CN106582328B - Composite separation membrane - Google Patents

Composite separation membrane Download PDF

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CN106582328B
CN106582328B CN201510690171.6A CN201510690171A CN106582328B CN 106582328 B CN106582328 B CN 106582328B CN 201510690171 A CN201510690171 A CN 201510690171A CN 106582328 B CN106582328 B CN 106582328B
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separation membrane
filler
molecular sieve
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CN106582328A (en
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杨维慎
班宇杰
李砚硕
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention discloses a composite separation membrane, which comprises a high polymer phase, a molecular sieve phase and a filler, wherein the molecular sieve phase consists of microporous materials which are continuously or discontinuously dispersed in the high polymer phase, and the filler is fixedly carried in a molecular sieve pore passage and partially occupies the space in a molecular sieve pore. The composite separation membrane is a three-phase composite separation membrane containing molecular sieve-filler-polymer, wherein the filler is positioned in the pore canal of the porous material and partially occupies the pore space of the porous material; the molecular sieve phase is uniformly distributed in the polymer phase, and the three phases are organically combined to form the three-phase composite separation membrane. The three-phase composite membrane has obvious molecular sieving effect on gas molecules with different sizes, and has more excellent permeability compared with a molecular sieve-polymer two-phase composite membrane and a pure polymer membrane. The significance of the actual separation process is profound.

Description

Composite separation membrane
Technical Field
The invention relates to a multi-phase high-efficiency composite separation membrane containing a microporous material.
Background
Two-phase composite membranes formed from microporous materials and polymeric materials are one of the most potential composite separation membranes in recent years. It has molecular transmission channels of two materials and unique microscopic membrane structure. Two basic parameters, permeability and separation selectivity, are commonly used in the art to measure composite membrane performance. The performance of a composite membrane is determined by the properties of both materials,
the polymer material is separated by a mixture through transporting molecules by virtue of holes formed by free volumes among chains. Thus, the permeability of the polymer film is low. When a porous molecular sieve material is doped into a polymer to make a dual-phase composite membrane, the permeability of the membrane is significantly increased. Unfortunately, however, the separation selectivity of such a two-phase composite membrane tends to not increase or even decrease compared to a pure polymer membrane, since the difference in the permeation rates of the porous molecular sieve material for different gas molecules is not significant. This greatly hinders the use of composite membranes in the field of practical separations.
The invention content is as follows:
the invention aims to provide a composite separation membrane with excellent permeability and selectivity.
The present invention first provides a composite separation membrane comprising:
a high polymer phase,
a molecular sieve phase comprised of a microporous material dispersed continuously or discontinuously in a polymer phase, and,
and the filler is supported in the pore channels of the molecular sieve and partially occupies the space in the pore space of the molecular sieve.
In another aspect, the present invention provides a method for preparing the composite separation membrane, comprising the steps of:
(1) uniformly dispersing a microporous material or a raw material for preparing the microporous material, a high polymer or a raw material for preparing the high polymer and a filler into a solvent at the temperature of-10-200 ℃, and immobilizing the filler into a pore channel of the microporous material by using an impregnation method or an in-situ synthesis method, wherein the microporous material is simultaneously dispersed in a high polymer phase to form a three-phase composite membrane solution;
wherein the mass ratio of the microporous material, the filler, the high polymer and the solvent is 1: a: b: c, a is 0.001-1000, b is 0.01-10000, and c is 0.01-5000;
(2) and (4) film forming.
The composite separation membrane is prepared by the preparation method.
The composite separation membrane of the invention is a three-phase composite separation membrane containing molecular sieve-filler-polymer, wherein the filler is positioned in the pore canal of the porous material and partially occupies the pore space of the porous material; the molecular sieve phase is uniformly distributed in the polymer phase, and the three phases are organically combined to form the three-phase composite separation membrane. The three-phase composite membrane has obvious molecular sieving effect on gas molecules with different sizes, and has more excellent permeability compared with a molecular sieve-polymer two-phase composite membrane and a pure polymer membrane.
Based on this, it is an object of a further aspect of the present invention to provide the use of the above-described composite separation membrane in gas separation. The composite separation membrane of the present invention is far-reaching in significance to the actual separation process in view of its high permeability and separation selectivity.
Drawings
The invention is shown in figure 16:
FIG. 1 is an X-ray diffraction pattern of an IL @ ZIF-8-P84 three-phase composite film.
FIG. 2 is an IL @ ZIF-8-P84 three-phase composite membrane CO2/CH4Separation performance.
FIG. 3 is an IL @ ZIF-8-P84 three-phase composite membrane CO2/N2Separation performance.
FIG. 4 is an X-ray diffraction pattern of DMF @ ZIF-108.
FIG. 5 is a thermogravimetric plot of DMF @ ZIF-108.
FIG. 6 is a DMF @ ZIF-108-PSF three-phase composite membrane H2/CH4Separation performance.
FIG. 7 is a DMF @ ZIF-108-PSF three-phase composite membrane CO2/CH4Separation performance.
FIG. 8 is an X-ray diffraction pattern of IL @ ZIF-8.
FIG. 9 is a thermogravimetric plot of IL @ ZIF-8.
FIG. 10 is IL @ ZIF-81H NMR spectrum.
FIG. 11 is an IL @ ZIF-8-PSF three-phase composite membrane CO2/CH4Separation performance.
FIG. 12 is an IL @ ZIF-8-PSF three-phase composite membrane CO2/N2Separation performance.
FIG. 13 is I2@ ZIF-108.
FIG. 14 is I2@ ZIF-108 thermogravimetric curve.
FIG. 15 is I2@ ZIF-8-PSF three-phase composite membrane CO2/CH4Separation performance.
FIG. 16 is I2@ ZIF-8-PSF three-phase composite membrane CO2/N2Separation performance.
Detailed Description
The present invention first provides a composite separation membrane comprising:
a high polymer phase,
a molecular sieve phase comprised of a microporous material dispersed continuously or discontinuously in a polymer phase, and,
and the filler is supported in the pore channels of the molecular sieve and partially occupies the space in the pore space of the molecular sieve.
In particular embodiments, the microporous material is selected from the group consisting of a silicoaluminophosphate zeolite and a metal-organic framework material; preferably a metal-organic framework material; zeolitic imidazolate framework materials are most preferred.
In a specific embodiment, the filler mentioned in the composite separation membrane of the present invention may be iodine, metal ions, metal oxide nanoparticles, metal ion complexes, ionic liquids, and organic solvent molecules having a boiling point of not lower than 100 ℃. Iodine, ionic liquid, and organic solvent molecules having a boiling point of not less than 100 ℃ are preferable.
The ionic liquid is selected from quaternary ammonium cationic ionic liquid, quaternary phosphine cationic ionic liquid, pyridine cationic ionic liquid and imidazole cationic ionic liquid. Specific examples include, but are not limited to, [ bim][Tf2N]Ionic liquids or [ bim][PF6]An ionic liquid.
The organic solvent molecules mentioned therein having a boiling point of not less than 100 ℃ are particularly preferably N, N-dimethylformamide (DMF for short),
In a specific embodiment, the polymeric phase is composed of a rubbery or glassy high molecular weight polymer.
In one embodiment, the molecular sieve phase is non-continuously and uniformly dispersed in the polymer phase. Wherein the volume of the molecular sieve phase accounts for 3-80% of the total volume of the composite membrane; preferably 5 to 30%.
In another aspect, the present invention provides a method for preparing the composite separation membrane, comprising the steps of:
(1) uniformly dispersing a microporous material or a raw material for preparing the microporous material, a high polymer or a raw material for preparing the high polymer and a filler into a solvent at the temperature of-10-200 ℃, and immobilizing the filler into a pore channel of the microporous material by using an impregnation method or an in-situ synthesis method, wherein the microporous material is simultaneously dispersed in a high polymer phase to form a three-phase composite membrane solution;
wherein the mass ratio of the microporous material, the filler, the high polymer and the solvent is 1: a: b: c, a is 0.001-1000, b is 0.01-10000, and c is 0.01-5000;
preferably, the ratio a is 0.01 to 1000, b is 0.1 to 10000, and c is 0.1 to 500;
most preferably, the ratio a is 0.01 to 10, b is 1 to 1000, and c is 1 to 100;
the dispersing process is carried out by means of stirring, and the stirring time is 60-2592000 s;
the solvent is selected from hydrocarbon, halogenated hydrocarbon, alcohol, phenol, ether, glycol ether, ketone, aldehyde, acid, ester, nitrogen-containing and sulfur-containing solvents; halogenated hydrocarbons, ketones, nitrogen-containing and sulfur-containing solvents are preferred; most preferred are chloroform, dichloromethane, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone;
(2) and (4) film forming.
The unsupported or supported composite separation membrane is prepared by conventional techniques such as pulling, spraying, spin coating, knife coating, and the like.
The starting materials for preparing the microporous materials described in the above preparation methods are selected according to the target microporous material to be prepared as generally understood in the art.
The raw materials for preparing the high polymer comprise polymer monomers, a catalyst and a cross-linking agent, and the specific selection of various raw materials is implemented according to the prior art in the field.
As an alternative embodiment, the composite separation membrane according to the present invention may also be prepared by:
(1) uniformly dispersing the microporous material or raw materials and fillers for preparing the microporous material into a solvent at the temperature of-10-200 ℃, or directly taking the fillers as the solvent and stirring for 60-2592000 s;
wherein the mass ratio of the microporous material, the filler and the solvent is 1: a: b, wherein a is 0.001-1000, and b is 0.001-5000;
preferably, a is 0.01 to 1000, and b is 0.001 to 500;
most preferably, a is 0.01 to 500, and b is 0.001 to 100;
the solvent is selected from hydrocarbon, halogenated hydrocarbon, alcohol, phenol, ether, glycol ether, ketone, aldehyde, acid, ester, nitrogen-containing and sulfur-containing solvents; halogenated hydrocarbons, alcohols, ketones, nitrogen-containing and sulfur-containing solvents are preferred; most preferably methanol, N-dimethylformamide;
(2) separating and washing the microporous material with the filler immobilized in the pore channel;
(3) dissolving a high polymer or a raw material for preparing the high polymer in a solvent to form a uniformly dispersed mixed solution;
the solvent is selected from hydrocarbon, halogenated hydrocarbon, alcohol, phenol, ether, glycol ether, ketone, aldehyde, acid, ester, nitrogen-containing and sulfur-containing solvents; halogenated hydrocarbons, ketones, nitrogen-containing and sulfur-containing solvents are preferred; most preferably chloroform, dichloromethane, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide or N-methylpyrrolidone;
(4) adding the filler-immobilized molecular sieve into the mixed solution prepared in the step (3) at the temperature of-10-200 ℃, and stirring at 100-1000 r/min to prepare a uniform three-phase composite membrane solution; stirring for 60-2592000 s;
(5) and (4) film forming.
The unsupported or supported composite separation membrane is prepared by conventional techniques such as pulling, spraying, spin coating, knife coating, and the like.
The raw materials for preparing the microporous material and the raw materials for preparing the high polymer described in the above preparation methods are also carried out according to the prior art in the related art.
The following specific examples further illustrate the invention and should not be construed as limiting it in any way.
Example 1 preparation of a ZIF-8-Ionic liquid-polyimide three-phase composite film
Zinc nitrate hexahydrate (Zn for short) as a synthetic raw material of ZIF-82+) 2-methylimidazole (mim for short), filler Ionic Liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate [ bmim][PF6]The high polymer polyimide P84 is simultaneously dissolved in DMF solvent. Wherein the mass ratio of each substance is Zn2+Mim IL: P84: DMF 1:3.5:0.5: 10: 80. the mixture was stirred at 25 ℃ for 86400 s. White solid is generated in the mixed solution and is evenly dividedDispersed in polymer phase to form homogeneous three-phase composite film solution. And (3) taking an alumina ceramic wafer as a carrier, and preparing the support type three-phase composite membrane by dipping-lifting. And (5) slowly airing the wet film at room temperature, and curing and forming.
For comparison, a ZIF-8-polyimide two-phase composite membrane was prepared at the same time. The preparation method is as follows. Zinc nitrate hexahydrate (Zn for short) as a synthetic raw material of ZIF-82+) 2-methylimidazole (mim) and high polymer polyimide P84 dissolved in DMF solvent. Wherein the mass ratio of each substance is Zn2+Mim: P84: DMF 1:3.5:10: 80. The mixture was stirred at 25 ℃ for 86400 s. White solid is generated in the mixed solution and is uniformly dispersed in the polymer phase to form uniform two-phase composite membrane solution. And (3) taking an alumina ceramic wafer as a carrier, and preparing the support type biphase composite membrane by dipping-lifting. And (5) slowly airing the wet film at room temperature, and curing and forming.
FIG. 1 shows X-ray diffraction patterns of an IL @ ZIF-8-P84 three-phase composite film and a ZIF-8-P84 two-phase composite film, in the former case, the IL occupying the space in the ZIF-8 hole scatters electrons, and the intensity of the ZIF-8 lattice diffraction peak is attenuated and even reduced to zero. FIG. 2 and FIG. 3 are IL @ ZIF-8-P84 three-phase composite membrane CO respectively2/CH4And CO2/N2The separation performance of (3). Compared with a pure P84 membrane, the gas permeability and selectivity of the three-phase composite membrane are obviously improved. And the gas permeability of the ZIF-8-P84 two-phase composite membrane is improved, and the selectivity is almost unchanged or even reduced.
Example 2 preparation of a ZIF-108-dimethylformamide-polysulfone three-phase composite membrane
Zinc nitrate hexahydrate (Zn for short) as a synthetic raw material of ZIF-1082+) 2-nitroimidazole is dissolved in dimethylformamide (abbreviated as DMF), wherein DMF is used as a filler and a solvent simultaneously. Wherein the mass ratio of each substance Zn2+Nim: DMF 1:1.0: 80. The mixture was stirred at 25 ℃ for 3600 s. The solid was centrifuged from the solvent. And washing the mixture for three times by using a DMF solvent to obtain a molecular sieve material DMF @ ZIF-108 with DMF filled in the ZIF-108 holes. Adding DMF @ ZIF-108 solid to a previously prepared Polysulfone (PSF) -chloroform (CHCl)3) Stirring the solution at 25 deg.C under high speedThe stirring speed is 500r/min, and the stirring time is 86400 s. DMF @ ZIF-108 PSF: CHCl31:10: 110. And (3) taking an alumina ceramic wafer as a carrier, and preparing the support type three-phase composite membrane by dipping-lifting. And (5) slowly airing the wet film at room temperature, and curing and forming.
For comparison, a ZIF-108-polysulfone two-phase composite membrane was prepared at the same time. The preparation method is as follows. Zinc nitrate hexahydrate (Zn for short) as a synthetic raw material of ZIF-1082+) And 2-nitroimidazole is simultaneously dissolved in dimethylformamide (DMF for short). Wherein, Zn2+Nim: DMF 1:1.0: 80. The mixture was stirred at 25 ℃ for 3600 s. The solid was centrifuged from the solvent. And (3) putting the solid material in a vacuum oven at 150 ℃ for vacuumizing for 2 days, and removing DMF filled in pores to obtain the ZIF-108 molecular sieve material with unoccupied pore channels. Adding ZIF-108 solid to a pre-prepared Polysulfone (PSF) -chloroform (CHCl)3) Stirring the solution at a high speed and a high speed at 25 ℃ for 86400s at a stirring speed of 500 r/min. ZIF-108 PSF CHCl31:10: 110. And (3) taking an alumina ceramic wafer as a carrier, and preparing the support type three-phase composite membrane by dipping-lifting. And (5) slowly airing the wet film at room temperature, and curing and forming.
FIG. 4 shows the X-ray diffraction pattern of DMF @ ZIF-108, which confirms the crystal structure of the material for long range order. FIG. 5 shows the thermogravimetric curve of DMF @ ZIF-108, from which it can be seen that the filling molar ratio of DMF in the ZIF-108 channels is ZIF-108.1.2 DMF (Table 1). FIG. 6 and FIG. 7 are respectively a DMF @ ZIF-108-PSF three-phase composite membrane H2/CH4And CO2/CH4The separation performance of (3). Compared with a pure polymer membrane, the gas permeability and selectivity of the three-phase composite membrane are obviously improved. And the ZIF-108-PSF two-phase composite membrane only has improved gas permeability and almost unchanged or even reduced selectivity.
Example 3 preparation of ZIF-8-Ionic liquid-polysulfone three-phase composite Membrane
Zinc nitrate hexahydrate (Zn for short) as a synthetic raw material of ZIF-82+) 2-methylimidazole (mim) is dissolved in Ionic Liquid (IL) 1-butyl-3-methylimidazole bistrifluoromethanesulfonylimide [ bmim][Tf2N]Among them. Here IL acts as both filler and solvent. Wherein the mass ratio of each substance is Zn2+:mim IL 1:3.5: 80. The mixture was stirred at 25 ℃ for 7200 s. The solid was centrifuged from the solvent. And washing the mixture for three times by using a methanol solvent to obtain the molecular sieve material IL @ ZIF-8 with IL filled in the holes of the ZIF-8. Adding IL @ ZIF-8 solid to a previously prepared Polysulfone (PSF) -chloroform (CHCl)3) Stirring the solution at a high speed and a high speed of 25 ℃ uniformly, wherein the stirring speed is 600r/min, and the stirring time is 86400 s. IL @ ZIF-8 PSF: CHCl31:10: 110. And (3) taking an alumina ceramic wafer as a carrier, and preparing the support type three-phase composite membrane by dipping-lifting. And (5) slowly airing the wet film at room temperature, and curing and forming.
For comparison, a ZIF-8-polysulfone two-phase composite membrane was prepared at the same time. The preparation method is as follows. Zinc nitrate hexahydrate (Zn for short) as a synthetic raw material of ZIF-82+) And 2-methylimidazole are dissolved in methanol (MeOH for short). Wherein, Zn2+Nim: MeOH: 1:3.5: 80. The mixture was stirred at 25 ℃ for 7200 s. The solid was centrifuged from the solvent. And because the solvent methanol is volatile, the MeOH in the pores of the material can be removed by completely drying at room temperature, and the ZIF-8 molecular sieve material with unoccupied pore channels is obtained. Adding ZIF-8 solid to a pre-prepared Polysulfone (PSF) -chloroform (CHCl)3) Stirring the solution at a high speed and a high speed of 25 ℃ uniformly, wherein the stirring speed is 600r/min, and the stirring time is 86400 s. ZIF-8 PSF CHCl31:10: 110. And (3) taking an alumina ceramic wafer as a carrier, and preparing the support type three-phase composite membrane by dipping-lifting. And (5) slowly airing the wet film at room temperature, and curing and forming.
FIG. 8 shows the X-ray diffraction pattern of IL @ ZIF-8, which confirms the crystal structure of the material for long range order. FIGS. 9 and 10 show the thermogravimetric curves and1from the H NMR spectrum, it was found that the filling amount of IL in the ZIF-8 channels was ZIF-8.0.235 IL (Table 1). FIG. 11 and FIG. 12 are IL @ ZIF-8-PSF three-phase composite membrane CO, respectively2/CH4And CO2/N2The separation performance of (3). Compared with a pure polymer membrane, the gas permeability and selectivity of the three-phase composite membrane are obviously improved at the same time. And the ZIF-8-PSF two-phase composite membrane only has improved gas permeability and reduced selectivity.
Example 4 preparation of ZIF-8-iodine-Silicone rubber three-phase composite film
ZIF-8 and iodine simple substance (I)2) Dissolving in ethanol (EtOH) at the same time, wherein the mass ratio of the substances is ZIF-8: I2EtOH 1:0.5: 80. The mixture was stirred at 25 ℃ for 86400 s. The solid was centrifuged from the solvent. Washing with ethanol solvent for three times to obtain ZIF-8 pore filling I2Molecular sieve material I2@ ZIF-8. Will I2@ ZIF-8 solid is added into isooctane solution containing silicon rubber, organic tin catalyst and ethyl orthosilicate cross-linking agent, and stirred uniformly at high speed at 25 ℃, the stirring speed is 600r/min, and the stirring time is 86400 s. I is2@ZIF-8:PSF:CHCl31:10: 110. And (3) taking an alumina ceramic wafer as a carrier, and preparing the support type three-phase composite membrane by dipping-lifting. And (5) slowly airing the wet film at room temperature, and curing and forming.
For comparison, a ZIF-8-silicone rubber two-phase composite membrane was prepared at the same time. The preparation method is as follows. And (3) completely drying the ZIF-8 to obtain the ZIF-8 molecular sieve material with unoccupied pore channels. Adding the ZIF-8 solid into an isooctane solution containing silicon rubber, an organotin catalyst and an ethyl orthosilicate cross-linking agent, and uniformly stirring at a high speed of 600r/min and 86400s at the temperature of 25 ℃. ZIF-8 silicone rubber isooctane 1:10: 110. And (3) taking an alumina ceramic wafer as a carrier, and preparing the support type three-phase composite membrane by dipping-lifting. And (5) slowly airing the wet film at room temperature, and curing and forming.
FIG. 13 shows I2The X-ray diffraction pattern of @ ZIF-8, which confirms the long-range ordered crystal structure of the material. FIG. 14 shows I2The thermogravimetric curve of @ ZIF-108, from which I can be learned2The filling amount in the ZIF-8 pore canal is ZIF-8.0.7I2(Table 1). FIG. 15 and FIG. 16 are respectively an I2@ ZIF-8-silicon rubber three-phase composite membrane CO2/CH4And CO2/N2Separation performance. Compared with a pure polymer membrane, the gas permeability and selectivity of the three-phase composite membrane are obviously improved at the same time. And the ZIF-8-silicon rubber two-phase composite membrane only has improved gas permeability and reduced selectivity.
TABLE 1 filling amount of filler and channel occupancy of molecular sieves
Figure BDA0000826082150000081
aThe molar ratio.

Claims (9)

1. A composite separation membrane comprising:
a high polymer phase,
a molecular sieve phase comprised of a microporous material dispersed continuously or discontinuously in a polymer phase, and,
the filler is fixedly loaded in the pore canal of the molecular sieve and partially occupies the space in the pore canal of the molecular sieve;
the microporous material is selected from metal-organic framework materials.
2. The composite separation membrane according to claim 1, wherein the filler is selected from the group consisting of iodine, metal ions, metal oxide nanoparticles, metal ion complexes, ionic liquids, and organic solvent molecules having a boiling point of not less than 100 ℃.
3. The composite separation membrane of claim 2, wherein the filler is selected from the group consisting of iodine, ionic liquids, and organic solvent molecules having a boiling point of not less than 100 ℃.
4. The composite separation membrane according to claim 3, wherein the ionic liquid is selected from the group consisting of quaternary ammonium cationic ionic liquids, quaternary phosphine cationic ionic liquids, pyridine cationic ionic liquids and imidazole cationic ionic liquids.
5. The composite separation membrane according to claim 4, wherein the filler is selected from the group consisting of iodine, N-dimethylformamide, [ bim [ ]][Tf2N]Ionic liquids or [ bim][PF6]An ionic liquid.
6. The composite separation membrane of claim 1, wherein the polymeric phase is comprised of a rubbery or glassy high molecular polymer.
7. The composite separation membrane of claim 1, wherein the molecular sieve phase is non-continuously and uniformly dispersed in the polymer phase.
8. A method for preparing the composite separation membrane of claim 1, comprising the steps of:
(1) uniformly dispersing a microporous material or a raw material for preparing the microporous material, a high polymer or a raw material for preparing the high polymer and a filler into a solvent at the temperature of-10-200 ℃, and immobilizing the filler into a pore channel of the microporous material by using an impregnation method or an in-situ synthesis method, wherein the microporous material is simultaneously dispersed in a high polymer phase to form a three-phase composite membrane solution;
wherein the mass ratio of the microporous material, the filler, the high polymer and the solvent is 1: a: b: c, a is 0.001-1000, b is 0.01-10000, and c is 0.01-5000;
(2) and (4) film forming.
9. Use of the composite separation membrane of claim 1 in gas separation.
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