.09 9.0% separation composite membrane (XIII) water 1:20 1.10 1.15 4.5% separation composite membrane (XIV) water 1:40 1.17 1.19 1.7% separation composite membrane (XV) water 1:80 1.24 1.21 2.5% separation composite membrane (XVI)
[0045] Table 3
[0046] As shown in Table 2 and Table 3, the water separation composite membrane (I) having the selective layer without the organic compound (ethanedial or 1,3-propanediamine) has a relative high swelling degree of the interval. To the contrary, with the increase of the weight of the organic compound (ethanedial or 1,3-propanediamine), the swelling degree of the interval of the dehumidifying composite membrane is reduced. It means the addition of the organic compound can indeed bridge between two adjacent graphene oxide layers to maintain the interval width between any two adjacent graphene oxide layers within a specific range. As a result, a passageway, through which water molecules pass, can be formed between two adjacent graphene oxide layers, resulting in improving the water vapor permeance and water/air separation factor of the dehumidifying composite membrane.
EXAMPLE 18
Dehumidification Performance Test
[0047] The water vapor permeance and the water/air separation factor of the dehumidifying composite membranes (V) and (XII) of Examples 6 and 13 were evaluated by the dehumidification device 100 as shown in
TABLE-US-00004 TABLE 4 water water separation separation water composite composite water separation membrane (V) membrane (V) separation composite (measured at (measured at composite membrane 25 C./ 29 C./ membrane (II) 80% RH) 60% RH) (XII) thickness ~800 nm ~800 nm ~800 nm ~800 nm of the selective layer water vapor 8 10.sup.6 1.24 10.sup.5 1.19 10.sup.5 9 10.sup.6 permeance (mol/m.sup.2sPa) water/air ~1000 ~5.75 10.sup.6 ~3.79 10.sup.6 ~2000 separation factor
[0048] As shown in Table 4, the water separation composite membrane of the disclosure having the selective layer including the organic compound exhibits higher water vapor permeance and water/air separation factor in comparison with the water separation composite membrane without the organic compound having the structure represented by Formula (I) or (II) within the selective layer. Furthermore, the water separation composite membrane (V) has a water/air separation factor about 3.7910.sup.6 when being measured at 29 C./60% RH.
EXAMPLE 19
Water Separation Composite Membrane (XVII)
[0049] Example 19 was performed in the same manner as Example 6 except that the thickness was increased from about 800 nm to about 1400 nm, obtaining the water separation composite membrane (XVII).
EXAMPLE 20
Water Separation Composite Membrane (XVIII)
[0050] Example 20 was performed in the same manner as Example 6 except that the thickness was increased from about 800 nm to about 3000 nm, obtaining the water separation composite membrane (XVIII).
EXAMPLE 21
Dehumidification Performance Test
[0051] The water vapor permeance and the water/air separation factor of the dehumidifying composite membranes (XVII) and (XVIII) of Examples 19 and 20 were evaluated by the dehumidification device 100 as shown in
TABLE-US-00005 TABLE 5 water water water separation separation separation composite composite composite membrane membrane membrane (V) (XVII) (XVIII) thickness ~800 nm ~1400 nm ~3000 nm of the selective layer water vapor 1.24 10.sup.5 1.05 10.sup.5 1.0 10.sup.5 permeance (mol/m.sup.2sPa) water/air ~5.75 10.sup.6 ~5.12 10.sup.6 ~5.0 10.sup.6 separation factor
[0052] It will be clear that various modifications and variations can be made to the disclosed methods and materials. It is intended that the specification and examples be considered as exemplary only, with a true scope of the disclosure being indicated by the following claims and their equivalents.