CN105727758A - Preparation method and application of graphene oxide composite membrane - Google Patents
Preparation method and application of graphene oxide composite membrane Download PDFInfo
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- CN105727758A CN105727758A CN201610235203.8A CN201610235203A CN105727758A CN 105727758 A CN105727758 A CN 105727758A CN 201610235203 A CN201610235203 A CN 201610235203A CN 105727758 A CN105727758 A CN 105727758A
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- 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
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—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
- B01D53/22—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
- 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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- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
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- 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
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
- B01D71/14—Esters of organic acids
- B01D71/16—Cellulose acetate
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- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
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- 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
Abstract
The invention discloses a preparation method and application of a graphene oxide composite membrane, and belongs to the technical field of gas separation membranes.The preparation method of the graphene oxide composite membrane comprises the steps that an aqueous dispersion liquid of graphene oxide is prepared through a Hummer method, and ultrasonic dispersion is conducted; metal salt or oxysalt is added, and heating and mixing are conducted; the surface of a micro-filtration membrane is covered with the prepared dispersion liquid through a vacuum filtration method; the membrane is put into a drying oven to be dried.The preparation method of the graphene oxide composite membrane has the advantages that the preparation method is simple, the thickness of the obtained membrane is smaller than 10 nm, the space between graphene sheet layers is adjustable, the obtained composite membrane is used for gas separation and has excellent comprehensive performance.Particularly, the graphene oxide composite membrane prepared from sodium tetraborate has high CO2 permeation flux and CO2/CH4 and CO2/N2 selectivity, and it is obtained through mixed gas tests under the humidifying condition that the CO2 permeation flux can reach 650 GPU, CO2/CH4 selectivity is 75, and CO2/N2 selectivity is 58.
Description
Technical field
The present invention relates to the preparation of a kind of graphene oxide composite membrane and application, belong to gas membrane Seperation Technology field.
Background technology
In recent years, along with industrial expansion, combustion of fossil fuel, create a large amount of CO2Gas.It is badly in need of the carbon trapping technique of high efficiency, low cost at present.Membrane technology gets the attention due to the advantage such as green, energy consumption is low, equipment investment is low, is one of technology being expected to extensive employing at present.At present owing to membrane material separating property is not high, limit it and develop further.Design preparation tool high osmosis and the selective membrane material of height are the focuses of research at present.For realizing the high osmosis of film and high selectivity, membrane material should possess ultra-thin separating layer structure and film pore size rule, it is easy to accomplish size is sieved.
Grapheme material is that one possesses superthin section Rotating fields, the material with carbon element mechanically and thermally having good stability.Its wide material sources, are expected to be prepared into membrane material, with large-scale application.Graphene oxide lamella is covered in the surface of micro-filtration membrane by spin coating or vacuum ultrafiltration by the preparation of current graphene film mostly.Prepared film is uncontrollable due to interlamellar spacing, and the size sieving capacity causing film is weak, selectivity is not high.Little molecule is many in film to be realized separating with physical mechanism, and the research of chemical mechanism (faciliated diffusion mechanism) is less.Need easy controlled film preparation means at present badly, Chemical Decomposition mechanism is introduced in film preparation, it is achieved graphene film permeability and optionally simultaneously promoting.
Summary of the invention
It is an object of the invention to the preparation method and application of a kind of graphene oxide composite membrane.The graphene oxide composite membrane prepared in this approach is for separating CO2/CH4、CO2/N2Mixture, has higher CO2Infiltration rate and separation factor.
A kind of graphene oxide composite membrane that the present invention proposes, key component is graphene oxide, and bivalent metal ion or oxyacid radical ion, and this composite membrane is prepared in micro-filtration membrane substrate by vacuum filtration method；Wherein, graphene oxide lamella be sized to 500nm-5 μm.
Wherein, described bivalent metal ion is Mg2+、Ca2+、Zn2+、Co2+、Ni2+And Fe2+In one, described oxyacid radical ion is B4O7 2-Or TeO3 2-；Described micro-filtration membrane material is the one in polysulfones, polyether sulfone, Kynoar and cellulose acetate, it is preferred to polyether sulfone.
The preparation method of a kind of graphene oxide composite membrane of the present invention, comprises the following steps:
(1) graphene oxide aqueous dispersions, ultrasonic disperse 2h are prepared by Hummer method；(2) the bivalent metal ion chlorate of certain mass or oxyacid sodium salt are joined obtained solution A in the graphene oxide aqueous dispersions that graphene oxide mass volume ratio is 1mg/L-50mg/L, wherein, the mass ratio of added bivalent metal ion chlorate or oxyacid sodium salt and graphene oxide is 10/1；Heating this solution A to 40 DEG C, mechanical agitation is completely dissolved to bivalent metal ion chlorate therein or oxyacid sodium salt, is cooled to room temperature；(3) micro-filtration membrane is fixed in vacuum filtration cup, the solution A that step (2) prepares is poured in vacuum filtration cup, open vacuum pump, after the complete sucking filtration of water, continue sucking filtration 20min；Film prepared by step (3) is put in baking oven and cross-links dry 2h, obtain graphene oxide composite membrane.
Graphene oxide composite membrane of the present invention is used for gas separate, is particularly well-suited to CO2/CH4, CO2/N2Separation.
It is an advantage of the current invention that: preparation method is simple, and obtained film thickness is at below 10nm, and graphene film interlamellar spacing is adjustable, obtained composite membrane separates for gas, has the combination property of excellence.Especially, graphene oxide composite membrane prepared by sodium tetraborate is used to have high CO2Permeation flux and CO2/CH4、CO2/N2Selectivity, gaseous mixture test CO under humidified condition2Permeation flux is up to 650GPU, CO2/CH4Selectivity is 75, CO2/N2Selectivity is 58.
Detailed description of the invention
A kind of graphene oxide composite membrane that the present invention proposes, key component is graphene oxide, and bivalent metal ion or oxyacid radical ion, and this composite membrane is prepared in micro-filtration membrane substrate by vacuum filtration method；Wherein, the size (owing to the plane geometric shape of graphene oxide lamella is not the circle of specification, therefore the size dimension at this place actually refers to the diameter of graphene oxide sheet layer plane shape profile circumscribed circle) of graphene oxide lamella is for 500nm-5 μm；The thickness of film is less than 10nm.Described bivalent metal ion is Mg2+、Ca2+、Zn2+、Co2+、Ni2+And Fe2+In one, described oxyacid radical ion is B4O7 2-Or TeO3 2-；Described micro-filtration membrane material is the one in polysulfones, polyether sulfone, Kynoar and cellulose acetate, it is preferable that polyether sulfone.
Preparation and the application of the above-mentioned graphene oxide composite membrane present invention proposed below in conjunction with specific embodiment are described in further detail, and the present invention is only explained by described specific embodiment, not in order to limit the present invention.
Embodiment 1, graphene oxide composite membrane preparation method, comprise the following steps:
Step one, prepared the aqueous dispersions of graphene oxide by Hummer method, graphene oxide lamella be sized to 500nm, being placed in supersonic frequency is dispersion 2h in 30kHz ultrasonic cleaning instrument；
Step 2, by MgCl2Join in the graphene oxide aqueous dispersions that graphene oxide mass volume ratio is 1mg/L and obtain solution A, wherein added MgCl2It is 10/1 with the mass ratio of graphene oxide；Heat this solution A to 40 DEG C, mechanical agitation 1h to MgCl therein2It is completely dissolved, is cooled to room temperature standby；
Step 3, polyether sulfone micro-filtration membrane is fixed in vacuum filtration cup, takes the solution A that 40ml step 2 prepares and pour in vacuum filtration cup, open vacuum pump, after the complete sucking filtration of water, continue sucking filtration 20min；
Step 4, it is put in baking oven by the film that step 3 sucking filtration is good 50 DEG C of dry 2h of crosslinking, final prepares graphene oxide composite membranes.
Graphene oxide composite membrane embodiment 1 prepared, under the dry state test condition that room temperature, test pressure are 1bar, separates CO2Volume fraction is the N of 20%2-CO2Binary gas, CO2Infiltration rate is 60GPU (1GPU=10-6cm3(STP)/(cm2ScmHg)), CO2/N2Separation factor is 20, under the same conditions, separates CO2Volume fraction is the CH of 30%4-CO2Binary gas, CO2Infiltration rate is 60GPU, CO2/CH4Separation factor is 23.
Embodiment 2, graphene oxide composite membrane preparation method, preparation process and embodiment 1 are basically identical, are different in that: salt added in step 2 is CaCl2。
Test condition is identical with embodiment 1, separates CO2Volume fraction is the N of 20%2-CO2Binary gas, CO2Infiltration rate is 52GPU, CO2/N2Separation factor is 16, under the same conditions, separates CO2Volume fraction is the CH of 30%4-CO2Binary gas, CO2Infiltration rate is 51GPU, CO2/CH4Separation factor is 13.
Embodiment 3, graphene oxide composite membrane preparation method, preparation process and embodiment 1 are basically identical, are different in that: salt added in step 2 is ZnCl2。
Test condition is identical with embodiment 1, separates CO2Volume fraction is the N of 20%2-CO2Binary gas, CO2Infiltration rate is 70GPU, CO2/N2Separation factor is 28, under the same conditions, separates CO2Volume fraction is the CH of 30%4-CO2Binary gas, CO2Infiltration rate is 72GPU, CO2/CH4Separation factor is 31.
Embodiment 4, graphene oxide composite membrane preparation method, preparation process and embodiment 1 are basically identical, are different in that: salt added in step 2 is CoCl2。
Test condition is identical with embodiment 1, separates CO2Volume fraction is the N of 20%2-CO2Binary gas, CO2Infiltration rate is 57GPU, CO2/N2Separation factor is 13, under the same conditions, separates CO2Volume fraction is the CH of 30%4-CO2Binary gas, CO2Infiltration rate is 59GPU, CO2/CH4Separation factor is 16.
Embodiment 5, graphene oxide composite membrane preparation method, preparation process and embodiment 1 are basically identical, are different in that: salt added in step 2 is NiCl2。
Test condition is identical with embodiment 1, separates CO2Volume fraction is the N of 20%2-CO2Binary gas, CO2Infiltration rate is 46GPU, CO2/N2Separation factor is 23, under the same conditions, separates CO2Volume fraction is the CH of 30%4-CO2Binary gas, CO2Infiltration rate is 49GPU, CO2/CH4Separation factor is 25.
Embodiment 6, graphene oxide composite membrane preparation method, preparation process and embodiment 1 are basically identical, are different in that: salt added in step 2 is Na2B4O7。
Test condition is unstripped gas and purges gas humidification state, separates CO2Volume fraction is the N of 20%2-CO2Binary gas, CO2Infiltration rate is 730GPU, CO2/N2Separation factor is 38, under the same conditions, separates CO2Volume fraction is the CH of 30%4-CO2Binary gas, CO2Infiltration rate is 762GPU, CO2/CH4Separation factor is 33.
Embodiment 7, graphene oxide composite membrane preparation method, preparation process and embodiment 6 are basically identical, are different in that: graphene oxide lamella used in step one is 5 μm.
Test condition is identical with embodiment 6, separates CO2Volume fraction is the N of 20%2-CO2Binary gas, CO2Infiltration rate is 650GPU, CO2/N2Separation factor is 55, under the same conditions, separates CO2Volume fraction is the CH of 30%4-CO2Binary gas, CO2Infiltration rate is 639GPU, CO2/CH4Separation factor is 53.
Embodiment 8, graphene oxide composite membrane preparation method, preparation process and embodiment 6 are basically identical, are different in that: graphene oxide lamella used in step one is 1 μm.
Test condition is identical with embodiment 6, separates CO2Volume fraction is the N of 20%2-CO2Binary gas, CO2Infiltration rate is 710GPU, CO2/N2Separation factor is 42, under the same conditions, separates CO2Volume fraction is the CH of 30%4-CO2Binary gas, CO2Infiltration rate is 662GPU, CO2/CH4Separation factor is 48.
Embodiment 9, graphene oxide composite membrane preparation method, preparation process and embodiment 7 are basically identical, are different in that: in step 4, and crosslinking temperature is 70 DEG C.
Test condition is identical with embodiment 7, separates CO2Volume fraction is the N of 20%2-CO2Binary gas, CO2Infiltration rate is 650GPU, CO2/N2Separation factor is 58, under the same conditions, separates CO2Volume fraction is the CH of 30%4-CO2Binary gas, CO2Infiltration rate is 652GPU, CO2/CH4Separation factor is 75.
The preparation method of embodiment 10 graphene oxide composite membrane, preparation process is basically identical with embodiment 7, is different in that: in step 4, and crosslinking temperature is 90 DEG C.
Test condition is identical with embodiment 7, separates CO2Volume fraction is the N of 20%2-CO2Binary gas, CO2Infiltration rate is 352GPU, CO2/N2Separation factor is 64, under the same conditions, separates CO2Volume fraction is the CH of 30%4-CO2Binary gas, CO2Infiltration rate is 357GPU, CO2/CH4Separation factor is 85.
Embodiment 11, graphene oxide composite membrane preparation method, preparation process and embodiment 9 are basically identical, are different in that: salt added in step 2 is Na2TeO3。
Test condition is identical with embodiment 6, separates CO2Volume fraction is the N of 20%2-CO2Binary gas, CO2Infiltration rate is 235GPU, CO2/N2Separation factor is 48, under the same conditions, separates CO2Volume fraction is the CH of 30%4-CO2Binary gas, CO2Infiltration rate is 246GPU, CO2/CH4Separation factor is 53.
Comparative example 1, a kind of graphene oxide composite membrane, key component is graphene oxide, and is prepared in a micro-filtration membrane substrate by vacuum filtration method, and preparation process is:
Prepared the aqueous dispersions of graphene oxide, graphene oxide lamella size 2 μm by Hummer method, being placed in supersonic frequency is dispersion 2h in 30kHz ultrasonic cleaning instrument；The micro-filtration membrane that one material is polyether sulfone is fixed in vacuum filtration cup, the aqueous dispersions taking graphene oxide above-mentioned for 40ml is poured in vacuum filtration cup, open vacuum pump, sucking filtration 20min is continued after the complete sucking filtration of water, it is put in baking oven by the film that sucking filtration is good 50 DEG C of dry 2h of crosslinking, obtains graphene oxide composite membrane.
Graphene oxide composite membrane comparative example 1 prepared, under the dry state test condition that room temperature, test pressure are 1bar, separates CO2Volume fraction is the N of 20%2-CO2Binary gas, CO2Infiltration rate is 30GPU (1GPU=10-6cm3(STP)/(cm2ScmHg)), CO2/N2Separation factor is 18, under the same conditions, separates CO2Volume fraction is the CH of 30%4-CO2Binary gas, CO2Infiltration rate is 32GPU, CO2/CH4Separation factor is 22.
Graphene oxide composite membrane comparative example 1 prepared, room temperature, test pressure are under the dry state test condition of 1bar, separate CO2Volume fraction is the N of 20%2-CO2Binary gas, CO2Infiltration rate is 85GPU (1GPU=10-6cm3(STP)/(cm2ScmHg)), CO2/N2Separation factor is 13 under the same conditions, separates CO2Volume fraction is the CH of 30%4-CO2Binary gas, CO2Infiltration rate is 88GPU, CO2/CH4Separation factor is 15.
To sum up, in preparation process of the present invention, increase with graphene oxide slice plane size, CO in film application2Infiltration rate reduce, CO2/CH4And CO2/N2Separation factor increases.Increase with crosslinking temperature, CO2Infiltration rate reduce, CO2/CH4And CO2/N2Selectivity increase.Select Na2B4O7The CO of film prepared by cross-linked graphene2Infiltration rate and CO2/CH4And CO2/N2Separation factor is all maximum, Na2TeO3Take second place.
Although above, invention has been described; but the invention is not limited in above-mentioned detailed description of the invention; above-mentioned detailed description of the invention is merely schematic; rather than it is restrictive; those of ordinary skill in the art is under the enlightenment of the present invention; without deviating from the spirit of the invention, it is also possible to make many variations, these belong within the protection of the present invention.
Claims (7)
1. a graphene oxide composite membrane, it is characterised in that key component is graphene oxide, and bivalent metal ion or oxyacid radical ion, this composite membrane is prepared in micro-filtration membrane substrate by vacuum filtration method；Wherein, graphene oxide lamella be sized to 500nm-5 μm, the thickness of film is less than 10nm.
2. graphene oxide composite membrane as claimed in claim 1, it is characterised in that described bivalent metal ion is Mg2+、Ca2+、Zn2+、Co2+、Ni2+And Fe2+In one, described oxyacid radical ion is B4O7 2-Or TeO3 2-。
3. graphene oxide composite membrane as claimed in claim 1, it is characterised in that described micro-filtration membrane material is the one in polysulfones, polyether sulfone, Kynoar and cellulose acetate.
4. one kind arbitrary in claim 1-3 as described in the preparation method of graphene oxide composite membrane, it is characterised in that comprise the following steps:
Step one, prepared graphene oxide aqueous dispersions by Hummer method, ultrasonic disperse 2h, wherein, graphene oxide lamella used be sized to 500nm-5 μm；
Step 2, bivalent metal ion chlorate or the oxyacid sodium salt of certain mass are joined obtained solution A in the graphene oxide aqueous dispersions that graphene oxide mass volume ratio is 1mg/L-50mg/L, wherein, the mass ratio of added bivalent metal ion chlorate or oxyacid sodium salt and graphene oxide is 10/1；Heating this solution A to 40 DEG C, mechanical agitation is completely dissolved to bivalent metal ion chlorate therein or oxyacid sodium salt, is cooled to room temperature；
Step 3, micro-filtration membrane is fixed in vacuum filtration cup, the solution A that step 2 prepares is poured in vacuum filtration cup, open vacuum pump, after the complete sucking filtration of water, continue sucking filtration 20min；
Step 4, film step 3 prepared are put in baking oven and cross-link dry 2-4h, obtain graphene oxide composite membrane.
5. the preparation method of graphene oxide composite membrane as claimed in claim 4, it is characterised in that in step 4, crosslinking temperature is 50-90 DEG C.
6. claim 4 or 5 preparation method prepare as described in the application of graphene oxide composite membrane, it is characterised in that this graphene oxide composite membrane is used for gas and separates.
7. the application of graphene oxide composite membrane as claimed in claim 6, it is characterised in that this graphene oxide composite membrane is used for CO2/CH4Or CO2/N2Separation.
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