CN106582307A - Blend membrane preparation method and application of blend membrane - Google Patents
Blend membrane preparation method and application of blend membrane Download PDFInfo
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- CN106582307A CN106582307A CN201710085798.8A CN201710085798A CN106582307A CN 106582307 A CN106582307 A CN 106582307A CN 201710085798 A CN201710085798 A CN 201710085798A CN 106582307 A CN106582307 A CN 106582307A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
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- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
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- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention provides a blend membrane preparation method and application of a blend membrane. The blend membrane is prepared by blending of basic materials including polyether-b-polyamide and ether bond functional ionic liquid. Ether bond cations are led into the ionic liquid, and CO2 permeability coefficient is increased under interaction of four dipole moments between ether bond and CO2. The blend membrane is excellent in CO2 separation performance, the CO2 permeability coefficient is more than two times of an original CO2 permeability coefficient, excellent membrane separation performance and stability in chemical performances are realized, and industrialization is benefited.
Description
Technical field
The present invention relates to gas separation membrane technology, specifically a kind of polyether-b-polyamide/ether-oxygen bond functionalization ion
Liquid blend film.
Background technology
Global warming has become the severe challenge of facing mankind, and the main cause for causing climate warming is greenhouse gases
(mainly CO2) greenhouse effect that causes, the burning of Fossil fuel (oil, natural gas and coal) is CO2Main source.And
CCS(CO2Capture and storage) it is then a kind of effectively reduction CO2The method of discharge, its process includes CO2Trapping,
Transport and its storage.CO2Separation be related to CO in flue gas2/N2Separation, CO in synthesis gas2/H2Separation and natural gas in
CO2Separation.CO2Detached method, including chemical absorbing, pressure-variable adsorption, cryogenic separation and membrane separating method；Compare its other party
Method, membrane separating method has low energy consumption, is easy to amplify and advantages of environment protection.
The core of membrane separation technique is polymeric film, and polymeric film is limited between infiltration coefficient and separation factor
The Robeson upper limits (infiltration coefficient increases and selectivity declines).Therefore, exploitation can break through the novel film materials of the Robeson upper limits
It is the important topic in membrance separation field.At present, ether-oxygen bond and CO2Stronger interaction between molecule contributes to CO2Infiltration is said
Method has been widely accepted.And polyether-b-polyamide (PEBA) is a kind of block copolymer of commercialization, by polyethers (PE) segment
Form with polyamide (PA) segment copolymerization, not only with ether-oxygen bond, also with preferable acid-proof alkaline and thermo mechanical stability.
Ionic liquid be into the organic salt of liquid under a big class room temperature condition, it is typically organic by a larger organic cation and one
Or inorganic anion composition, imidazole salts sun the features such as with heat stability, highly dissoluble and extremely low vapour pressure, in ionic liquid
Ion ([BMIM]-) or fluo anion all to CO2Molecule has stronger interaction, so as to promote CO2Dissolving.But,
Fluoride ion liquid is mixed into the blend film of PEBA preparations, CO2/CH4And CO2/H2Selectivity decline it is more.So, by the sunny side
Introduce ether-oxygen bond in ion to improve ionic liquid to CO2Interaction, reduce CO2/CH4And CO2/H2It is selective to decline.
Research PEBA and the method for ether-oxygen bond functionalized ion liquid blending, prepare the CO having compared with high separability energy2Seperation film, due to
The Modulatory character of ionic liquid structure, further can transform membrane structure as needed and be actually needed to meet.
The content of the invention
The permeance property and selectivity of gas separation membrane can be taken into account, and the present invention provides a kind of blend film, with polyethers-b-
Polyamide (PEBA)/ionic liquid is raw material, and introduces ether-oxygen bond in ionic liquid, keeps its film heat stability, permeability
On the basis of, reduce to the selective decline of specific gas.
The technical purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of blend film, comprises the following steps：
(1) by polyether-b-polyamide heating for dissolving in solvent, the solution that mass concentration is 0.1%～20% is prepared；
(2) during ether-oxygen bond functionalized ion liquid to be added the solution of (1), the wherein matter of ether-oxygen bond functionalized ion liquid
Measure as 0.01～4 times of polyether-b-polyamide quality, stirring obtains casting solution, casting film and vacuum heat remove remaining
Solvent, obtains blend film；
The ether-oxygen bond functionalized ion liquid is made up of the cation and anion for introducing ether-oxygen bond, the introducing ether oxygen
The cation of key is the R to the cation shown in formula I～formula IV structural formula1～R5The cation obtained after middle introducing ether-oxygen bond, its
Middle R1～R5Separately selected from the alkyl of H or C1～C6；
The anion is selected from bis-trifluoromethylsulfoandimide anion [Tf2N]-, hexafluorophosphoric acid anion [PF6]-, tetrafluoro
Acid anion [BF4]-In at least one.
In the preparation method of above-mentioned blend film, as preferred embodiment, the cation of the introducing ether-oxygen bond
At least one in the cation shown in the structural formula of formula V, VI, VII：
In the preparation method of above-mentioned blend film, described polyether-b-polyamide (PEBA) is with following structural formula
Product：
Wherein, PA (amide segment) be nylon-6 (PA6), nylon-11 (PA11) or PA-12 (PA12), PE (polyether chains
Section) it is poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO) or polybutylene oxide (PTMO)；The molecular weight of copolymer is decided by altogether
The content of PA and PE in polymers molecule, the molecular weight ranges 300～15000 of PA segments in copolymer molecule, in copolymer molecule
The molecular weight ranges 200～6000 of PE segments.
Can make or buy the product having been commercialized by oneself in practical application, the polyether-b-polyamide used by the present invention is
PEBA1657, PEBA2533 or PEBA1074 product of Arkema companies.
In the preparation method of above-mentioned blend film, as preferred embodiment, in step (2) ether-oxygen bond functionalization from
The addition of sub- liquid is 0.1～3 times, more preferably 0.25～2 times of polyether-b-polyamide quality.
In the preparation method of above-mentioned blend film, used as preferred embodiment, solvent described in step (1) is selected from N,
Dinethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, 1-1-2- trichloroethanes, formic acid, acetic acid, 1- fourths
At least one in alcohol, n-butyl alcohol and 1- propanol solvent mixtures, chloroform, tetrafluoroacetate and ethanol/water mixed solvent, preferably
For ethanol/water mixed solvent.As more specifically embodiment, ethanol in solvent：The mass ratio of water is 5～8:2～4, as
Most preferably embodiment, is 7:3.
In the preparation method of above-mentioned blend film, as preferred embodiment, polyether-b-polyamide in step (1)
Mass concentration be 1～10%；In solution in step (2) mass fraction of ether-oxygen bond functionalized ion liquid be 0.01～
80%, preferably 5～60%.
In the preparation method of above-mentioned blend film, gather as dissolving polyethers-b- in preferred embodiment, step (1)
The temperature of amide is 5～120 DEG C, preferably 35～90 DEG C；The temperature of vacuum heat is 30～100 DEG C in step (2).
In the preparation method of above-mentioned blend film, casting film time control masking thickness is 50～300 μm.
The technical purpose of another aspect of the present invention is to provide blend film the answering as gas separation membrane of said method preparation
With, the blend film can be applicable to the separation of the admixture of gas for including preferentially permeating gas and non-preferential infiltration gas composition, from
And realize the separation and removing of preferential infiltration gas；Preferential infiltration gas includes CO2、SO2And H2At least one in S；Non-preferential
Infiltration gas includes N2, C1～C4 hydrocarbon gas and H2At least one of.
In above-mentioned application, used as more specifically, the hybrid films are to CO2/N2、SO2/N2、H2S/CH4、CO2/CH4、CO2/
H2There is higher separating property etc. system.
Compared with prior art, it is an advantage of the current invention that：
1st, the present invention is using ether-oxygen bond and CO2Between four dipole moments interaction, draw in the cation of ionic liquid
Enter ether-oxygen bond, to improve CO2Infiltration coefficient.
2nd, the present invention adopts two kinds of materials of polyether-b-polyamide PEBA and ether-oxygen bond functionalized ion liquid as system
The material of standby blend film, it is all and CO2Have compared with strong interaction, improve CO2Dissolubility.
3rd, blend film of the invention has excellent CO2Separating property, CO2Infiltration coefficient can reach original 2 times with
On, membrane separating property is excellent, and stable chemical performance, beneficial to industrialization.
Description of the drawings
Fig. 1 is the test device figure that gas separates blend film, wherein 1 is No. 1 valve；2 is No. 2 valves；3 is No. 3 valves；
4 is No. 4 valves；5 is No. 5 valves；6 is No. 6 valves；7 is No. 7 valves；8 is No. 8 valves；9 is No. 9 valves；10 is 1L gases
Tank；11 is 50mL gas tanks；12 is 100mL gas tanks；13 is pressure gauge；14 is pressure transducer；15 is osmotic cell；
Fig. 2 is the DSC collection of illustrative plates of film prepared by various embodiments of the present invention, wherein：
A is the PEBA films of embodiment 1；
B is blend film PEBA/ [the EOEIM] [Tf of embodiment 22N] (90wt%/10wt%)；
C is blend film PEBA/ [the EOEIM] [Tf of embodiment 32N] (80wt%/20wt%)；
D is blend film PEBA/ [the EOEIM] [Tf of embodiment 52N] (60wt%/40wt%)；
E is blend film PEBA/ [the EOEIM] [Tf of embodiment 62N] (40wt%/60wt%).
Fig. 3 is the XRD spectrum of film prepared by various embodiments of the present invention, wherein：
A is the PEBA films of embodiment 1；
B is blend film PEBA/ [the EOEIM] [Tf of embodiment 22N] (90wt%/10wt%)；
C is blend film PEBA/ [the EOEIM] [Tf of embodiment 32N] (80wt%/20wt%)；
D is blend film PEBA/ [the EOEIM] [Tf of embodiment 42N] (70wt%/30wt%)；
E is blend film PEBA/ [the EOEIM] [Tf of embodiment 52N] (60wt%/40wt%)；
F is blend film PEBA/ [the EOEIM] [Tf of embodiment 62N] (40wt%/60wt%).
Specific embodiment
The specific embodiment of the present invention is described in detail below in conjunction with technical scheme and accompanying drawing.
Polyether-b-polyamide PEBA/ ether-oxygen bond functionalized ion liquid blend film passes through for gas separation in the present invention
Equal-volume-transformation method obtains infiltration coefficient, and process is as shown in Figure 1.Testing process is as follows：
A) film is loaded into osmotic cell, closes No. 6 valves and No. 9 valves, remaining valve is fully open, and evacuation is persistently taken out
12h。
B) hunt leak：No. 5, No. 7 and No. 4 valves are closed, while osmotic lateral pressure change is recorded, when osmotic lateral pressure is less than finger
Fixed number value, illustrates that system is air tight, then can start test.
C) test：Control to permeate Side Volume by control 1 and No. 2 valves, close all valves, open No. 9 valves,
Pressure in gas tank is controlled by pressure gauge, temperature is adjusted by temperature control system；When starting test, No. 7, No. 8 valves are opened, led to
Excess pressure sensor record osmotic lateral pressure changes, and then calculates infiltration coefficient and separation of the gas in film.
In formula：
Infiltration coefficient Barrer [1Barrer=10 of P --- the gas in film-10cm3(STP)·cm/(cm2·s·
cmHg)]
V --- volume cm of gas per-meate side3
A --- effective membrane area, cm2
Δ p --- the pressure differential of film both sides, cmHg
The thickness of l --- film, cm
The temperature of T --- osmotic cell, DEG C
The speed that dp/dt --- osmotic lateral pressure increases, cmHg/s
PA--- infiltration coefficient Barrer [1Barrer=10s of the gas A in film-10cm3(STP)·cm/(cm2·s·
cmHg)]
PB--- infiltration coefficient Barrer [1Barrer=10s of the gas B in film-10cm3(STP)·cm/(cm2·s·
cmHg)]
αA/B--- separation
The raw material information being related in following embodiments：
Polyether-b-polyamide (PEBA)：Arkema companies, product type1657。
Ether-oxygen bond functionalized ion liquid：1- ethyl diethyldithiocarbamates ether -3- Methylimidazole .s bis-trifluoromethylsulfoandimide salt [EOEIM]
[Tf2N], upper marine origin victory Chemical Co., Ltd.；1- nitriles propyl group -3- Methylimidazole .s bis-trifluoromethylsulfoandimide salt [CPMIM]
[Tf2N], upper marine origin victory Chemical Co., Ltd..
Embodiment 1
Weigh PEBA granules to be added in ethanol/water (70wt%/30wt%) ,～70 DEG C or so stirring 6h obtain uniform
The PEBA solution of transparent 5wt%, casting solution is poured on tetrafluoro plate, solvent flashing under room temperature condition, it is to be filmed after remove, put
Enter at least 48h in 40 DEG C of vacuum drying ovens, remove residual solvent, obtain pure PEBA films.
35 DEG C, during admission pressure 0.3MPa, the gas permeability test result of pure PEBA films is shown in Table 1, the DSC collection of illustrative plates of film
As shown in Fig. 2 (a), shown in XRD spectrum such as Fig. 3 (a).
Embodiment 2
The PEBA granules for weighing certain mass are added in ethanol/water (70wt%/30wt%), and at～70 DEG C 6h is stirred,
Addition accounts for PEBA and [EOEIM] [Tf2N] quality sum 10wt% [EOEIM] [Tf2N], heated and stirred 2h obtains homogeneous transparent
5wt% PEBA solution, casting solution is poured on tetrafluoro plate, solvent flashing under room temperature condition, it is to be filmed after remove, be put into 40
At least 48h in DEG C vacuum drying oven, removes residual solvent, obtains blend film PEBA/ [EOEIM] [Tf2N] (90wt%/10wt%).
Shown in DSC collection of illustrative plates such as Fig. 2 (b) of blend film, shown in XRD spectrum such as Fig. 3 (b).
Embodiment 3
The PEBA granules for weighing certain mass are added in ethanol/water (70wt%/30wt%), and at～70 DEG C 6h is stirred,
Addition accounts for PEBA and [EOEIM] [Tf2N] quality sum 20wt% [EOEIM] [Tf2N], heated and stirred 2h obtains homogeneous transparent
5wt% PEBA solution, casting solution is poured on tetrafluoro plate, solvent flashing under room temperature condition, it is to be filmed after remove, be put into 40
At least 48h in DEG C vacuum drying oven, removes residual solvent, obtains blend film PEBA/ [EOEIM] [Tf2N] (80wt%/20wt%).
Shown in DSC collection of illustrative plates such as Fig. 2 (c) of blend film, shown in XRD spectrum such as Fig. 3 (c).
Embodiment 4
The PEBA granules for weighing certain mass are added in ethanol/water (70wt%/30wt%), and at～70 DEG C 6h is stirred,
Addition accounts for PEBA and [EOEIM] [Tf2N] quality sum 30wt% [EOEIM] [Tf2N], heated and stirred 2h obtains homogeneous transparent
5wt% PEBA solution, casting solution is poured on tetrafluoro plate, solvent flashing under room temperature condition, it is to be filmed after remove, be put into 40
At least 48h in DEG C vacuum drying oven, removes residual solvent, obtains blend film PEBA/ [EOEIM] [Tf2N] (70wt%/30wt%).
35 DEG C, during admission pressure 0.3MPa, PEBA/ [EOEIM] [Tf2N] gas of (70wt%/30wt%) blend film oozes
Thoroughly the performance test results are shown in Table 1, shown in XRD spectrum such as Fig. 3 (d) of blend film..
Embodiment 5
The PEBA granules for weighing certain mass are added in ethanol/water (70wt%/30wt%), and at～70 DEG C 6h is stirred,
Addition accounts for PEBA and [EOEIM] [Tf2N] quality sum 40wt% [EOEIM] [Tf2N], heated and stirred 2h obtains homogeneous transparent
5wt% PEBA solution, casting solution is poured on tetrafluoro plate, solvent flashing under room temperature condition, it is to be filmed after remove, be put into 40
At least 48h in DEG C vacuum drying oven, removes residual solvent, obtains blend film PEBA/ [EOEIM] [Tf2N] (60wt%/40wt%).
Shown in DSC collection of illustrative plates such as Fig. 2 (d) of blend film, shown in XRD spectrum such as Fig. 3 (e).
Embodiment 6
The PEBA granules for weighing certain mass are added in ethanol/water (70wt%/30wt%), and at～70 DEG C 6h is stirred,
Addition accounts for PEBA and [EOEIM] [Tf2N] quality sum 60wt% [EOEIM] [Tf2N], heated and stirred 2h obtains homogeneous transparent
5wt% PEBA solution, casting solution is poured on tetrafluoro plate, solvent flashing under room temperature condition, it is to be filmed after remove, be put into 40
At least 48h in DEG C vacuum drying oven, removes residual solvent, obtains blend film PEBA/ [EOEIM] [Tf2N] (40wt%/60wt%).
35 DEG C, during admission pressure 0.3MPa, PEBA/ [EOEIM] [Tf2N] gas of (40wt%/60wt%) blend film oozes
Thoroughly the performance test results are shown in Table 1, shown in DSC collection of illustrative plates such as Fig. 2 (e) of blend film, shown in XRD spectrum such as Fig. 3 (f).
Embodiment 7
The PEBA granules for weighing certain mass are added in ethanol/water (70wt%/30wt%), and at～70 DEG C 6h is stirred,
Addition accounts for PEBA and [CPMIM] [Tf2N] quality sum 60wt% [CPMIM] [Tf2N], heated and stirred 2h obtains homogeneous transparent
5wt% PEBA solution, casting solution is poured on tetrafluoro plate, solvent flashing under room temperature condition, it is to be filmed after remove, be put into 40
At least 48h in DEG C vacuum drying oven, removes residual solvent, obtains PEBA/ [CPMIM] [Tf2N] (40wt%/60wt%) blend film.
35 DEG C, during admission pressure 0.3MPa, PEBA/ [CPMIM] [Tf2N] gas of (40wt%/60wt%) blend film oozes
Thoroughly the performance test results are shown in Table 1.
Table 1.
Table 1 is PEBA/ [EOEIM] [Tf in embodiment 4,62N] blend film, PEBA/ [CPMIM] [Tf in embodiment 72N] altogether
Mixed film compares with the gas permeability test result of pure PEBA films in embodiment 1.As can be seen from Table 1, [EOEIM] [Tf2N]
Content has large effect to the gas permeability of blend film, with [EOEIM] [Tf2N] content increase, the infiltration of gas
Coefficient substantially rises.In embodiment 4 and 6, CO2、N2And CH4Infiltration coefficient gradually increase, and increase amplitude is it is obvious that this is
Due to [EOEIM] [Tf in PEBA segments2N] appearance, the hydrogen bond between polyether segment be destroyed, cause the unformed of polymer
Mutually increase (can find out, the glass transition temperature T of blend film from the dsc analysis of the blend film of accompanying drawing 2gIt is gradually reduced), knot
Brilliant degree reduces (can find out from the XRD analysis of the blend film of accompanying drawing 3, the crystallization peak intensity of blend film is gradually reduced), free body
Product and ether oxygen content increase.In conjunction with the embodiments 1,4,6, with [EOEIM] [Tf2N] content increase, CO2/N2And CO2/CH4
All decrease.Meanwhile, by comparative example 1,6,7, ionic liquid [EOEIM] [Tf is mixed into respectively2N] and [CPMIM]
[Tf2N] after, equal volume (60wt%) PEBA/ [EOEIM] [Tf2N] blend film gas permeability than PEBA/ [CPMIM]
[Tf2N] blend film is substantially higher, and illustrates the ionic liquid of ether-oxygen bond functionalization to lifting blend film gas permeability effect more
Substantially.
Table 2 is PEBA/ [the EOEIM] [Tf of the present invention2N] blend film and PEBA/PEG blend film (come from document：
Journal of Membrane Science,2008,307(1):Comparison 88-95).
Table 2
As can be seen from Table 2, PEBA/PEG (Polyethylene Glycol) blend film, PEBA/ [EOEIM] [Tf are compared2N] blend film
Bigger (the test temperature of infiltration coefficient increase rate：30 DEG C of PEBA/PEG blend film, 35 DEG C of the present invention), beyond test temperature
Impact of the degree difference to blend film gas permeability coefficient, while PEBA/ [EOEIM] [Tf2N] and two kinds of blend film of PEBA/PEGSelectivity be more or less the same.Therefore, PEBA/ [EOEIM] [Tf2N] blend film shows more preferable permeability and separation
Energy.
Claims (10)
1. a kind of preparation method of blend film, comprises the following steps：
(1) by polyether-b-polyamide heating for dissolving in solvent, the solution that mass concentration is 0.1%～20% is prepared；
(2) during ether-oxygen bond functionalized ion liquid to be added the solution of (1), the quality of wherein ether-oxygen bond functionalized ion liquid is
0.01～4 times of polyether-b-polyamide quality, stirring obtains casting solution, casting film and vacuum heat removing residual solvent,
Obtain blend film；
The ether-oxygen bond functionalized ion liquid is made up of the cation and anion for introducing ether-oxygen bond, the introducing ether-oxygen bond
Cation is the R to the cation shown in formula I～formula IV structural formula1～R5The cation obtained after middle introducing ether-oxygen bond, wherein R1
～R5Separately selected from the alkyl of H or C1～C6；
The anion is selected from bis-trifluoromethylsulfoandimide anion [Tf2N]-, hexafluorophosphoric acid anion [PF6]-, Tetrafluoroboric acid it is cloudy
Ion [BF4]-In at least one.
2. preparation method according to claim 1, it is characterised in that the cation for introducing ether-oxygen bond is selected from formula
Vth, at least one in the cation shown in VI, VII structural formula：
3. preparation method according to claim 1, it is characterised in that ether-oxygen bond functionalized ion liquid in step (2)
Addition is 0.1～3 times of polyether-b-polyamide quality.
4. preparation method according to claim 1, it is characterised in that solvent described in step (1) is selected from N, N- dimethyl
Methanamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, 1-1-2- trichloroethanes, formic acid, acetic acid, n-butyl alcohol, n-butyl alcohol
With at least one in 1- propanol solvent mixtures, chloroform, tetrafluoroacetate and ethanol/water mixed solvent.
5. preparation method according to claim 4, it is characterised in that it is molten that solvent described in step (1) is that ethanol/water mixes
Agent.
6. preparation method according to claim 1, it is characterised in that the mass concentration of polyether-b-polyamide in step (1)
For 1～10%；The mass fraction of ether-oxygen bond functionalized ion liquid is 0.01～80%, preferably 5 in solution in step (2)
～60%.
7. preparation method according to claim 1, it is characterised in that the temperature of dissolving polyether-b-polyamide in step (1)
For 5～120 DEG C, the temperature of vacuum heat is 30～100 DEG C in step (2).
8. preparation method according to claim 1, it is characterised in that casting film time control masking thickness is in step (2)
50～300 μm.
9. application of the blend film that prepared by the method described in claim 1～8 any one claim as gas separation membrane.
10. application according to claim 9, it is characterised in that the blend film be applied to include preferentially to permeate gas and
The separation of the admixture of gas of non-preferential infiltration gas composition, preferential infiltration gas includes CO2、SO2And H2At least one in S；
Non-preferential infiltration gas includes N2, C1～C4 hydrocarbon gas and H2At least one of.
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