CN114602337A - Mixed matrix gas separation membrane, preparation method and application thereof in ethane-ethylene separation - Google Patents
Mixed matrix gas separation membrane, preparation method and application thereof in ethane-ethylene separation Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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Classifications
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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
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
-
- 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
-
- 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
-
- 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
- B01D71/028—Molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/144—Purification; Separation; Use of additives using membranes, e.g. selective permeation
Abstract
The invention relates to a mixed matrix gas separation membrane, a preparation method and application thereof in ethane-ethylene separation, belonging to the technical field of membrane separation. A mixed matrix gas separation membrane comprising a polymer, and UTSA-280 nanoparticles mixed in the polymer, the polymer being a polyimide-based polymer, the membrane material exhibiting excellent selectivity and permeability for ethylene/ethane separation. The invention also provides a method for predicting the permeability coefficient of the mixed matrix membrane prepared by UTSA-280 under different polyimide matrix conditions, and the method can predict the gas permeability of the prepared separation membrane according to the permeability of different matrixes.
Description
Technical Field
The invention relates to a mixed matrix gas separation membrane, a preparation method and application thereof in ethane-ethylene separation, belonging to the technical field of membrane separation.
Background
Compared with the traditional separation technology, the membrane separation process is regarded as a novel separation technology with development prospect in the petrochemical separation process by people due to the characteristics of convenient operation, small occupied area of equipment, easy integration, energy conservation, consumption reduction and the like. Taking an industrial production process of ethylene as an example, long-chain alkane passes through a steam cracking furnace to generate a large amount of mixed gas of ethylene and ethane. If the traditional low-temperature rectification technology is adopted to separate the two, the operation is required to be carried out at the temperature of minus 160 ℃, and the energy consumption is much higher than that of the membrane process. Therefore, the development of advanced membrane materials for C2H4/C2H6 separations has received extensive attention and has made significant progress in recent years. Currently, polymer membrane materials take absolute advantage in the market, but are limited by the trade-off effect between permeability coefficient and selectivity, and separation of ethylene and ethane by polymer membranes is very open to the forefront.
In recent years, the development of high-performance nano-filler particles is diversified, and particularly, the successive emergence of Metal Organic Framework (MOF) and Graphene Oxide (GO) materials, and the influence of a mixed matrix membrane on the high-performance nano-filler particles is greatly developed. Long et al [1] prepared by incorporating M-MOF-74(M ═ Mg, Mn, Ni and Co) into 6FDA-DAM polymers, using the interaction between ethylene molecules and unsaturated metal sites to improve the separation ability of the membrane from ethylene/ethane. Meanwhile, the unsaturated metal sites enhance the interaction between the filler particles and the polymer phase, thereby improving the plasticization resistance of the mixed matrix membrane.
Despite some success in mixed matrix membranes, there are still some mixed matrix membranes with good phase interfaces that have not been improved in separation performance. At this time, another important factor: matching of the gas transport properties of the filler particles and the polymer phase needs to be taken into account. Reference herein to "transport properties" includes both permeability coefficient and selectivity. In most cases, the pore structure is such that the selectivity of the nano-filler particles is higher than that of the polymer matrix. Thus, the transport property matching problem is generally manifested in permeability coefficientAnd (5) carrying out the following steps. Koros et al [2-3 ]]On a 4A molecular sieveIt is recognized in the design and manufacture of mixed matrix membranes that filler particles having a low permeability coefficient can impede the gas transport rate of the polymer in the mixed matrix membrane and thereby reduce the gas permeability coefficient of the mixed matrix membrane as a whole.
[1]Bachman J E,Smith Z P,Li T,Xu T,Long J R.Enhanced ethylene separation and plasticization resistance in polymer membranes incorporating metal–organic framework nanocrystals.Nature Materials.2016;15(8):845-849.
[2]Zimmerman C M,Singh A,Koros W J.Tailoring mixed matrix composite membranes for gas separations.Jouranl of Membrane Science.1997;137(1-2):145-154.
[3]Mahajan R,Koros W J.Factors Controlling Successful Formation of Mixed-Matrix Gas Separation Materials.Industrial&Engineering Chemistry Research.2000;39(8):2692-2696.
Disclosure of Invention
One aspect of the present invention is to provide a UTSA-280/6FDA type polyimide mixed matrix membrane for ethylene/ethane separation based on molecular sieving effect, which exhibits excellent selectivity and permeability for ethylene/ethane separation.
Another aspect proposes a method for predicting the permeability coefficient of a mixed matrix membrane prepared from UTSA-280 under different polyimide matrix conditions, which is capable of predicting the gas permeability of the prepared separation membrane based on the permeability of the different matrices.
Another aspect proposes a method for calculating a gas diffusion coefficient in a membrane in a separation process.
A mixed matrix gas separation membrane comprising a polymer and UTSA-280 nanoparticles mixed in the polymer.
The concentration of the UTSA-280 nanoparticles in the polymer ranges from 0.5 to 40 wt%, preferably ranges from 5 to 30 wt%, and more preferably ranges from 10 to 25 wt%.
The polymer is a polyimide-based polymer.
The preparation method of the polyimide polymer comprises the following steps:
1) mixing hexafluoro dianhydride and a monomer in an organic solvent for reaction; the monomer is selected from one or the mixture of two of 2,4, 6-trimethyl-1, 3-phenylenediamine or 3, 5-diaminobenzoic acid;
2) adding acetic anhydride, and carrying out imidization reaction on the reactant in the step 1) under the action of a catalyst;
3) the reaction mixture was brought into contact with methanol to cause phase inversion, thereby obtaining a polyimide-based polymer.
The concentration of the total amount of the hexafluorodianhydride and the monomer in the organic solvent is 10 to 30 wt%.
The molar ratio of the hexafluorodianhydride to the monomer ranges from 0.8 to 1.2: 1.
the monomer is obtained by mixing 2,4, 6-trimethyl-1, 3-phenylenediamine and 3, 5-diaminobenzoic acid, and the molar ratio of the two is 3: (1.5-2.5).
The catalyst is triethylamine.
The preparation method of the mixed matrix gas separation membrane comprises the following steps:
dispersing UTSA-280 powder in a solvent to obtain a first solution;
dispersing a polymer in a solvent to obtain a second solution;
and uniformly mixing the two solutions, coating the mixture on a substrate, drying, and drying to obtain the separation membrane.
The concentration of the UTSA-280 powder in the first solution is 1-10 wt%.
The concentration of the polymer in the first solution is 10-30 wt%.
The solvent is tetrahydrofuran.
The mixed matrix gas separation membrane described above is in C2H4And C2H6Use in separation.
The application also comprises a process of calculating the diffusion coefficient of the components in the separation membrane; the step of calculating the diffusion coefficient comprises:
Di=Pi/Si;
pi is the permeability coefficient of the i component, Di is the diffusion coefficient of the i component, and Si is the solubility of the i component;
ciis the amount of gas adsorbed per unit mass of membrane material, fiIs the fugacity of component i;
kD,iis the Henry coefficient of component i, c'H,iIs langmuir saturation constant, b is langmuir interaction coefficient.
The application also comprises a process for predicting the permeability of the separation membrane, and the predicting the permeability of the two-phase permeability coefficient matched mixed matrix membrane comprises the following steps:
wherein, PpIs the permeability coefficient of the polymer phase, PsIs the permeability coefficient of the filling particles in the mixed matrix membrane,is the volume fraction of filler particles incorporated in the mixed matrix membrane.
When the prediction of the permeability of the mixed matrix membrane with filler particles far below the permeability coefficient of the polymer phase comprises:
wherein, PpIs the permeability coefficient of the polymer phase and,is the volume fraction of filler particles incorporated in the mixed matrix membrane.
The permeability coefficient of the polymer phase is determined by the following method:
dispersing a polymer in a solvent, coating the obtained solution on a substrate, drying, and drying to obtain a separation membrane; determining the separation membrane pair C2H4And C2H6The mixed gas was separated and calculated by the following formula:
wherein P is C2H4Dp/dt is the slope of the change in osmotic pressure (from instrumental testing), l is the membrane thickness, V is the permeate gas volume, a is the membrane area, T is the temperature, and Δ p is the transmembrane pressure difference.
Advantageous effects
UTSA-280 is a MOF material with a one-dimensional rigid channel structure.
Two high-performance 6FDA type polyimides with different permeability coefficients are selected: 6FDA-DAM and 6FDA-DAM DABA (3:2) as polymer phases. We have found that the two mixed matrix membranes exhibit diametrically opposed mixed matrix effects, a phenomenon that further justifies the importance of matching transport properties, particularly permeability coefficients.
Drawings
Fig. 1, morphology of (a) UTSA-280 crystals and (b) milled UTSA-280 particles. (c) FT-IR spectra of UTSA-280 and squaric acid. (d) C2H4(red open circles) and C2H6(black solid squares) single component adsorption isotherm of milled UTSA-280 particles at 35 ℃ from 0 to 5 bar.
FIG. 2, (a-c) SEM pictures of 6FDA-DAM: DABA (3:2) pure membrane, (d-f)21.80 wt% UTSA-280/6FDA-DAM: DABA (3:2), and (g-I)28.39 wt% UTSA-280/6FDA-DAM: DABA (3:2)
FIG. 3 (a) XRD patterns and (b) TGA plots of 6FDA-DAM: DABA (3:2) and its mixed matrix membranes with different UTSA-280 loadings.
FIG. 4 UTSA-280/6FDA-DAM: DABA (3:2) Mixed matrix Membrane C at different loadings2H4/C2H6Pure gas permeability.
FIG. 5 (a) C of pure 6FDA-DAM: DABA (3:2) membranes and mixed matrix membranes of varying loadings thereof2H4And (b) C2H6Adsorption isotherms.
FIG. 6, (a) C2H4/C2H6Solubility and diffusivity of; (b) c2H4/C2H6Adsorption and diffusion selectivity in a 6FDA-DAM: DABA (3:2) membrane and its mixed matrix membrane at 2.5bar and 35 ℃.
FIG. 7, equimolar C2H4/C2H6 mixed gas separation performance, using 21.80 wt% UTSA-280/6FDA-DAM: DABA (3:2) mixed matrix membrane (a) at different feed pressures of 35 ℃ and (b) at a temperature of 2.5 bar.
FIG. 8, C of 21.80 wt% UTSA-280/6FDA-DAM DABA (3:2) Mixed matrix Membrane between lnP and 1/T at different temperatures2H4And C2H6And (4) linearly fitting the graph.
FIG. 9, UTSA-280/6FDA-DAM Mixed matrix Membrane at different loads experiment and Maxwell Limit prediction C2H4/C2H6Pure gas separation performance.
FIG. 10, C of UTSA-280/6FDA-DAM Mixed matrix Membrane and UTSA-280/6FDA-DAM: DABA (3:2) Mixed matrix Membrane2H4Permeability and C2H4/C2H6Selectivity, and Maxwell prediction of UTSA-280, UTSA-280/6FDA-DAM Mixed matrix membranes and UTSA-280/6FDA-DAM: DABA (3:2) Mixed matrix membranes.
FIG. 11, 6 FDA-polyimide matrix best matching UTSA-280 phase in permeability as predicted by Maxwell model.
FIG. 12, lg P (C2H4) and lg C2H4/C2H6Graph relating to DABA content.
Detailed Description
EXAMPLE 1 preparation of two polyimide hybrid matrices
The reactive monomers employed include: hexafluoro dianhydride (6FDA), 2,4, 6-trimethyl-1, 3-phenylenediamine (DAM), 3, 5-diaminobenzoic acid (DABA);
the synthesis of two polyimide substrates 6FDA-DAM DABA (3:2) and 6FDA-DAM was carried out by condensation of a dianhydride (6FDA) with a diamine (DAM, DABA).
DABA 3:2, 6 molar ratio of the total of FDA, DAM and DAMA 1: 1; in 6FDA-DAM, the molar ratio of 6FDA to DAM is 1: 1;
specifically, a stoichiometric amount of the monomers was dissolved in NMP solution (the total monomer concentration was controlled to 20 wt%) and added to N2The reaction was carried out at 5 ℃ for 24 hours under a purge to obtain a high-viscosity polyamic acid (PAA) solution. Triethylamine catalyzed the chemical imidization of PAA in the presence of acetic anhydride (polymer mass: acetic anhydride mass ═ 1:2) for 24h (25 ℃). Finally, the resulting solution is converted to polymer by a phase inversion process in methanol. The polymer was washed and soaked thoroughly with methanol and then dried under vacuum at 200 ℃ overnight. Another polyimide, 6FDA-DABA, was also synthesized according to this procedure.
EXAMPLE 2 preparation of pure Polymer films
For both polymers prepared in example 1, a pure polyimide polymer film was prepared and the polyimide was dried under vacuum at 120 ℃ overnight and dissolved in tetrahydrofuran to form a 20 wt% solution in a vial. The vial was placed on a rolling mixer overnight to allow the polyimide to dissolve completely without any air bubbles. After that, the resulting polyimide solution was poured onto a glass plate covered with a PTFE coating, and then knife-coated with a doctor blade. The formed film was dried at room temperature overnight and then heated in a vacuum oven at 100 ℃ for 2 hours before testing.
Example 3 preparation of Mixed matrix Membrane
The preparation of UTSA-280 powder was performed in the literature. (Lin R-B, Li L, Zhou H-L, et al, molecular scaling of ethylene from ethylene using a vertical metal-organic frame. Nature materials.2018; 17(12):1128-1133.) the specific steps are:
mixing squaric acid C4H2O4(5.00g,43.86mmol) and NaOH (3.51g,87.75mmol) were mixed in 250mL of water to obtain Na2C4O4. Then, 75mL of Na was added over 10 minutes at room temperature2C4O4(1.58g, 10mmol) of aqueous solution with 60mLCa (NO)3)2·4H2Aqueous O (7.08g, 30mmol) was mixed to yield UTSA-280 immediately. Then, the crystals were filtered, then washed thoroughly with water and dried under air. Prior to the adsorption test, the crystal samples were activated under vacuum at 100 ℃ for 3 hours.
For the UTSA-280/polyimide mixed matrix membrane, a quantity of pre-treated UTSA-280 powder was dispersed in THF with magnetic stirring to form a 5 wt% dispersion and stirred for 24 hours. Simultaneously, a polyimide/THF solution was prepared as described above. The filler suspension and the polymer solution were then mixed homogeneously and the concentration of the particles in the polymer was adjusted in the experiment. The preparation and activation process of the mixed matrix membrane is consistent with that of a pure polyimide membrane.
Performance test method
In this work, membrane separation performance was examined by pure and mixed gas permeation tests. The permeability coefficient of the pure gas is measured by a constant volume variable pressure method. After activation, the membrane was sandwiched between aluminum foil and nonwoven in the test cell. The entire apparatus was then evacuated overnight until the leak gas permeability was two orders of magnitude lower than that of the slow composition fraction (ethane). A certain amount of C2H4Or C2H6Pure gas (transmembrane pressure Δ p of 2.5bar) was flowed upstream. The permeability coefficient test was performed at least 5 hours later to ensure that the membrane reached steady state. By definition, the gas permeability coefficient can be determined by the constant volume pressure swing method by the following equation.
Wherein P is the gas permeability coefficient (Barrer)=10-10cm3(STP)·cm·cm-2·s-1·cmHg-1) Dp/dt is the slope of the change in osmotic pressure (from instrumental testing), l is the membrane thickness, V is the permeate gas volume, A is the membrane area, T is the temperature, Δ p is the transmembrane pressure differential, αijIs the selectivity in the ideal case, defined by the formula:
pi and Pj are the permeability coefficients of the two gases, respectively.
Mixed gas (C)2H4/C2H650/50 vol%) permeation testing was similar to pure gas operation except that the permeate components needed further analysis by gas chromatography (Agilent 8890 GC). In addition, the stage cut-off (defined as the flow rate ratio of permeate to feed) was kept below 1% to eliminate concentration polarization.
The relationship between permeability coefficient and temperature can be expressed by the arrhenius equation:
p is the gas permeability coefficient, P0Is a pre-exponential factor, EaR is the gas permeation activation energy, R is the gas constant, and T is the temperature in degrees Kelvin.
Taking the logarithm of both sides of equation (3), the equation becomes the following form:
According to the solution diffusion theory, the permeability coefficient (P) can be regarded as the product of the solubility (S) and the diffusion coefficient (D). Here we used the gas adsorption test to determine the solubility of the membrane and thus to reverse the diffusion coefficient of the membrane. The single-component adsorption isotherm was determined using BELSORP-HP.
The solubility is defined as:
ciis the concentration of adsorbed gas, fiIs the fugacity of component i. A dual adsorption model can be used to describe this adsorption behavior:
kD,iis the Henry coefficient of component i, c'H,iIs langmuir saturation constant, b is langmuir interaction coefficient.
Characterization of materials
The crystals of UTSA-280 (a in FIG. 1) were obtained as colorless rods, the morphology and the crystal size of which were consistent with those in the literature. It is clear that the as-synthesized crystals cannot be incorporated directly into the film due to the unsatisfactory particle size (50-100 μm long). Too large a filler is liable to cause phase defects or to cause high transmission resistance due to the increase in film thickness required for defect-free morphology. To reduce the filler size, the synthesized UTSA-280 crystals were ground at low temperature provided by liquid nitrogen to maintain their crystal structure. As shown in fig. 1b, SEM images show that a substantial reduction in particle size below 1 μm is beneficial for filler dispersion and elimination of interfacial defects. The XRD pattern of the synthesized and milled UTSA-280 crystals was consistent with the results in the literature, confirming that the phase purity and size of our product maintained a good topology after processing (b of fig. 3).
Gas adsorption Performance test
The gas adsorption isotherms were collected from 0 to 5bar at 35 ℃ taking into account the permeation conditions of the membrane. As expected, the milled UTSA-280 particles exhibited higher C than ethane2H4Capacity, thus showing better C2H4/C2H6Adsorption componentAnd (d) from the action (fig. 1). UTSA-280 particles adsorbed 39.34cm at 2.5bar (transmembrane pressure of permeation)3/gC2H4And 8.44cm3(ii) in terms of/g. This property is attributed to the molecular sieving effect provided by the fine rigid cylindrical channels, their precise cross-sectional areaIs located atAndin the meantime. However, there is a clear difference between the adsorption properties of our milled particles and the crystals reported in the literature. The most intuitive phenomenon is that the milled UTSA-280 particles have a non-negligible C2H6Capacity, whereas the samples in the literature exclude almost all C in the wells2H6A molecule. This is due to the essential requirement of the mixed matrix membrane for sub-micron fillers, which require milling, which may destroy the original fine-structured crystals to some extent. On the other hand, 6FDA based polyimide films generally require drying at high temperatures to remove the solvent, and UTSA-280 fillers should also be subjected to such treatment. However, it has been found that relatively harsh activation conditions (e.g., high temperature or excessive vacuum) can break down the precise pore structure, resulting in loss of molecular sieving efficiency, particularly for small size particles. It is well known that a high performance dispersed phase is a prerequisite for successful mixing of the matrix film. In this respect, the actual separation properties of the filler after the necessary post-treatment processes (e.g. milling or activation) should be of interest when selecting the dispersed phase.
C2H4And C2H6Penetration test
Pure C2H4And C2H6Permeation tests were performed on 6FDA-DAM: DABA (3:2) membranes and their mixed matrix membranes with various UTSA-280 loadings. As expected, the addition of UTSA-280 induced better mixed matrix effects with increasing loading while enhancing C2H4Permeability coefficient and C2H4/C2H6And (4) selectivity. At a load of 21.80 wt% UTSA-280, C2H4Permeability and C2H4/C2H6The selectivity peaks were 6.49Barrer and 4.94, respectively. This further confirms that UTSA-280 constructs mixed matrix membranes as a dispersed phase to achieve high efficiency C2H4/C2H6Potential for separation. However, when the loading is higher than 21.8 wt%, C2H4/C2H6Selectivity tends to decrease disadvantageously, while C2H4The permeability continues to rise. The compromise in selectivity of the mixed matrix membrane at high loading may be due to the presence of subtle interfacial defects that may not be revealed by SEM images.
Establishment of prediction model
To reveal the intrinsic cause of improved separation performance, the gas permeability coefficient was divided into the product of solubility and diffusivity according to the solution diffusion model. Notably, fig. 6 shows that the mixed matrix membrane exhibits increased C with increased UTSA-280 doping2H4Adsorption capacity. This phenomenon is, of course, attributed to the excellent C of UTSA-2802H4Adsorption capacity. However, C of the mixed matrix membrane was compared with that of the 6FDA-DAM: DABA (3:2) pure membrane2H6The capacity showed no significant change.
To reveal the specific solubility (S) and diffusivity (D) under the test conditions, adsorption data were collected from 0 to 5bar at 35 ℃. The adsorption concentration is then derived from the fitted isotherm curve from the adsorption data to determine the value of solubility S. And fitting the adsorption isotherm by adopting a dual-mode model. The fitting parameters are shown in table 1. The Langmuir volume parameter c 'of the mixed matrix film to ethylene can be found'HHigher than 6FDA-DAM DABA (3:2) pure membrane and significant with increasing load, which means UTSA-280 vs C2H4Has preferential adsorption capacity. In contrast, introduction of UTSA-280 resulted in c'H(C2H6) Is decreased, indicating that it is a pair C2H6Effective rejection of (1). Furthermore, with UTSA-280 loadingIncrease of (A), C2H6K of (a)DIncrease indicates C of mixed matrix membrane2H6The adsorption behavior gradually follows henry's law.
TABLE 16 FDA-DAM DABA (3:2) membranes and C of the mixed matrix membranes of different loadings thereof2H4/C2H6Parameters of a dual mode adsorption model
The corresponding diffusion coefficient (D) was calculated according to the solution-diffusion model. FIG. 6 summarizes C of 6FDA-DAM: DABA (3:2) membranes and their mixed matrix membranes2H4And C2H6Solubility and diffusion coefficient, the optimum loading was 21.8 wt%. It is clear that with the addition of UTSA-280, C2H4Is improved in solubility, and C2H6The solubility of UTSA-280 was maintained, confirming that C was present in the sample2H4Preferential adsorption of (1). However, the gas diffusivity in the UTSA-280/6FDA-DAM: DABA (3:2) mixed matrix membrane decreased. This may be due to UTSA-280 pore sizeLess than 6FDA-DAM: DABA (3:2) As a result, the adsorption selectivity was significantly improved, which mainly contributes to the improvement of the osmotic selectivity of the UTSA-280/6FDA-DAM: DABA (3:2) mixed matrix membrane.
Equimolar C was performed on a 21.80 wt% UTSA-280/6FDA-DAM: DABA (3:2) mixed matrix membrane at 35 ℃ and 2.5bar2H4/C2H6And (4) testing the mixed gas. Permeability coefficient of ethylene and C2H4/C2H6The selectivity was lower than that of the pure gas test, which is probably due to C2H4And C2H6As a result of the contention transmission. Operating temperature and pressure are two key factors that affect the actual performance of the membrane. As shown in a of fig. 7, the change in permeability with pressure can be divided into two stages. In the first stage, the permeability decreases with increasing feed pressure, which is consistent with the prediction of the dual mode adsorption and transport model. Thereafter, a rise in permeability coefficient was observed due to the plasticizing effect induced by the highly condensable C2 molecule. The plasticization of the UTSA-280/6FDA-DAM: DABA (3:2) mixed matrix membrane occurred at 15 bar.
As shown in b of FIG. 7, C2H4And C2H6The permeability coefficient of (a) gradually increases with increasing temperature. This indicates that temperature-accelerated gas diffusion dominates the final permeability, although gas adsorption is reduced. According to the Arrhenius equation, C2H4And C2H6The activation energies of the transport processes were 14.49kJ/mol and 17.77kJ/mol, respectively (FIG. 8). C2H4Lower activation energy of (B) indicates a ratio of C2H6More readily penetrate the membrane.
6FDA-DAM is a more osmotic polymer matrix than 6FDA-DAM DABA (3:2) because of the larger inter-chain distanceIndicating that the segment stack is loose. C of the prepared 6FDA-DAM pure membrane at 35 ℃ and 2.5bar2H4Permeability coefficient of 108.1Barrer, C2H4/C2H6The selectivity was 2.62. However, addition of UTSA-280 did not improve C2H4/C2H6But even lower C with increasing load2H4Permeability coefficient of (a).
The invention adopts a Maxwell model to analyze the phenomenon.
In combination with the above, it can be seen that this is due to the permeability mismatch between UTSA-280 and 6 FDA-DAM. More specifically, perhaps the UTSA-280 phase itself has significant transport resistance, forcing gas molecules to pass only through the polymer phase in the UTSA-280/6FDA-DAM mixed matrix membrane.The invention also provides a prediction method based on permeability, which must obtain C of UTSA-280 filler phase2H4/C2H6Permeability performance, this performance was determined using Maxwell's model.
As is well known, maxwell models were originally proposed to evaluate the dielectric properties of composite materials and were then considered as an effective tool for predicting the performance of mixed matrix membranes. The transport equation in the mixed matrix membrane is as follows:
PMMMis the permeability coefficient, P, of the mixed matrix membranepIs the permeability coefficient of the polymer phase, PsIs the permeability coefficient (P) of the packed particlesMMM、PpObtained by reverse calculation),is the volume fraction of filler particles incorporated in the mixed matrix membrane. Given the significant permeability coefficient difference with 6FDA-DAM, UTSA-280 packing may introduce significant resistance, thereby impeding gas permeation through the UTSA-280 channels. To demonstrate this argument, we calculated the theoretical minimum limit of permeability in mixed matrix membranes by Maxwell model. By "limit" it is assumed that the permeability coefficient of the filler phase is much smaller than the permeability coefficient of the polymer phase (by far smaller is meant that the difference is at least 2 orders of magnitude), i.e. Ps<<Pp. In this case, Maxwell's equation can be simplified to the following form:
according to the equation, C in the mixed matrix membrane with different loading amounts is obtained2H4Permeability coefficient and C2H4/C2H6Minimum value of selectivity. As shown in FIG. 9 and Table 1, C2H4/C2H6The lower prediction limit of the permeability coefficient is consistent with the experimental result. UTSA-280 phase C was back-calculated using permeability coefficient data for UTSA-280/6FDA-DAM: DABA (3:2) mixed matrix membranes2H4/C2H6Permeability coefficient: c2H4Permeability coefficient of 8.5Barrer, C2H4/C2H6The permeability was 15.45. As expected, the UTSA-280 filler is on the same order of magnitude as compared to 6FDA-DAM: DABA (3:2), but has a much lower permeability coefficient (C) than the 6FDA-DAM matrix2H4Permeability coefficient of 108.1 Barrer). As shown in FIG. 10, different loadings of UTSA-280/6FDA-DAM or UTSA-280/6FDA-DAM: DABA (3:2) mixed matrix membrane for the permeable performance filler and 6FDA-DAM or 6FDA-DAM: DABA (3:2) matrix were predicted by Maxwell's model based on the permeability characteristics of UTSA-280. Generally, Maxwell's predictions are in good agreement with the experimental results of UTSA-280 mixed matrix membranes. Notably, the 6FDA-DAM: DABA (3:2) mixed matrix membrane became more permeable and selective, while the 6FDA-DAM mixed matrix membrane became more impermeable with increasing UTSA-280 loading.
The above results indicate that a good match in permeability coefficient between the filler and the matrix is a key factor for successful mixing of the matrix membrane. However, sometimes molecular sieve fillers exhibit excellent selectivity with low permeability coefficients, and thus it may not achieve a synergistic effect with high permeability coefficient polymers. Therefore, in developing or selecting filler particles for a mixed matrix membrane, both transport resistance and separation selectivity must be considered.
In view of permeability coefficient matching issues, here we tried to predict the best 6 FDA-polyimide matrix in terms of permeability coefficient for UTSA-280 filler. A series of 6FDA type polyimide pure membranes were fabricated and permeation tested: 6FDA-DAM, 6FDA-DAM: DABA (3:2) and 6 FDA-DABA. As shown in FIG. 11, the ethylene permeability coefficient of the 6 FDA-polyimide film was higher with increasing DAM fraction, while C was higher2H4/C2H6The selectivity decreases, which is determined essentially by the increase in the chain spacing. 6FDADAM DABA (x: y) polyimide permeability performance is related by linear fitting of experimental points. Maxwell's model was used to predict the permeation performance of a mixed matrix membrane composed of UTSA-280 and a selected polyimide on the hypothetical line. Thus, various UTSA-280/6 FDA-polyimide mixed matrix membrane permeance properties were obtained at different loadings. By comparing the performance of each mixed matrix membrane at the same UTSA-280 loading, a 6FDA type polyimide matrix with the best match in permeability coefficient was identified, with an ethylene permeability coefficient of 3.00Barrer, C2H4/C2H6The selectivity was 4.02. Such an optimal matrix can be obtained by adjusting the stoichiometry of the DAM and DABA monomers. As shown in FIG. 12, the optimum ratio of DAM to DABA is represented by lg P (C)2H4) And lg (C)2H4/C2H6) And determining the relationship graph of the content of the DABA. In view of the derivation, the optimum DABA content was found to be about 60 wt%. In addition, the prediction method provides guidance for developing an optimal filler/matrix permeability match.
Claims (10)
1. A mixed matrix gas separation membrane comprising a polymer and UTSA-280 nanoparticles mixed in the polymer.
2. The mixed matrix gas separation membrane of claim 1, wherein the concentration of UTSA-280 nanoparticles in the polymer is in the range of 0.5 to 40 wt%, preferably in the range of 5 to 30 wt%, and more preferably in the range of 10 to 25 wt%.
3. The mixed matrix gas separation membrane of claim 1, wherein the polymer is a polyimide-based polymer; the preparation method of the polyimide polymer comprises the following steps:
1) mixing hexafluoro dianhydride and a monomer in an organic solvent for reaction; the monomer is selected from one or a mixture of two of 2,4, 6-trimethyl-1, 3-phenylenediamine or 3, 5-diaminobenzoic acid;
2) adding acetic anhydride, and carrying out imidization reaction on the reactant in the step 1) under the action of a catalyst;
3) the reaction mixture was brought into contact with methanol to cause phase inversion, thereby obtaining a polyimide-based polymer.
4. The mixed matrix gas separation membrane according to claim 1, wherein the concentration of the total amount of the hexafluorodianhydride and the monomer in the organic solvent is 10 to 30 wt%; the molar ratio of the hexafluorodianhydride to the monomer ranges from 0.8 to 1.2: 1; the monomer is obtained by mixing 2,4, 6-trimethyl-1, 3-phenylenediamine and 3, 5-diaminobenzoic acid, and the molar ratio of the two is 3: (1.5-2.5); the catalyst is triethylamine.
5. A method of producing a mixed matrix gas separation membrane according to claim 1, comprising the steps of:
dispersing UTSA-280 powder in a solvent to obtain a first solution;
dispersing a polymer in a solvent to obtain a second solution;
and uniformly mixing the two solutions, coating the mixture on a substrate, drying, and drying to obtain the separation membrane.
6. The method of preparing a mixed matrix gas separation membrane according to claim 5, wherein the concentration of the UTSA-280 powder in the first solution is 1 to 10 wt%; the concentration of the polymer in the first solution is 10-30 wt%, and the solvent is tetrahydrofuran.
7. The mixed matrix gas separation membrane of claim 1 at C2H4And C2H6Use in separation.
8. The use of claim 7, further comprising the step of calculating the diffusion coefficient of the component in the separation membrane; the step of calculating the diffusion coefficient comprises:
Di=Pi/Si;
pi is the permeability coefficient of the i component, Di is the diffusion coefficient of the i component, and Si is the solubility of the i component;
ciis the amount of gas adsorbed per unit mass of membrane material, fiIs the fugacity of component i;
kD,iis the Henry coefficient of component i, c'H,iIs langmuir saturation constant, b is langmuir interaction coefficient.
9. The use of claim 7, further comprising predicting the permeability of a separation membrane, wherein predicting the permeability of a two-phase permeability coefficient-matched mixed matrix membrane comprises:
10. The use of claim 9, wherein predicting the permeability of the mixed matrix membrane when the filler particles are substantially below the permeability coefficient of the polymer phase comprises:
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115090265A (en) * | 2022-06-30 | 2022-09-23 | 太原理工大学 | Preparation method of refinery dry gas ethylene high-efficiency adsorbent |
CN115746318A (en) * | 2022-10-27 | 2023-03-07 | 南京工业大学 | Metal-organic framework nanosheet and preparation method and application thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110639475A (en) * | 2019-10-10 | 2020-01-03 | 太原理工大学 | UTSA-280 adsorbent material large-batch synthesis and forming method |
CN112156660A (en) * | 2020-09-25 | 2021-01-01 | 南京工业大学 | Metal organic framework M-gate mixed matrix membrane and preparation and application thereof |
CN113522064A (en) * | 2021-08-24 | 2021-10-22 | 天津工业大学 | Preparation method of novel MOF-based hydrogel gas separation membrane |
-
2022
- 2022-03-04 CN CN202210213497.XA patent/CN114602337A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110639475A (en) * | 2019-10-10 | 2020-01-03 | 太原理工大学 | UTSA-280 adsorbent material large-batch synthesis and forming method |
CN112156660A (en) * | 2020-09-25 | 2021-01-01 | 南京工业大学 | Metal organic framework M-gate mixed matrix membrane and preparation and application thereof |
CN113522064A (en) * | 2021-08-24 | 2021-10-22 | 天津工业大学 | Preparation method of novel MOF-based hydrogel gas separation membrane |
Non-Patent Citations (3)
Title |
---|
GONGPING LIU等: "Zeolite-like MOF nanocrystals incorporated 6FDA-polyimide mixed-matrix membranes for CO2/CH4 separation", JOURNAL OF MEMBRANE SCIENCE * |
JIAQI LIU等: "Ultrathin rigid UTSA-280/PEI-HPAN hybrid membranes with enhanced organic dye nanofiltration performance", JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING * |
冯孝权;刘金盾;张亚涛;: "基于MOFs的混合基质膜在C_3H_6/C_3H_8分离中的研究进展", 膜科学与技术 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115090265A (en) * | 2022-06-30 | 2022-09-23 | 太原理工大学 | Preparation method of refinery dry gas ethylene high-efficiency adsorbent |
CN115746318A (en) * | 2022-10-27 | 2023-03-07 | 南京工业大学 | Metal-organic framework nanosheet and preparation method and application thereof |
CN115746318B (en) * | 2022-10-27 | 2023-08-04 | 南京工业大学 | Metal-organic framework nano-sheet and preparation method and application thereof |
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