CN115198530A - MOF composite fiber membrane and preparation and application thereof - Google Patents

MOF composite fiber membrane and preparation and application thereof Download PDF

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CN115198530A
CN115198530A CN202210820718.XA CN202210820718A CN115198530A CN 115198530 A CN115198530 A CN 115198530A CN 202210820718 A CN202210820718 A CN 202210820718A CN 115198530 A CN115198530 A CN 115198530A
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mof
composite fiber
solution
spinning
polylactic acid
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CN115198530B (en
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刘宇清
周宁
郑帅
董伊航
张克勤
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Suzhou Best Color Nanotechnology Co ltd
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Suzhou Best Color Nanotechnology Co ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • B01J35/40—
    • B01J35/59—
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/005—Synthetic yarns or filaments
    • D04H3/009—Condensation or reaction polymers
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/005—Synthetic yarns or filaments
    • D04H3/009—Condensation or reaction polymers
    • D04H3/011—Polyesters
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/14—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic yarns or filaments produced by welding
    • D04H3/153—Mixed yarns or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/38—Polyurethanes
    • 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 belongs to the field of composite fiber materials, and particularly relates to an MOF composite fiber membrane and preparation and application thereof. The method comprises the steps of mixing polylactic acid and MOF powder for spun-bonding, simultaneously carrying out solution blowing spinning on polyurethane spinning solution, carrying out counter-spinning by two processes, forming a composite fiber layer by a collecting roller, depositing MOF substances on the surface of the composite fiber layer, and carrying out hot rolling to obtain the MOF composite fiber membrane. The composite fiber is used as a matrix layer to bear mechanical support, and the MOF layer is used as a gas selective filter layer, so that the gas separation capability is improved, and the mechanical property is improved.

Description

MOF composite fiber membrane and preparation and application thereof
Technical Field
The invention belongs to the field of composite fiber materials, and particularly relates to an MOF composite fiber membrane and preparation and application thereof.
Background
Carbon dioxide as (CO) 2 ) The capture, utilization and sequestration of major greenhouse gases and important carbon resources has been a challenge for human sustainable development. Compared with the traditional CO (carbon monoxide) method such as pressure swing adsorption method, low-temperature separation method and the like 2 Compared with the separation method, the membrane separation technology has the advantages of high efficiency, easy coupling, low cost and the like in CO 2 The capture aspect has competitive prospect. In various types of CO 2 In the separation membrane, metal organic framework Materials (MOFs) are considered as materials with great potential in various fillers due to unique properties, and have the characteristics of large specific surface area, high porosity, adjustable chemical function and good compatibility with polymers.
Related researchers have studied the adsorption of MOF and fiber composite materials, for example, patent CN202010010896.7 provides a structural design and a preparation method of a composite membrane for selective separation of ultra-high carbon dioxide gas, the membrane of the present invention is structurally designed as a three-layer composite membrane, a PAN fiber membrane is used as a matrix layer as a mechanical support layer, a porous MOF layer has gas selective permeation capability, a polymer layer enables the composite membrane to have good mechanical properties, and the PAN fiber is prepared by electrostatic spinning, so that the mechanical properties of the membrane still need to be further improved. Patent CN201810657028.0 provides a preparation method of a metal organic framework material/alginate fiber cloth (MOFs/AFC) composite membrane, which is characterized in that alginate fibers are prepared by extracting sodium alginate from seaweed, a continuous and compact MOF membrane grows by taking the alginate fibers as a substrate, and uniform metal nucleation sites can be provided for target MOFs by utilizing the replaceability of metal ions of a special eggshell structure in the alginate fibers after metal ion exchange. When the MOF/AFCs are used as membranes for gas separation, the MOF/AFCs show higher flux for H, CO, N and CH. But the mechanical property of the fiber is poor, and the fiber is difficult to be used as mechanical support. For example, patent CN201710365208.7 provides a preparation method of a metal-organic framework fiber membrane, which realizes the preparation of MOF fiber membranes with different metal centers, ligands and structures, and has strong versatility, and the prepared MOF fiber membrane has the advantages of no polymer support, high MOF loading capacity and the like, thereby improving the adsorption separation performance and the catalytic performance of the fiber membrane. By using metal oxide fibers as the converted MOF fiber membrane, there is a deficiency in the mechanical properties of the fiber membrane.
Disclosure of Invention
The invention aims to solve the problems and provides an MOF composite fiber membrane and preparation and application thereof.
According to the technical scheme of the invention, the preparation method of the MOF composite fiber membrane comprises the following steps,
s1: carrying out spun-bonding by taking a mixture of polylactic acid master batches and MOF powder as a spun-bonding raw material to obtain polylactic acid fibers;
meanwhile, carrying out solution blowing spinning by taking a polyurethane solution as a spinning solution to obtain polyurethane fibers;
s2: compounding the polylactic acid fibers and the polyurethane fibers to form a composite fiber layer;
s3: spraying a solution for synthesizing MOF particles on the surface of the composite fiber layer, and depositing an MOF material to obtain an MOF composite fiber layer;
s4: rolling the MOF composite fiber layer to obtain an MOF composite fiber material;
s5: and carrying out hot rolling treatment on the MOF composite fiber material to obtain the MOF composite fiber membrane.
According to the invention, polylactic acid and MOF powder are mixed to serve as a mechanical support layer, and after spun-bonded, polylactic acid fibers are left with residual temperature to play a certain bonding role in polyurethane solution blow-jet spinning.
Specifically, the size of the MOF powder is 450-700nm, and the size of the deposited MOF material is 100-250nm.
Further, in the mixture of the polylactic acid master batch and the MOF powder, the molar ratio of the polylactic acid master batch to the MOF powder is 11:1-2.
Further, in step S1, the concrete operation of the spun-bonding is as follows: uniformly mixing the polylactic acid master batch and the MOF powder, and adding the mixture into a screw extruder for extrusion to obtain a solution; feeding the melt into a spinning manifold through a metering pump for spinning; and (3) leading the silk obtained by spinning to enter an airflow drafting device for airflow drafting to obtain the polylactic acid fiber.
Specifically, in the steps, the rotating speed of a metering pump is 10-20r/min, the spinning temperature is 165-190 ℃, the drafting frequency is 35-55Hz, and the drafting distance is 1-2m.
Further, the solvent of the polyurethane solution is DMF (N, N-dimethylformamide), dimethylacetamide or dimethylsulfoxide, and the concentration of the polyurethane solution is 8-13wt%.
Further, in the step S1, the air pressure of the solution blow-spinning is 0.3-0.55MPa, the flow rate is 3-8mL/h, and the receiving distance (the distance from the collecting roller) is 40-80cm.
Furthermore, the diameter of the polylactic acid fiber is 1000-1200nm, and the diameter of the polyurethane fiber is 600-700nm.
Further, the MOF powder is Cu-BTC MOF powder, and the size of the MOF powder is 500-650nm.
Further, cu-BTC is composed of Cu (NO) 3 ) 2 ·3H 2 O, 1,3, 5-benzenetricarboxylic acid (BTC) and ethanol, wherein Cu (NO) 3 ) 2 ·3H 2 The molar ratio of O to 1,3, 5-benzenetricarboxylic acid (BTC) is 9:4-5.
Specifically, the preparation of Cu-BTC MOF powder is as follows: adding Cu (NO) 3 ) 2 The solution is dropwise added into BTC solution and fully stirred; at room temperature (2)Stirring for 3-6 hours at 5 +/-5 ℃, collecting precipitate, washing for 3-6 times by using ethanol, removing unreacted ions, and drying the precipitate in a hot air oven at 110-130 ℃ for 10-20 hours to obtain Cu-BTC MOF powder.
Further, the solution for synthesizing the MOF particles is a solution for synthesizing ZIF-8, and the size of the synthesized ZIF-8 is 100-200nm.
Further, the solution for synthesizing the MOF particles comprises Zn (NO) 3 ) 2 ·6H 2 O, 2-methylimidazole and methanol, of which Zn (NO) 3 ) 2 ·6H 2 The molar ratio of O to 2-methylimidazole is 1:2-3.
Specifically, in step S3, the spraying process is as follows: adding Zn (NO) 3 ) 2 ·6H 2 The O solution is filled in one device, the 2-methylimidazole and methanol solutions are respectively sprayed in the other device, and the distance between the two devices and the collecting roller is 40-80cm. The solutions in the two devices are subjected to MOF reaction on the surface of the composite fiber layer to deposit MOF materials.
Further, in the step S4, the MOF composite fiber layer is rolled up by a collecting roller, and the rotating speed of the collecting roller is 10-20 r.min -1 。
Furthermore, the number of the MOF composite fiber layers in the MOF composite fiber material is 900-1500, namely the number of winding turns is 900-1500; preferably 900 to 1200 layers, and more preferably 900 to 1000 layers.
Further, in the step S5, the pressure of the hot rolling treatment is 90-110N/mm.
Further, in the step S5, the hot rolling treatment further includes a drying treatment, wherein the drying is performed in a hot air oven at a temperature of 100 to 120 ℃.
Specifically, the device adopted by the method can comprise a screw extruder, a metering pump, a spinning box body, an air flow drafting device, a collecting roller, a solution spraying device and a solution blowing and spraying spinning device.
The second aspect of the invention provides the MOF composite fiber membrane prepared by the preparation method.
Further, the thickness of the MOF composite fiber membrane is 0.5-1.2mm, and preferably 0.6-1mm.
In a third aspect, the invention provides the MOF composite fiber membrane in CO 2 Application in catalytic separation.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the MOF fiber composite membrane prepared by the invention has a multilayer structure, composite fibers are used as a mechanical supporting layer, and two MOF layers are used as gas selective separation capability;
the polylactic acid and polyurethane fibers selected by the invention have a microporous structure and are matched with the MOF layer, so that the gas separation capacity is improved;
the invention compounds the fiber obtained by spun-bonding and the fiber obtained by solution blowing spinning, the fiber of the spun-bonding is left with residual temperature and combined with the fiber obtained by solution blowing spinning to reduce the use of adhesive and carry out volatilization treatment on the solvent in the solution blowing spinning.
Drawings
FIG. 1 is a schematic view of an apparatus for carrying out the method of the present invention.
FIG. 2 is a schematic structural diagram of a MOF fiber composite membrane of the present invention.
Description of the reference numerals: 101-screw extruder, 102-metering pump, 103-spinning box, 104-air drafting device, 105-collecting roller, 106-solution spraying device, 107-solution blowing spinning device, 201-Cu-BTC MOF particles, 202-polyurethane fibers, 203-polylactic acid fibers and 204-ZIF-8MOF particles.
Detailed Description
The present invention is further described below in conjunction with the drawings and the embodiments so that those skilled in the art can better understand the present invention and can carry out the present invention, but the embodiments are not to be construed as limiting the present invention.
The apparatus used in the production method in the following examples is shown in FIG. 1, and includes a screw extruder 101, a metering pump 102, a spinning beam 103, an air draft device 104, a collecting roller 105, a solution spray device 106, and a solution blow-spinning device 107.
Wherein, the screw extruder 101 is used for extruding the spun-bonded raw material, the extruded spun-bonded raw material enters the metering pump 102 and enters the spinning manifold 103 under the control of the metering pump 102, the spun-bonded raw material is spun through a spinneret plate of the spinning manifold 103 and then enters the air flow drafting device 104 to spin the slender filaments under the action of high-speed air flow;
the solution blow-spinning device 107 is used for spinning the solution blow-spinning raw material; the collecting roller 105 is used for simultaneously collecting the spun filaments obtained from the spun-bonded raw material and the spun yarn (counter-spun) obtained from the solution-blown spinning raw material, and the solution spraying device 106 sprays the solution for synthesizing the MOF particles onto the surface of the composite layer obtained from the counter-spun.
Example 1MOF composite fibrous Material preparation
Polylactic acid master batches (purchased from Shanghai canal materials science and technology force supplier brand PM 4025) and prepared Cu-BTC powder are uniformly mixed and added into a screw extruder 101, melt is sent into a spinning box 103 by a metering pump 102 through screw extrusion and is spun by a spinneret plate, and the melt enters an air flow drafting device 104 to spin slender filaments under the action of high-speed air flow. And simultaneously mixing polyurethane (purchased from Shenzhen Shenda Sandy plastics Limited under the brand 1164D) with a DMF solvent to obtain a spinning solution, carrying out solution blowing spinning by a solution blowing spinning device 107, carrying out counter-spinning by two spinning processes, compounding the spun yarns into a film by a collecting roller 105, putting the prepared ZIF-8 solution into two solution spraying devices 106, spraying the solution on the surface layer of the composite fiber layer, rotating the collecting roller 1000 times to obtain 1000 layers of MOF composite fiber materials, carrying out hot rolling treatment until the ZIF-8 is fully reacted, obtaining a thin composite film, and drying by a hot air oven to obtain a finished product, wherein the thickness of the finished product is 0.6mm.
Wherein the molar ratio of the polylactic acid master batch to the MOF powder is 11:2, the spinning temperature is 180 ℃, the drafting frequency is 55Hz, the drafting distance is 2m, and the rotating speed of a collecting roller is 10 r.min -1 The rotating speed of the metering pump is 10r/min.
The solvent of the polyurethane solution adopts DMF, the concentration of the spinning solution is 10 percent, the solution is adopted for blowing and spinning, the air pressure is 0.4MPa, the flow rate is 5mL/h, and the receiving distance is 50cm.
The diameter of the polylactic acid fiber is 1000nm, and the diameter of the polyurethane fiber is 650nm.
The MOF material is Cu-BTC with the size of 550nm; ZIF-8 with the size of 200nm.
The solution used for the preparation of Cu-BTC is Cu (NO) 3 ) 2 ·3H 2 O, 1,3, 5-benzenetricarboxylic acid (BTC) and ethanol, wherein Cu (NO) 3 ) 2 ·3H 2 O:1,3, 5-benzene tricarboxylic acid (BTC) molar ratio of 9:4. adding Cu (NO) 3 ) 2 The solution was added dropwise to the BTC solution, with thorough stirring. Stirring at room temperature for 4 hours, collecting precipitate, washing with ethanol for 3 times, removing unreacted ions, and drying the precipitate in a hot air oven at 120 ℃ for 12 hours to obtain Cu-BTC powder.
The solution used for preparing ZIF-8 is Zn (NO) 3 ) 2 ·6H 2 O, 2-methylimidazole and methanol, in which Zn (NO) 3 ) 2 ·6H 2 O: the molar ratio of 2-methylimidazole is 1:2.
the MOF prepared solution was held in the solution spray apparatus at a distance of 50cm from the collection roller.
The pressure of the hot rolling treatment was 100N/mm.
And after the MOF reaction is finished, drying in a hot air oven at 110 ℃.
The gas separation performance of the membrane is tested by a gas separation performance testing device, and the CO is tested under the conditions of 35 ℃ and 0.1MPa 2 Transmission coefficient 425barrer, for N 2 Transmittance of 2.8barrer for CH 4 The transmittance is 3.5barrer, CO is obtained 2 /N 2 The selectivity is 150,CO 2 /CH 4 The selectivity was 120.
Example 2MOF composite fiber Material preparation
On the basis of example 1, the number of times of rotation of the collecting roller was adjusted to 900 times, and the thickness of the finished film was 0.5mm.
The gas separation performance of the membrane is tested by a gas separation performance testing device, and the CO is tested under the conditions of 35 ℃ and 0.1MPa 2 Transmittance of 394barrer, for N 2 Transmittance of 2.7barrer for CH 4 The transmittance is 3.4barrer, CO is obtained 2 /N 2 Selectivity was 146,CO 2 /CH 4 The selectivity was 115.
Example 3MOF composite fiber Material preparation
The number of times of rotation of the collecting roller was adjusted to 1500 times on the basis of example 1, and the thickness of the finished film was 0.9mm.
The gas separation performance of the membrane is tested by a gas separation performance testing device, and the CO is tested under the conditions of 35 ℃ and 0.1MPa 2 Transmittance 346barrer, for N 2 Transmittance of 2.6barrer for CH 4 The transmittance is 3.4barrer, CO is obtained 2 /N 2 Selectivity of 133,CO 2 /CH 4 The selectivity was 101.
Example 4MOF composite fiber Material preparation
The polylactic acid master batches and the prepared Cu-BTC powder are uniformly mixed and added into a screw extruder 101, and the melt is sent into a spinning box 103 by a metering pump 102 through screw extrusion, spun by a spinneret plate and enters an airflow drafting device 104 to spin slender filaments under the action of high-speed airflow. Simultaneously, mixing polyurethane and a DMF solvent to obtain a spinning solution, carrying out solution blowing spinning through a solution blowing spinning device 107, carrying out pair spinning on the two spinning processes, carrying out composite film formation on the spun yarn through a collecting roller 105, loading the prepared ZIF-8 solution into two solution spraying devices 106, spraying the solution on the surface layer of a composite fiber layer, rotating the collecting roller 1000 times to obtain 1000 layers of MOF composite fiber materials, carrying out hot rolling treatment until the ZIF-8 fully reacts, obtaining a thin composite film, and drying through a hot air oven to obtain a finished product, wherein the thickness of the finished product is 0.6mm.
Wherein the molar ratio of the polylactic acid master batch to the MOF powder is 11:1, the spinning temperature is 180 ℃, the drafting frequency is 55Hz, the drafting distance is 2m, and the rotating speed of a collecting roller is 10 r.min -1 And the rotating speed of the metering pump is 10r/min.
The solvent of the polyurethane solution adopts DMF, the concentration of the spinning solution is 10 percent, the solution is adopted for blowing and spinning, the air pressure is 0.4MPa, the flow rate is 5mL/h, and the receiving distance is 50cm.
The diameter of the polylactic acid fiber is 1000nm, and the diameter of the polyurethane fiber is 650nm.
The MOF material is Cu-BTC with the size of 550nm; ZIF-8 with the size of 200nm.
The solution used for the preparation of Cu-BTC is Cu (NO) 3 ) 2 ·3H 2 O, 1,3, 5-benzeneTricarboxylic acid (BTC) and ethanol, wherein Cu (NO) 3 ) 2 ·3H 2 O: the molar ratio of 1,3, 5-benzene tricarboxylic acid (BTC) is 9:5. adding Cu (NO) 3 ) 2 The solution was added drop wise to the BTC solution and stirred well. Stirring at room temperature for 4 hours, collecting precipitate, washing with ethanol for 3 times, removing unreacted ions, and drying the precipitate in a hot air oven at 120 ℃ for 12 hours to obtain Cu-BTC powder.
The solution used for preparing ZIF-8 is Zn (NO) 3 ) 2 ·6H 2 O, 2-methylimidazole and methanol, in which Zn (NO) 3 ) 2 ·6H 2 O: the molar ratio of 2-methylimidazole is 1:3.
the MOF prepared solution was loaded in the solution spraying apparatus at a distance of 50cm from the collection roller.
The pressure of the hot rolling treatment was 100N/mm.
And (3) after the MOF reaction is finished, drying in a hot air oven at the drying temperature of 110 ℃.
The gas separation performance of the membrane is tested by a gas separation performance testing device, and the CO is tested under the conditions of 35 ℃ and 0.1MPa 2 Transmittance 356barrer, for N 2 Transmittance of 2.6barrer for CH 4 The transmittance is 3.2barrer, CO is obtained 2 /N 2 Selectivity 137, CO 2 /CH 4 Selectivity 109.
Comparative example 1MOF composite fiber Material preparation
The polylactic acid master batches and the prepared Cu-BTC powder are uniformly mixed and added into a screw extruder 101, and extruded by a screw, a melt is sent into a spinning box 103 by a metering pump 102 and spun by a spinneret plate, and then enters an airflow drafting device 104 to spin a slender filament under the action of high-speed airflow. And simultaneously mixing polyurethane and a DMF solvent to obtain a spinning solution, carrying out solution blowing spinning by a solution blowing spinning device 107, carrying out counter-spinning on the two spinning processes, compounding the spun filaments into a film by a collecting roller 105, rotating the collecting roller 1000 times to obtain 1000 layers of composite fiber materials, carrying out hot rolling treatment to obtain a thin composite film, soaking the composite film in a ZIF-8 solution to cover the surface layer of the film, and drying by a hot air oven to obtain a finished product. (film thickness 1.0 mm)
Wherein the molar ratio of the polylactic acid master batch to the MOF powder is 11:1, the spinning temperature is 180 ℃, the drafting frequency is 55Hz, the drafting distance is 2m, and the rotating speed of a collecting roller is 10 r.min -1 And the rotating speed of the metering pump is 10r/min.
The solvent of the polyurethane solution adopts DMF, the concentration of the spinning solution is 10 percent, the solution is adopted for blowing and spinning, the air pressure is 0.4MPa, the flow rate is 5mL/h, and the receiving distance is 50cm.
The diameter of the polylactic acid fiber is 1000nm, and the diameter of the polyurethane fiber is 650nm.
The MOF material is Cu-BTC with the size of 550nm; ZIF-8 with the size of 200nm.
The solution used for the preparation of Cu-BTC is Cu (NO) 3 ) 2 ·3H 2 O, 1,3, 5-benzenetricarboxylic acid (BTC) and ethanol, wherein Cu (NO) 3 ) 2 ·3H 2 O: the molar ratio of 1,3, 5-benzene tricarboxylic acid (BTC) is 9:5. adding Cu (NO) 3 ) 2 The solution was added drop wise to the BTC solution and stirred well. Stirring at room temperature for 4 hours, collecting precipitate, washing with ethanol for 3 times, removing unreacted ions, and drying the precipitate in a hot air oven at 120 ℃ for 12 hours to obtain Cu-BTC powder.
The solution used for preparing ZIF-8 is Zn (NO) 3 ) 2 ·6H 2 O, 2-methylimidazole and methanol, in which Zn (NO) 3 ) 2 ·6H 2 O: the molar ratio of 2-methylimidazole is 1:2.
the pressure of the hot rolling treatment was 100N/mm.
And (3) after the MOF reaction is finished, drying in a hot air oven at the drying temperature of 110 ℃.
The gas separation performance of the membrane is tested by a gas separation performance testing device, and CO is tested under the conditions of 35 ℃ and 0.1MPa 2 Transmission coefficient of 298barrer, for N 2 Transmittance of 2.5barrer for CH 4 The transmittance is 3.0barrer, CO is obtained 2 /N 2 Selectivity of 119,CO 2 /CH 4 The selectivity was 99.
Comparative example 2MOF composite fiber Material preparation
The polylactic acid master batches and the prepared Cu-BTC powder are uniformly mixed and added into a screw extruder 101, and extruded by a screw, a melt is sent into a spinning box 103 by a metering pump 102 and spun by a spinneret plate, and then enters an airflow drafting device 104 to spin a slender filament under the action of high-speed airflow. And simultaneously mixing polyurethane and a DMF solvent to obtain a spinning solution, carrying out solution blowing spinning by using a solution blowing spinning device 107, carrying out pair spinning on the two spinning processes, carrying out composite film formation on the spun yarns by using a collecting roller 105, rotating the collecting roller for 1000 times to obtain 1000 layers of composite fiber materials, carrying out hot rolling treatment to obtain a thin composite film, and drying by using a hot air oven to obtain a finished product.
Wherein the molar ratio of the polylactic acid master batch to the MOF powder is 11:2, the spinning temperature is 180 ℃, the drafting frequency is 55Hz, the drafting distance is 2m, and the rotating speed of a collecting roller is 10 r.min -1 The rotating speed of the metering pump is 10r/min.
The solvent of the polyurethane solution adopts DMF, the concentration of the spinning solution is 10 percent, the solution is adopted for blowing and spinning, the air pressure is 0.4MPa, the flow rate is 5mL/h, and the receiving distance is 50cm.
The diameter of the polylactic acid fiber is 1000nm, and the diameter of the polyurethane fiber is 650nm.
The MOF material is Cu-BTC with the size of 550nm.
The solution used for the preparation of Cu-BTC is Cu (NO) 3 ) 2 ·3H 2 O, 1,3, 5-benzenetricarboxylic acid (BTC) and ethanol, wherein Cu (NO) 3 ) 2 ·3H 2 O:1,3, 5-benzene tricarboxylic acid (BTC) molar ratio of 9:4. adding Cu (NO) 3 ) 2 The solution was added drop wise to the BTC solution and stirred well. Stirring at room temperature for 4 hours, collecting precipitate, washing with ethanol for 3 times, removing unreacted ions, and drying the precipitate in a hot air oven at 120 ℃ for 12 hours to obtain Cu-BTC powder.
The pressure of the hot rolling treatment was 100N/mm.
And (3) after the MOF reaction is finished, drying in a hot air oven at the drying temperature of 110 ℃.
The gas separation performance of the membrane is tested by a gas separation performance testing device, and CO is tested under the conditions of 35 ℃ and 0.1MPa 2 Transmittance of 105barrer, for N 2 Transmittance of 1.4barrer for CH 4 The transmittance is 1.9barrer, CO is obtained 2 /N 2 The selectivity was set to be 75 f,CO 2 /CH 4 the selectivity was 54.
Analysis of results
1. Gas selectivity
Because the size in two kinds of MOF holes differs in this application, the pore structure of different diameters can promote gaseous separation, is favorable to gaseous passing through, and simultaneously, polylactic acid and polyurethane are biodegradable materials, because these two kinds of material inner structure also have certain microporous structure, can be fine agree with the MOF material to strengthen gaseous selectivity.
Comparative example 1 by impregnating ZIF-8 on the membrane surface, the membrane thickness will become thicker, and since the pressure difference across the membrane will also be affected at the fiber surface, the pressure difference will become slightly larger, thereby affecting the gas permeability coefficient and thus the gas selectivity; comparative example 2 removing ZIF-8 would lack a substance to separate gas, however, lack of ZIF-8 would seriously affect the gas separation performance; the thickness is affected by the reduction of the number of layers in example 2, the transmembrane pressure difference becomes large, the permeability coefficient becomes small, and the gas selectivity is affected, and if the number of layers is large (example 3), the thickness becomes large, the molar flow rate becomes small, and the transmembrane pressure difference becomes large, and therefore, the number of layers is preferably 900 to 1200 layers, and more preferably 900 to 1000 layers.
2. Mechanical properties
The films of examples and comparative examples were subjected to mechanical property tests, the results of which are shown in the following table:
breaking strength N/5cm
Example 1 83
Example 2 80
Example 3 88
Example 4 83
Comparative example 1 83
Comparative example 2 83
The same spinning method is adopted in the embodiment and the comparative example, compared with the common electrostatic spinning, the mechanical property of the composite material is in a higher level, and meanwhile, the mechanical property and the layer number are positively correlated due to the same material.
In conclusion, the composite MOF fiber composite membrane with the multilayer structure is prepared by compounding the fibers obtained by spun bonding and the fibers obtained by solution blowing and spinning, wherein the composite fibers are used as a matrix layer to bear mechanical support, and the MOF layer is used as a gas selective filter layer, so that the gas separation capability is improved, and meanwhile, the mechanical property is improved.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Various other modifications and alterations will occur to those skilled in the art upon reading the foregoing description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims (10)

1. A preparation method of an MOF composite fiber membrane is characterized by comprising the following steps,
s1: carrying out spun-bonding by taking a mixture of polylactic acid master batches and MOF powder as a spun-bonding raw material to obtain polylactic acid fibers;
meanwhile, carrying out solution blowing spinning by taking a polyurethane solution as a spinning solution to obtain polyurethane fibers;
s2: compounding the polylactic acid fibers and the polyurethane fibers to form a composite fiber layer;
s3: spraying a solution for synthesizing MOF particles on the surface of the composite fiber layer, and depositing an MOF material to obtain an MOF composite fiber layer;
s4: rolling the MOF composite fiber layer to obtain an MOF composite fiber material;
s5: and carrying out hot rolling treatment on the MOF composite fiber material to obtain the MOF composite fiber membrane.
2. The method for preparing the MOF composite fiber membrane of claim 1, wherein in the mixture of the polylactic acid master batch and the MOF powder, the molar ratio of the polylactic acid master batch to the MOF powder is 11:1-2.
3. The method for preparing the MOF composite fiber membrane according to claim 1, wherein in the step S1, the concrete operation of the spun-bonding is as follows: uniformly mixing the polylactic acid master batch and the MOF powder, and adding the mixture into a screw extruder for extrusion to obtain a solution; feeding the melt into a spinning manifold through a metering pump for spinning; and (3) leading the silk obtained by spinning to enter an airflow drafting device for airflow drafting to obtain the polylactic acid fiber.
4. The method of making a MOF composite fibrous membrane according to claim 1, wherein the diameter of the polylactic acid fiber is 1000-1200nm and the diameter of the polyurethane fiber is 600-700nm.
5. The method of making a MOF composite fibrous membrane of claim 1, wherein the MOF powder is a Cu-BTC MOF powder and the solution of synthetic MOF particles is a solution of synthetic ZIF-8.
6. The method for preparing the MOF composite fiber membrane according to claim 1, wherein the number of MOF composite fiber layers in the MOF composite fiber material is 900-1500.
7. The method of making a MOF composite fibrous membrane according to claim 1, wherein the pressure of the hot rolling process in step S5 is 90-110N/mm.
8. The method for preparing the MOF composite fiber membrane according to claim 1, wherein in the step S5, the hot rolling treatment is followed by a drying treatment, and the drying temperature is 100-120 ℃.
9. An MOF composite fiber membrane made by the method of any one of claims 1-8.
10. The MOF composite fibrous membrane of claim 9 in CO 2 Application in catalytic separation.
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