CN104722215B - Preparation method of carbon dioxide separation film based on graphene material - Google Patents
Preparation method of carbon dioxide separation film based on graphene material Download PDFInfo
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- CN104722215B CN104722215B CN201410526519.3A CN201410526519A CN104722215B CN 104722215 B CN104722215 B CN 104722215B CN 201410526519 A CN201410526519 A CN 201410526519A CN 104722215 B CN104722215 B CN 104722215B
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- 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
Abstract
The invention relates to a preparation method of a carbon dioxide separation film based on a graphene material. The preparation method comprises the following steps: dispersing the graphene material into a polymer and coating on a porous carrier with a polymer to prepare a composite film; and applying the composite film to selective separation of carbon dioxide in mixed gas. The separation film ingeniously utilizes a specific molecule transmission property of the laminar graphene material and breaks through a limitation relation between the permeability and the selectivity in the carbon dioxide separation film, and a good carbon dioxide separation performance is performed. The method process is simple and economical, has a wide application range and is suitable for large-scale preparation.
Description
Technical field：
The present invention relates to a kind of preparation method of the carbon dioxide separation membrane based on grapheme material, prepared film
Can be used for the separation of carbon dioxide in gas mixture gas.
Background technology：
CO2It is a kind of main greenhouse gases.As the demand of Fossil fuel grows with each passing day, CO2Discharge capacity also drastically
Growth, the greenhouse effect for producing therewith, global warming issue are just increasingly seriously threaten the production and life of the mankind, so, subtract
Few CO2Discharge is to alleviate the maximally effective approach of global warming.The separation CO of industrial comparative maturity2Technology mainly has：Solvent
Absorption process, adsorption method of separation, Deep Cooling Method and membrane separation technique.Solvent absorption is to CO2Good separating effect, its have the disadvantage power consumption
Larger, processing cost is higher.Adsorption method of separation separates CO using solid absorbent2, its operational approach is simple, adaptable.
But which has the disadvantage that adsorption capacity is limited, substantial amounts of adsorbent is needed, frequently, automaticity requires very high adsorption-desorption.Deep cooling
Method is big due to energy consumption, and high cost is commonly available to CO in associated gas2Recovery.Compared with above-mentioned traditional separation method,
Gas membrane Seperation Technology has the advantages that simple, easily operated without phase transformation, low energy consumption, non-secondary pollution and equipment, is referred to as
Most third generation new gas isolation technics of development and application prospect.In gas membrane Seperation Technology, gas separation membrane is served
Topmost effect.At present, gas membrane Seperation Technology mainly adopts organic film material, such as polysiloxanes, polysulfones, polyacetylene, fibre
Dimension element, polyamide, polyimides, polyethers etc..Although organic membrane adds with good pliability, higher separation, excellent
Work performance, but its transmission rates is low, and non-refractory, corrosion resistance are poor.Pure organic polymer films seldom have and can surmount infiltration
The restriction of property-selection sexual balance.Inoranic membrane is being related to high temperature, has physics, the chemical property of uniqueness in the system of Korrosionsmedium
And with good permeability and selectivity, but higher manufacturing cost is the restraining factors of its large-scale application.
Graphene with the structure of its unique atomic layer, and its project electricity, calorifics and mechanical performance, not only in light
Have a wide range of applications in terms of electrical part, sensor, battery material, and huge potential value is there is also in film field.
But will be the operating condition of Graphene direct formation of film at surface more harsh, repeatability is poor, and stability is bad, and the stone of self-supporting
Black alkene material mechanicalness in actual environment is bad, causes which effectively can not apply in actual industrial.
The content of the invention：
The invention aims to improve the deficiencies in the prior art and provide a kind of titanium dioxide based on grapheme material
The preparation method of carbon gas separation membrane, the method are simple.Using the side that grapheme material is scattered in film forming in polymer
Method, with simple to operate, the advantage such as repeatability, good stability, is that one kind efficiently solves approach.
The technical scheme is that：A kind of preparation method of the carbon dioxide separation membrane based on grapheme material,
Which comprises the following steps that：
A) grapheme material is added in solvent, after being disperseed, the dispersion liquid of 0.1～3mg/ml is configured to；
B) organic polymer material is added in solvent, the solution that mass percentage concentration is 1～20% is configured to, in 70 DEG C
Heated and stirred 4～8 hours at～120 DEG C, obtain polymer solution set aside for use；
C) by step A) dispersion liquid be added to step B) polymer solution in, the heated and stirred at 70 DEG C～120 DEG C
10～16 hours, solution temperature is reduced to into standing and defoaming at 40 DEG C～60 DEG C again then, coating liquid is obtained；Wherein dispersion liquid
Addition is to control the mass ratio of grapheme material and organic polymer material for 0.1～3：100；
D) by step C) in coating liquid be coated on the side of supporter, dry naturally in atmosphere, be then heating and curing, Gu
Change obtains the carbon dioxide separation membrane based on grapheme material.
It is preferred that above-mentioned supporter is Kynoar (PVDF), polyether sulfone (PES), Polyetherimide (PEI), acetic acid fibre
Dimension plain (CA), mullite, Al2O3Or ZrO2In one or more compound support.It is preferred that supporter is shaped as
One kind of chip, tubular type or hollow fiber form.It is preferred that the average pore size of above-mentioned supporter is 20nm～2000nm.
It is preferred that above-mentioned organic polymer material is at least polyvinyl alcohol, Polyethylene Glycol, carboxymethyl cellulose, alginic acid
One kind in sodium, shitosan, polyimides, polyether co-polyamide or polydimethylsiloxane.
It is preferred that above-mentioned grapheme material is sulfhydrylation Graphene, graphene oxide, hydroxylating Graphene, carboxyl graphite
One kind in alkene or amination graphene.
It is preferred that above-mentioned solvent is the one kind in water, ethanol, DMF, DMSO, toluene or dimethylbenzene.
Grapheme material is added to into the preferred stirring of scattered mode in solvent and ultrasonic disperse in step A；It is preferred that described
Solidification temperature be 70 DEG C～120 DEG C, hardening time be 10～24 hours.
Preferred pair supporter of the present invention carries out pretreatment, and concrete grammar is to polish smooth supporting body surface, is cleaned by ultrasonic,
Its surface washing totally and is dried by deionized water again.
Beneficial effect：
Deficiency of the present invention for gas separation membrane material single varieties in the market, using new Graphene material
Material, and combine the advantage of polymeric film material, the operating condition that compensate for Graphene direct formation of film at surface is more harsh, repeatability compared with
Difference, not pressure in actual environment, mechanical performance is low, the shortcomings of stability is bad.Meanwhile, by adjusting a series of of coating liquid
Parameter and the associated operating steps of membrane process are applied controlling the thickness and compactness extent of seperation film, the gas of Effective Regulation composite membrane
Body separating property, to adapt to different separation requirements.The inventive method process is simple economy, it is applied widely.
Description of the drawings：
Transmission electron microscope photos of the Fig. 1 for composite membrane obtained in example 3.
Specific embodiment：
Embodiment 1
1) the carboxylated Graphenes of 0.1g are weighed to be added in 50ml deionized waters, carboxyl graphite are caused through stirring ultrasound
Alkene is fully dispersed in water.
2) 4g Polyethylene Glycol is added in 80g ethanol, heated and stirred 6 hours at 70 DEG C, solution left standstill is stand-by.
3) aqueous dispersions of the carboxylated Graphene in 1) are added into step 2) in polyglycol solution, at 70 DEG C plus
Thermal agitation 10 hours, then solution temperature is reduced to into standing and defoaming at 50 DEG C, coating liquid is obtained.
4) by step 3) in coating liquid be coated on average pore size be 20nm chip Al2O3The side of supporter, in atmosphere
Naturally dry, solidification temperature is 80 DEG C, and the time is 24 hours, obtains the gas separation membrane based on grapheme material.
Composite membrane obtained in this example is determined for CO2/N2、CO2/CH4And CO2/H2Gas separating property, when temperature is 25
DEG C, when pressure is 0.3MPa, CO2Permeability be 70Barrer, CO2/N2、CO2/CH4And CO2/H2Selectivity be respectively 82,
19 and 9.
Embodiment 2
1) 0.15g hydroxylating Graphenes are weighed to be added in 50ml DMF, carboxylated Graphene are caused through stirring ultrasound
It is fully dispersed in DMF.
2) 10g carboxymethyl celluloses are added in 40g toluene, heated and stirred 5 hours at 80 DEG C, solution left standstill is stand-by.
3) the DMF dispersion liquids of the hydroxylating Graphene in 1) are added into step 2) in cmc soln, in 90
Heated and stirred 15 hours at DEG C, then solution temperature is reduced to into standing and defoaming at 60 DEG C, coating liquid is obtained.
4) by step 3) in coating liquid be coated on average pore size be 200nm chip ZrO2The side of supporter, in air
Middle to dry naturally, solidification temperature is 90 DEG C, and the time is 10 hours, obtains the gas separation membrane based on grapheme material.
Composite membrane obtained in this example is determined for CO2/N2、CO2/CH4And CO2/H2Gas separating property, when temperature is 35
DEG C, when pressure is 0.2MPa, CO2Permeability be 82Barrer, CO2/N2、CO2/CH4And CO2/H2Selectivity be respectively 65,
16 and 8.
Embodiment 3
1) 0.005g sulfhydrylation Graphenes are weighed to be added in 50ml DMSO, sulfydryl graphite are caused through stirring ultrasound
Alkene is fully dispersed in DMSO.
2) 3g sodium alginates are added in 30g dimethylbenzene, heated and stirred 4 hours at 110 DEG C, solution left standstill is stand-by.
3) the DMSO dispersion liquids of the sulfhydrylation Graphene in 1) are added into step 2) in sodium alginate soln, at 85 DEG C
Heated and stirred 12 hours, then solution temperature is reduced to into standing and defoaming at 50 DEG C, coating liquid is obtained.
4) by step 3) in coating liquid be coated on average pore size be 1000nm tubular type mullite supporter side, in sky
Naturally dry in gas, solidification temperature is 75 DEG C, the time is 15 hours.Obtain the gas separation membrane based on grapheme material.
Composite membrane obtained in this example is determined for CO2/N2、CO2/CH4And CO2/H2Gas separating property, when temperature is 55
DEG C, when pressure is 0.1MPa, CO2Permeability be 55Barrer, CO2/N2、CO2/CH4And CO2/H2Selectivity be respectively 55,
15 and 7.5.Fig. 1 shows the transmission electron microscope photo of the composite membrane prepared by example 3.Can be clearly from figure
Go out, grapheme material is presented distinctive layer structure in polymeric film, so as to be effectively improved molecule transmission wherein
Speed, improves the separating property of the carbon dioxide of composite membrane.
Embodiment 4
1) 0.05g amination graphenes are weighed to enter in 50ml ethanol, causes amination graphene complete through stirring ultrasound
It is scattered in ethanol entirely.
2) 5g shitosans are added in 25g deionized waters, heated and stirred 4 hours at 95 DEG C, solution left standstill is stand-by.
3) alcohol dispersion liquid of the amination graphene in 1) is added into step 2) in chitosan solution, at 100 DEG C
Heated and stirred 12 hours, then solution temperature is reduced to into standing and defoaming at 40 DEG C, coating liquid is obtained.
4) by step 3) in coating liquid be coated on average pore size be 500nm hollow fiber form PEI supporters side,
Naturally dry in air, solidification temperature is 100 DEG C, and the time is 20 hours, obtains the gas separation membrane based on grapheme material.
Composite membrane obtained in this example is determined for CO2/N2、CO2/CH4And CO2/H2Gas separating property, when temperature is 55
DEG C, when pressure is 0.1MPa, CO2Permeability be 55Barrer, CO2/N2、CO2/CH4And CO2/H2Selectivity be respectively 55,
15 and 7.5.
Embodiment 5
1) 0.15g graphene oxides are weighed to enter in 50ml deionized waters, causes graphene oxide complete through stirring ultrasound
It is scattered in deionized water entirely.
2) 5g polydimethylsiloxane is added in 120g toluene, heated and stirred 8 hours at 90 DEG C, solution left standstill is treated
With.
3) the deionized water dispersion liquid of the graphene oxide in 1) is added into step 2) inside polydimethylsiloxane it is molten
In liquid, heated and stirred 16 hours at 100 DEG C, then solution temperature is reduced to into standing and defoaming at 40 DEG C, coating liquid is obtained.
4) by step 3) in coating liquid be coated on average pore size be 1900nm chip PVDF supporters side, in air
Middle to dry naturally, solidification temperature is 120 DEG C, and the time is 24 hours, obtains the gas separation membrane based on grapheme material.
Composite membrane obtained in this example is determined for CO2/N2、CO2/CH4And CO2/H2Gas separating property, when temperature is 25
DEG C, when pressure is 0.2MPa, CO2Permeability be 60Barrer, CO2/N2、CO2/CH4And CO2/H2Selectivity be respectively 72,
17 and 10.
Embodiment 6
1) 0.002g hydroxylating Graphenes are weighed to enter in 20ml ethanol, causes hydroxyl graphite complete through stirring ultrasound
It is scattered in ethanol.
2) 1.5g polyimides are added in 148.5g DMF, heated and stirred 6 hours at 90 DEG C, solution left standstill is stand-by.
3) alcohol dispersion liquid of the hydroxylating Graphene in 1) is added into step 2) inside polyimide solution in, in 75
Heated and stirred 14 hours at DEG C, then solution temperature is reduced to into standing and defoaming at 50 DEG C, coating liquid is obtained.
4) by step 3) in coating liquid be coated on average pore size be 1500nm doughnut PES supporters side,
Naturally dry in air, solidification temperature is 100 DEG C, and the time is 12 hours, obtains the gas separation membrane based on grapheme material.
Composite membrane obtained in this example is determined for CO2/N2、CO2/CH4And CO2/H2Gas separating property, when temperature is 25
DEG C, when pressure is 0.3MPa, CO2Permeability be 85Barrer, CO2/N2、CO2/CH4And CO2/H2Selectivity be respectively 85,
21 and 11.
Embodiment 7
1) the carboxylated Graphenes of 0.05g are weighed to enter in 50ml toluene, causes hydroxyl graphite complete through stirring ultrasound
It is scattered in ethanol.
2) 3g shitosans are added in 150g deionizations, heated and stirred 5 hours at 70 DEG C, solution left standstill is stand-by.
3) the toluene dispersion liquid of the carboxylated Graphene in 1) is added into step 2) inside chitosan solution in, in 90 DEG C
Lower heated and stirred 10 hours, then solution temperature is reduced to into standing and defoaming at 60 DEG C, coating liquid is obtained.
4) by step 3) in coating liquid be coated on average pore size be 1000nm chip ZrO2The side of supporter, in air
Middle to dry naturally, solidification temperature is 110 DEG C, and the time is 24 hours, obtains the gas separation membrane based on grapheme material.
Composite membrane obtained in this example is determined for CO2/N2、CO2/CH4And CO2/H2Gas separating property, when temperature is 45
DEG C, when pressure is 0.3MPa, CO2Permeability be 105Barrer, CO2/N2、CO2/CH4And CO2/H2Selectivity be respectively
65th, 16 and 8.5.
Claims (4)
1. based on grapheme material carbon dioxide separation membrane preparation method, which comprises the following steps that：
A) grapheme material is added in solvent, after dispersion, the dispersion liquid of 0.1～3mg/ml is configured to；Described stone
During black alkene material is sulfhydrylation Graphene, graphene oxide, hydroxylating Graphene, carboxylated Graphene or amination graphene
It is a kind of；
B) by organic polymer material add solvent in, be configured to the solution that mass percentage concentration is 1～20%, in 70 DEG C～
Heated and stirred 4～8 hours at 120 DEG C, obtain polymer solution set aside for use；Described organic polymer material is at least poly- second
Enol, Polyethylene Glycol, carboxymethyl cellulose, sodium alginate, shitosan, polyimides, polyether co-polyamide or poly dimethyl silicon
One kind in oxygen alkane；
C) by step A) dispersion liquid be added to step B) polymer solution in, at 70 DEG C～120 DEG C heated and stirred 10～
16 hours, solution temperature is reduced to into standing and defoaming at 40 DEG C～60 DEG C again then, coating liquid is obtained；The wherein addition of dispersion liquid
It is 0.1～3 to measure as the ratio for controlling grapheme material and organic polymer material quality：100；
D) by step C) in coating liquid be coated on the side of supporter, dry naturally in atmosphere, be then heating and curing, solidify
To the carbon dioxide separation membrane based on grapheme material；Wherein described solidification temperature is 70 DEG C～120 DEG C, hardening time
For 10～24 hours.
2. preparation method according to claim 1, is characterized in that described supporter is at least Kynoar, polyethers
Sulfone, Polyetherimide, cellulose acetate, mullite, Al2O3Or ZrO2In one kind.
3. preparation method according to claim 1, it is characterized in that described supporter average pore size be 20nm～
2000nm；One kind for being shaped as chip, tubular type or hollow fiber form of the supporter.
4. preparation method according to claim 1, it is characterized in that described solvent be water, ethanol, DMF, DMSO, toluene or
One kind in dimethylbenzene.
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| WO2012177033A2 (en) * | 2011-06-20 | 2012-12-27 | 주식회사 엘지화학 | Reverse osmosis membrane having superior salt rejection and permeate flow, and method for manufacturing same |
| US8979978B2 (en) * | 2012-01-26 | 2015-03-17 | Empire Technology Development Llc | Graphene membrane with regular angstrom-scale pores |
| CN102600734B (en) * | 2012-03-27 | 2014-12-10 | 南京工业大学 | Enhanced graphene oxide hollow fiber composite membrane and preparation method thereof |
| CN102688707A (en) * | 2012-05-23 | 2012-09-26 | 哈尔滨工业大学 | Preparation method for graphene oxide/polyvinylidene fluoride composite ultrafiltration membrane |
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| CN104069752B (en) * | 2014-06-27 | 2016-08-24 | 天津大学 | Sulfonated polyether-ether-ketone-amino acid modified graphene oxide hybridized film and preparation and application |
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