CN103846024A - Sulfonated polyetheretherketone/sulfonated chromium organic framework hybrid membrane, as well as preparation and applications thereof - Google Patents
Sulfonated polyetheretherketone/sulfonated chromium organic framework hybrid membrane, as well as preparation and applications thereof Download PDFInfo
- Publication number
- CN103846024A CN103846024A CN201410091943.XA CN201410091943A CN103846024A CN 103846024 A CN103846024 A CN 103846024A CN 201410091943 A CN201410091943 A CN 201410091943A CN 103846024 A CN103846024 A CN 103846024A
- Authority
- CN
- China
- Prior art keywords
- ether
- ketone
- sulfonation
- sulfonated polyether
- chromium organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000013384 organic framework Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000012528 membrane Substances 0.000 title abstract description 25
- 150000001844 chromium Polymers 0.000 title abstract 5
- 239000004696 Poly ether ether ketone Substances 0.000 claims abstract description 66
- 229920002530 polyetherether ketone Polymers 0.000 claims abstract description 66
- 239000011651 chromium Substances 0.000 claims abstract description 58
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical class [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 55
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 27
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000035699 permeability Effects 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000005266 casting Methods 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 52
- 238000006277 sulfonation reaction Methods 0.000 claims description 45
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- CUTSCJHLMGPBEJ-UHFFFAOYSA-N [N].CN(C)C=O Chemical compound [N].CN(C)C=O CUTSCJHLMGPBEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 3
- OXMGUTQVUIWQEK-UHFFFAOYSA-N [N].CC(=O)N(C)C Chemical compound [N].CC(=O)N(C)C OXMGUTQVUIWQEK-UHFFFAOYSA-N 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 229910001430 chromium ion Inorganic materials 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000010345 tape casting Methods 0.000 abstract 1
- RRSSHLQOTMHHKS-UHFFFAOYSA-N CC(C)C(N)=O.CC(C)C(N)=O.CC(C)C(N)=O.N Chemical compound CC(C)C(N)=O.CC(C)C(N)=O.CC(C)C(N)=O.N RRSSHLQOTMHHKS-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001764 infiltration Methods 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 238000013019 agitation Methods 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 229920002521 macromolecule Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/148—Organic/inorganic mixed matrix membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/52—Polyethers
- B01D71/522—Aromatic polyethers
- B01D71/5222—Polyetherketone, polyetheretherketone, or polyaryletherketone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Polyethers (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a sulfonated polyetheretherketone/sulfonated chromium organic framework hybrid membrane, as well as preparation and applications thereof. The hybrid membrane is composed of sulfonated polyetheretherketone and a sulfonated chromium metal organic framework. The preparation of the hybrid membrane comprises the following steps: reacting Cr(NO3)3.9H2O, terephthalic acid and hydrofluoric acid in water to obtain a chromium organic framework material; modifying by trifluoromethanesulfonic anhydride and concentrated sulfuric acid to obtain a sulfonated chromium organic framework material; mixing the sulfonated chromium organic framework material with a sulfonated polyetheretherketone solution to obtain a membrane casting solution, thereby preparing the hybrid membrane by tape casting. The hybrid membrane and the preparation of the hybrid membrane have the following advantages: raw materials are easy to obtain, the preparation process is simple and controllable, and the prepared sulfonated polyetheretherketone/sulfonated chromium organic framework hybrid membrane is applicable to CO2/N2 gas separation and has high selectivity and high permeability.
Description
Technical field
The present invention relates to a kind of sulfonated polyether-ether-ketone/sulfonation chromium organic backbone hybridized film and preparation and application, belong to gas separation membrane technical field.
Background technology
Hybrid organic-inorganic film is to point in polymer matrix to introduce inorganic component, thereby makes hybridized film can possess the toughness of organic film and the high-temperature stability of inoranic membrane simultaneously, also can improve gas permeability and the separating property of film simultaneously.Compatibility between high molecular polymer and inorganic particulate is very large on the impact of hybridized film separating property, the content that increases inorganic particulate in is to a certain degree conducive to the improvement of high molecular polymerization physical performance, but along with the increasing of the content of inorganic component, the trend of particle aggregation also increases, be embodied in formation agglomerated particle particle diameter increase and also inhomogeneous, in addition, between organic and inorganic component, the degree that is separated also can increase, interface compatibility variation.Interface compatibility variation will cause inorganic particulate to exist many holes, the existence in these holes to reduce the selective of infiltration component around.In order to solve the problem of interface compatibility variation, researcher has done a lot of effort, comprises the compatibility performance that adopts sol-gel and improve two-phase with coupling agent in the process of preparation.In order to prepare, inorganic particle disperses more evenly, more preferably hybridized film of macromolecule-inorganic interface configuration, researcher prepares and has studied a greater variety of inorganic particulates, comprise active carbon, zeolite, molecular sieve, nanotube, Graphene etc., probe into membrane structure performance structure-activity relationship separated from the gas, promote the development of membrane technology.
Sulfonated polyether-ether-ketone is obtained after sulfonation by polyether-ether-ketone, there is good heat endurance and mechanical strength, in sulfonated polyether-ether-ketone, fill inorganic particulate and prepare hybrid organic-inorganic film, make hybridized film have pliability and the film forming that sulfonated polyether-ether-ketone film is good concurrently, and the feature such as the high temperature resistant and high mechanical properties of inoranic membrane, and inorganic particulate is carried out after functionalization, not only can improve boundary defect, improve interface compatibility, can also improve permeability of the membrane and Selective Separation performance.
Metal-organic framework materials becomes as a kind of novel porous material the focus that various countries researcher pays close attention to.Due to the metal site that metal-organic framework materials pore structure is controlled, specific area large, contain unsaturated coordination, make it aspect adsorbing separation and gas storage, there is very large application potential.In metal-organic framework materials, organic ligand, as the syndeton of metal ion, can improve organic and inorganic interface compatibility to a certain extent.By to metal-organic framework materials functionalization, introduce and there is the functional group of polarity effect and improve it and CO
2polarity effect, construct the CO of high-efficiency and continuous in hybridized film
2transmit site, thereby improve CO
2gas separative efficiency.Up to the present, sulfonated polyether-ether-ketone/sulfonation chromium organic backbone hybridized film separates and has no bibliographical information for gas.
Summary of the invention
The object of the present invention is to provide a kind of sulfonated polyether-ether-ketone/sulfonation chromium organic backbone hybridized film and preparation and application.This hybridized film is for separating of CO
2/ N
2mist, has good separating effect.This preparation method's process is easy to be controlled.
The present invention is achieved through the following technical solutions, a kind of sulfonated polyether-ether-ketone/sulfonation chromium organic backbone hybridized film, it is characterized in that, this sulfonated polyether-ether-ketone/sulfonation chromium organic backbone hybridized film thickness is 55 ~ 75 microns, it is to be made up of sulfonated polyether-ether-ketone and sulfonation chromium organic backbone, sulfonation chromium organic backbone particle diameter 500 nanometers, wherein sulfonated polyether-ether-ketone and sulfonation chromium organic backbone mass ratio are (0.80 ~ 0.95): (0.20 ~ 0.05) described sulfonated polyether-ether-ketone sulfonation degree is 69.4 %.
The preparation method of above-mentioned sulfonated polyether-ether-ketone/sulfonation chromium organic backbone hybridized film, is characterized in that comprising following process:
1). the preparation of sulfonation chromium organic backbone
By Cr (NO
3)
39H
2o, the aqueous solution of the mass fraction that terephthalic acid (TPA) and hydrofluoric acid are mixed with chromium ion concentration by the mol ratio of 1:1:1 between 0.8%-1.2%, solution is transferred in reactor and stirred after 30 minutes, under 220 ℃ of conditions, react 8 hours, filter, obtain green flour powder crystal, with nitrogen, nitrogen-dimethyl formamide washes away the not terephthalic acid (TPA) of complete reaction 100 ℃ of backflows, residual nitrogen in being swapped out crystal with ethanol at 78 ℃ again, nitrogen-dimethyl formamide, put into drying box in 150 ℃ of freeze-day with constant temperature 24h, remove ethanol molecule residual in crystal, obtain the chromium organic framework material of pure particle diameter 500 nanometers,
2). the chromium organic framework material that step 1) is made, mass concentration is that 98% sulfuric acid and trifluoromethanesulfanhydride anhydride are by a mole 1:3:4.5 ratio, stirring reaction 1-3h under room temperature in nitromethane, through centrifugation, absolute ethanol washing, put into drying box in 150 ℃ of freeze-day with constant temperature 24h, obtain sulfonation chromium organic framework material;
3). under stirring at room temperature, the sulfonated polyether-ether-ketone that is 69.4% by sulfonation degree joins nitrogen, is mixed with mass concentration and is 10% sulfonated polyether-ether-ketone solution in nitrogen-dimethylacetamide solvent; By sulfonated polyether-ether-ketone and step 2 in sulfonated polyether-ether-ketone solution) the sulfonation chromium organic backbone mass ratio that makes is in (0.80 ~ 0.95): (0.20 ~ 0.05), sulfonation chromium organic backbone adds in sulfonated polyether-ether-ketone, ultrasonic dispersion 12 h, leave standstill 1h deaeration, obtain sulfonated polyether-ether-ketone/sulfonation chromium organic backbone casting solution, this casting solution is poured in glass culture dish, be dried 12 hours at temperature 60 C, be dried 12 hours 80 ℃ of temperature afterwards, obtain sulfonated polyether-ether-ketone/sulfonation chromium organic backbone hybridized film.
With the application of the prepared sulfonated polyether-ether-ketone/sulfonation of above-mentioned preparation method chromium organic backbone hybridized film, for CO
2/ N
2separation, be selectively 32 ~ 40, permeability is 16 ~ 24 barrer.
The invention has the advantages that: raw material is easy to get, preparation process is easy to be controlled, mild condition, and the sulfonated polyether-ether-ketone/sulfonation chromium organic backbone hybridized film making is applied to CO
2/ N
2gas separates, and introduces the sulfonate radical more with polarity effect, improves CO
2dissolving selective, introduce and there is the chromium organic framework material of microcellular structure, improve the permeability of gas, there is excellent combination property.Particularly this hybridized film has higher CO
2permeability and CO
2/ N
2selectively, purer sulfonated polyether-ether-ketone film, has improved respectively 71.43 % and 32.35 %.
Accompanying drawing explanation
Fig. 1 is the local SEM photo of the section of sulfonated polyether-ether-ketone/sulfonation chromium organic backbone hybridized film of making of embodiment 4.
Fig. 2 is the local SEM photo of the section of the pure sulfonated polyether-ether-ketone homogeneous membrane that makes of comparative example 1.
Fig. 3 is the local SEM photo of the section of sulfonated polyether-ether-ketone/chromium organic backbone hybridized film of making of comparative example 5.
The specific embodiment
embodiment 1
Prepare the sulfonation chromium organic backbone of particle diameter approximately 500 nanometers.Process is as follows: 4.0 g nine water chromic nitrates and 1.64 g terephthalic acid (TPA)s are added in 48 mL deionized waters and add the hydrofluoric acid that 0.2 ml mass fraction is 40%, after stirring 30min, mixed solution is transferred in reactor, put into 220 ℃ of isothermal reaction 8h of drying box, after reaction finishes, reactor is left standstill and is cooled to room temperature, sample nitrogen, nitrogen-dimethyl formamide washes away the not terephthalic acid (TPA) of complete reaction 100 ℃ of backflows, residual nitrogen in being swapped out crystal with ethanol at 78 ℃ again, nitrogen-dimethyl formamide, put into drying box in 150 ℃ of freeze-day with constant temperature 24h, obtain green chromium organic framework material.Get this green chromium organic framework material 1.0 g and add in round-bottomed flask, in flask, add 60 mL nitromethanes, then add 0.503mL mass concentration 98% sulfuric acid, 1.45mL trifluoromethyl sulfonic acid anhydride, 30
oc reacts 2 h, centrifugal, and then ethanol washing, puts into drying box in 150 ℃ of freeze-day with constant temperature 24h, obtains sulfonation chromium organic framework material.
Take 0.6 g sulfonated polyether-ether-ketone and 8 g nitrogen, nitrogen-dimethylacetylamide is stirring at room temperature 12 h under 500 r/min magnetic agitation, and sulfonated polyether-ether-ketone is all dissolved.By above-mentioned sulfonation chromium organic framework material 0.03 g making, add 4 g nitrogen, nitrogen-dimethylacetylamide, ultrasonic 12 h, the organic backbone solution of sulfonation chromium is joined in above-mentioned sulfonated polyether-ether-ketone solution, after 24 h, stop stirring, with copper mesh filtration, leave standstill 1 h deaeration, be poured in clean glass culture dish (Φ 100 mm), be placed in baking oven, dry 12 h at 60 ℃ and 80 ℃ respectively, obtaining thick is 63 μ m homogeneous membranes.Under room temperature, 1.5 bar conditions, carry out pure CO
2with pure N
2permeance property test, wherein CO
2infiltration coefficient is 17 barrer(1 barrer=10
-10cm
3(STP) cm/ (cm
2s cmHg)), CO
2/ N
2ideal selectivity is 34.22.
embodiment 2
Take 0.6 g sulfonated polyether-ether-ketone and 8 g nitrogen, nitrogen-dimethylacetylamide is stirring at room temperature 12 h under 500 r/min magnetic agitation, and sulfonated polyether-ether-ketone is all dissolved.By sulfonation chromium organic framework material 0.06 g obtaining according to the method for embodiment 1, add 4 g nitrogen, nitrogen-dimethylacetylamide, ultrasonic 12 h, join in above-mentioned sulfonated polyether-ether-ketone solution, after 24 h, stop stirring, with copper mesh filtration, leave standstill 1 h deaeration, be poured in clean glass culture dish (Φ 100 mm), be placed in baking oven, dry 12 h at 60 ℃ and 80 ℃ respectively, obtaining thick is 65 μ m homogeneous membranes.Under room temperature, 1.5 bar conditions, carry out pure CO
2with pure N
2permeance property test, wherein CO
2infiltration coefficient is 19barrer(1 barrer=10
-10cm
3(STP) cm/ (cm
2s cmHg)), CO
2/ N
2ideal selectivity is 35.51.
embodiment 3
Take 0.6 g sulfonated polyether-ether-ketone and 8 g nitrogen, nitrogen-dimethylacetylamide is stirring at room temperature 12 h under 500 r/min magnetic agitation, and sulfonated polyether-ether-ketone is all dissolved.By sulfonation chromium organic framework material 0.09 g making according to the method for embodiment 1, add 4 g nitrogen, nitrogen-dimethylacetylamide, ultrasonic 12 h, join in above-mentioned sulfonated polyether-ether-ketone solution, after 24 h, stop stirring, with copper mesh filtration, leave standstill 1 h deaeration, be poured in clean glass culture dish (Φ 100 mm), be placed in baking oven, dry 12 h at 60 ℃ and 80 ℃ respectively, obtaining thick is 68 μ m homogeneous membranes.Under room temperature, 1.5 bar conditions, carry out pure CO
2with pure N
2permeance property test, wherein CO
2infiltration coefficient is 21 barrer(1 barrer=10
-10cm
3(STP) cm/ (cm
2s cmHg)), CO
2/ N
2ideal selectivity is 38.
embodiment 4
Take 0.6 g sulfonated polyether-ether-ketone and 8 g nitrogen, nitrogen-dimethylacetylamide is stirring at room temperature 12 h under 500 r/min magnetic agitation, and sulfonated polyether-ether-ketone is all dissolved.By sulfonation chromium organic framework material 0.12 g making according to the method for embodiment 1, add 4 g nitrogen, nitrogen-dimethylacetylamide, ultrasonic 12 h, join in above-mentioned sulfonated polyether-ether-ketone solution, after 24 h, stop stirring, with copper mesh filtration, leave standstill 1 h deaeration, be poured in clean glass culture dish (Φ 100 mm), be placed in baking oven, dry 12 h at 60 ℃ and 80 ℃ respectively, obtaining thick is 70 μ m homogeneous membranes.Under room temperature, 1.5 bar conditions, carry out pure CO
2with pure N
2permeance property test, wherein CO
2infiltration coefficient is 24 barrer(1 barrer=10
-10cm
3(STP) cm/ (cm
2s cmHg)), CO
2/ N
2ideal selectivity is 40.
comparative example 1
Take 0.6 g sulfonated polyether-ether-ketone and 12 g nitrogen, nitrogen-dimethylacetylamide is stirring at room temperature 12 h under 500 r/min magnetic agitation, macromolecule is all dissolved, obtain sulfonated polyether-ether-ketone solution, with copper mesh filtration, leave standstill 1 h deaeration, be poured in clean glass culture dish (Φ 100 mm), be placed in baking oven, dry 12 h at 60 ℃ and 80 ℃ respectively, obtaining thick is 60 μ m homogeneous membranes.Under room temperature, 1.5 bar conditions, carry out pure CO
2with pure N
2permeance property test, wherein CO
2infiltration coefficient is 16 barrer(1 barrer=10
-10cm
3(STP) cm/ (cm
2s cmHg)), CO
2/ N
2ideal selectivity is 32.69.
comparative example 2
Prepare the chromium organic framework material of particle diameter approximately 500 nanometers.Process is as follows: 4.0 g nine water chromic nitrates and 1.64 g terephthalic acid (TPA)s are added in 48 mL deionized waters and add the hydrofluoric acid that 0.2 ml mass fraction is 40%, after stirring 30min, mixed solution is transferred in reactor, after sealing, put into the constant temperature blast drying oven isothermal reaction 8h that has been heated to 220 ℃, after reaction finishes, reactor is left standstill and is cooled to room temperature, sample is through nitrogen, nitrogen-dimethyl formamide and ethanol are put into drying box in 150 ℃ of freeze-day with constant temperature 24h after fully washing, obtain green chromium organic framework material.
Take 0.6 g sulfonated polyether-ether-ketone and 8 g nitrogen, nitrogen-dimethylacetylamide, under magnetic agitation, stirring at room temperature 12 h, all dissolve macromolecule.Take above-mentioned chromium organic framework material 0.03 g making, add 4g nitrogen, nitrogen-dimethylacetylamide, ultrasonic 12h, joins in above-mentioned sulfonated polyether-ether-ketone solution, after 12h, stop stirring, with copper mesh filtration, leave standstill 1 h deaeration, be poured in clean glass culture dish (Φ 100 mm), dry 12 h at 60 ℃ and 80 ℃ respectively, obtaining thick is 63 μ m homogeneous membranes.Under room temperature, 1.5 bar conditions, carry out pure CO
2with pure N
2permeance property test, wherein CO
2infiltration coefficient is 17barrer(1 barrer=10
-10cm
3(STP) cm/ (cm
2s cmHg)), CO
2/ N
2ideal selectivity is 33.34.
comparative example 3
Take 0.6 g sulfonated polyether-ether-ketone and 8 g nitrogen, nitrogen-dimethylacetylamide, under magnetic agitation, stirring at room temperature 12 h, all dissolve macromolecule.Chromium organic framework material 0.06 g that the method for comparative example 2 is made, add 4g nitrogen, nitrogen-dimethylacetylamide, ultrasonic 12h, joins in above-mentioned sulfonated polyether-ether-ketone solution, after 12h, stop stirring, with copper mesh filtration, leave standstill 1 h deaeration, be poured in clean glass culture dish (Φ 100 mm), dry 12 h at 60 ℃ and 80 ℃, obtain thick approximately 65 μ m homogeneous membranes respectively.Under room temperature, 1.5 bar conditions, carry out pure CO
2with pure N
2permeance property test, wherein CO
2infiltration coefficient is 18 barrer(1 barrer=10
-10cm
3(STP) cm/ (cm
2s cmHg)), CO
2/ N
2ideal selectivity is 34.
comparative example 4
Take 0.6 g sulfonated polyether-ether-ketone and 8 g nitrogen, nitrogen-dimethylacetylamide, under magnetic agitation, stirring at room temperature 12 h, all dissolve macromolecule.Chromium organic framework material 0.09 g that the method for comparative example 2 is made, add 4g nitrogen, nitrogen-dimethylacetylamide, ultrasonic 12h, joins in above-mentioned sulfonated polyether-ether-ketone solution, after 12h, stop stirring, with copper mesh filtration, leave standstill 1 h deaeration, be poured in clean glass culture dish (Φ 100 mm), dry 12 h at 60 ℃ and 80 ℃ respectively, obtaining thick is 67 μ m homogeneous membranes.Under room temperature, 1.5 bar conditions, carry out pure CO
2with pure N
2permeance property test, wherein CO
2infiltration coefficient is 20 barrer(1 barrer=10
-10cm
3(STP) cm/ (cm
2s cmHg)), CO
2/ N
2ideal selectivity is 34.34.
comparative example 5
Take 0.6 g sulfonated polyether-ether-ketone and 8 g nitrogen, nitrogen-dimethylacetylamide, under magnetic agitation, stirring at room temperature 12 h, all dissolve macromolecule.Chromium organic framework material 0.12 g that the method for comparative example 2 is made, add 4g nitrogen, nitrogen-dimethylacetylamide, ultrasonic 12h, joins in above-mentioned sulfonated polyether-ether-ketone solution, after 12h, stop stirring, with copper mesh filtration, leave standstill 1 h deaeration, be poured in clean glass culture dish (Φ 100 mm), dry 12 h at 60 ℃ and 80 ℃ respectively, obtaining thick is 70 μ m homogeneous membranes.Under room temperature, 1.5 bar conditions, carry out pure CO
2with pure N
2permeance property test, wherein CO
2infiltration coefficient is 23 barrer(1 barrer=10
-10cm
3(STP) cm/ (cm
2s cmHg)), CO
2/ N
2ideal selectivity is 33.42.
Claims (3)
1. sulfonated polyether-ether-ketone/sulfonation chromium organic backbone hybridized film, a kind of sulfonated polyether-ether-ketone/sulfonation chromium organic backbone hybridized film, it is characterized in that, this sulfonated polyether-ether-ketone/sulfonation chromium organic backbone hybridized film thickness is 55 ~ 75 microns, it is to be made up of sulfonated polyether-ether-ketone and sulfonation chromium organic backbone, sulfonation chromium organic backbone particle diameter 500 nanometers, wherein sulfonated polyether-ether-ketone and sulfonation chromium organic backbone mass ratio are (0.80 ~ 0.95): (0.20 ~ 0.05) described sulfonated polyether-ether-ketone sulfonation degree is 69.4 %.
2. by a preparation method for sulfonated polyether-ether-ketone/sulfonation chromium organic backbone hybridized film described in claim 1, it is characterized in that comprising following process:
1). the preparation of sulfonation chromium organic backbone
By Cr (NO
3)
39H
2o, the aqueous solution of the mass fraction that terephthalic acid (TPA) and hydrofluoric acid are mixed with chromium ion concentration by the mol ratio of 1:1:1 between 0.8%-1.2%, solution is transferred in reactor and stirred after 30 minutes, under 220 ℃ of conditions, react 8 hours, filter, obtain green flour powder crystal, with nitrogen, nitrogen-dimethyl formamide washes away the not terephthalic acid (TPA) of complete reaction 100 ℃ of backflows, residual nitrogen in being swapped out crystal with ethanol at 78 ℃ again, nitrogen-dimethyl formamide, put into drying box in 150 ℃ of freeze-day with constant temperature 24h, remove ethanol molecule residual in crystal, obtain the chromium organic framework material of pure particle diameter 500 nanometers,
2). the chromium organic framework material that step 1) is made, mass concentration is that 98% sulfuric acid and trifluoromethanesulfanhydride anhydride are by a mole 1:3:4.5 ratio, stirring reaction 1-3h under room temperature in nitromethane, through centrifugation, absolute ethanol washing, put into drying box in 150 ℃ of freeze-day with constant temperature 24h, obtain sulfonation chromium organic framework material;
3). under stirring at room temperature, the sulfonated polyether-ether-ketone that is 69.4% by sulfonation degree joins nitrogen, is mixed with mass concentration and is 10% sulfonated polyether-ether-ketone solution in nitrogen-dimethylacetamide solvent; By sulfonated polyether-ether-ketone and step 2 in sulfonated polyether-ether-ketone solution) the sulfonation chromium organic backbone mass ratio that makes is in (0.80 ~ 0.95): (0.20 ~ 0.05), sulfonation chromium organic backbone adds in sulfonated polyether-ether-ketone, ultrasonic dispersion 12 h, leave standstill 1h deaeration, obtain sulfonated polyether-ether-ketone/sulfonation chromium organic backbone casting solution, this casting solution is poured in glass culture dish, be dried 12 hours at temperature 60 C, be dried 12 hours 80 ℃ of temperature afterwards, obtain sulfonated polyether-ether-ketone/sulfonation chromium organic backbone hybridized film.
3. by an application for the prepared sulfonated polyether-ether-ketone/sulfonation of claim 2 chromium organic backbone hybridized film, for CO
2/ N
2separation, be selectively 32 ~ 40, permeability is 16 ~ 24 barrer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410091943.XA CN103846024A (en) | 2014-03-13 | 2014-03-13 | Sulfonated polyetheretherketone/sulfonated chromium organic framework hybrid membrane, as well as preparation and applications thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410091943.XA CN103846024A (en) | 2014-03-13 | 2014-03-13 | Sulfonated polyetheretherketone/sulfonated chromium organic framework hybrid membrane, as well as preparation and applications thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103846024A true CN103846024A (en) | 2014-06-11 |
Family
ID=50854418
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410091943.XA Pending CN103846024A (en) | 2014-03-13 | 2014-03-13 | Sulfonated polyetheretherketone/sulfonated chromium organic framework hybrid membrane, as well as preparation and applications thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103846024A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104084063A (en) * | 2014-06-18 | 2014-10-08 | 天津大学 | Sulfonated poly(ether ether ketone)-amino loaded chromium organic skeleton hybrid membrane, and preparation and application thereof |
| CN109928859A (en) * | 2017-12-15 | 2019-06-25 | 万华化学集团股份有限公司 | A kind of processing method that isobutene refining kettle is residual |
| CN112574054A (en) * | 2019-09-30 | 2021-03-30 | 北京大学 | Efficient nitriding reagent and application thereof |
| CN113506904A (en) * | 2021-06-02 | 2021-10-15 | 华南理工大学 | Proton exchange membrane and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101313013A (en) * | 2005-11-25 | 2008-11-26 | Gkss-盖斯特哈赫特研究中心有限责任公司 | Polymer electrolyte membrane comprising coordination polymer |
| CN103474696A (en) * | 2013-08-27 | 2013-12-25 | 中南大学 | Organic-inorganic hybrid polymeric solid electrolyte material and application thereof |
-
2014
- 2014-03-13 CN CN201410091943.XA patent/CN103846024A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101313013A (en) * | 2005-11-25 | 2008-11-26 | Gkss-盖斯特哈赫特研究中心有限责任公司 | Polymer electrolyte membrane comprising coordination polymer |
| CN103474696A (en) * | 2013-08-27 | 2013-12-25 | 中南大学 | Organic-inorganic hybrid polymeric solid electrolyte material and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| G.FÉREY,ETAL.: ""A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area"", 《SCIENCE》, vol. 309, 23 September 2005 (2005-09-23), pages 2040 - 2043 * |
| HONG WU, ETAL.: ""Composite proton conductive membranes composed of suffocated poly(ether ether ketone) and phosphotungstic acid-loaded imidazole microcapsules as acid reservoirs"", 《JOURNAL OF MEMBRANE SCIENCE》, vol. 451, 7 October 2013 (2013-10-07), pages 74 - 84 * |
| MAARTEN G. GOESTEN,ETAL.: ""Sulfation of metal–organic frameworks: Opportunities for acid catalysis and proton conductivity"", 《JOURNAL OF CATALYSIS》, vol. 281, 24 May 2011 (2011-05-24), pages 177 - 187 * |
| 王朝阳等: ""磺酸功能化金属-有机骨架吸附脱氮性能"", 《物理化学学报》, vol. 29, 2 September 2013 (2013-09-02), pages 2422 - 2428 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104084063A (en) * | 2014-06-18 | 2014-10-08 | 天津大学 | Sulfonated poly(ether ether ketone)-amino loaded chromium organic skeleton hybrid membrane, and preparation and application thereof |
| CN104084063B (en) * | 2014-06-18 | 2016-08-17 | 天津大学 | Sulfonated polyether-ether-ketone-amino loads chromium organic backbone hybridized film and preparation and application |
| CN109928859A (en) * | 2017-12-15 | 2019-06-25 | 万华化学集团股份有限公司 | A kind of processing method that isobutene refining kettle is residual |
| CN109928859B (en) * | 2017-12-15 | 2021-07-23 | 万华化学集团股份有限公司 | Treatment method of isobutene refining kettle residues |
| CN112574054A (en) * | 2019-09-30 | 2021-03-30 | 北京大学 | Efficient nitriding reagent and application thereof |
| CN113506904A (en) * | 2021-06-02 | 2021-10-15 | 华南理工大学 | Proton exchange membrane and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106823863B (en) | Metal organic framework hybridized film, preparation method and application | |
| CN104084063A (en) | Sulfonated poly(ether ether ketone)-amino loaded chromium organic skeleton hybrid membrane, and preparation and application thereof | |
| CN104069752B (en) | Sulfonated polyether-ether-ketone-amino acid modified graphene oxide hybridized film and preparation and application | |
| CN106390768A (en) | Zeolite imidazate framework/polyamide composite membrane and preparation method thereof | |
| CN104028113B (en) | Two filling inorganic particle hybrid film and preparation method and application | |
| CN109126469B (en) | Preparation method and application of polyimide/inorganic particle pervaporation hybrid membrane | |
| CN107866154B (en) | A kind of polyimides-zinc organic backbone load graphene oxide hybridized film and preparation and application | |
| CN105289337A (en) | Crosslinking polyimide gas separation membrane and preparation method | |
| CN110951089B (en) | Method for promoting synthesis of ZIF-8 in aprotic polar solvent | |
| CN113209841B (en) | Mixed matrix membrane of aminated ZIF-8 and polyvinyl alcohol, and preparation method and application thereof | |
| CN103846024A (en) | Sulfonated polyetheretherketone/sulfonated chromium organic framework hybrid membrane, as well as preparation and applications thereof | |
| CN103554831A (en) | Sulfonated polyetheretherketone/amino-functionalized TiO2 hybrid membrane, as well as preparation and applications of hybrid membrane | |
| CN103521100B (en) | High-molecular-functional mesoporous silica hybrid membrane, preparation method and applications | |
| CN112316745B (en) | Metal-organic molecule cage complex mixed matrix membrane and preparation method and application thereof | |
| Wang et al. | Hydrogen-bonded polyamide 6/Zr-MOF mixed matrix membranes for efficient natural gas dehydration | |
| CN105694458A (en) | TiO2/fluorine-containing polyether sulphone, preparation method and hybrid ultrafiltration membrane | |
| CN110756059B (en) | Preparation method of mixed matrix membrane with porous ionic polymer as disperse phase and application of mixed matrix membrane in gas separation | |
| CN112675720B (en) | Preparation method and application of mixed matrix membrane filled with bimetallic strip material | |
| Huang et al. | Two‐dimensional microporous material‐based mixed matrix membranes for gas separation | |
| CN110479109A (en) | The preparation method for the Kynoar mixed substrate membrane containing nano-grade molecular sieve that flux is high, resistance tocrocking is strong | |
| CN112979985A (en) | Composite metal organic framework material and preparation method thereof | |
| Thomas et al. | Processing of thermally stable 3D hierarchical ZIF-8@ ZnO structures and their CO2 adsorption studies | |
| Jia et al. | In-situ interfacial crosslinking of NH2-MIL-53 and polyimide in MOF-incorporated mixed matrix membranes for efficient H2 purification | |
| CN104212154B (en) | Sulfonated polyether-ether-ketone-amination silicon dioxide microsphere hybridized film and preparation and application | |
| CN110327792B (en) | Tree-structure mixed matrix membrane constructed by bi-component nano additive and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140611 |