CN109603444B - Method for promoting oxygen and nitrogen separation of transfer membrane by using axial chlorine-containing metalloporphyrin as oxygen carrier - Google Patents
Method for promoting oxygen and nitrogen separation of transfer membrane by using axial chlorine-containing metalloporphyrin as oxygen carrier Download PDFInfo
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- 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
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
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- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/12—Oxygen
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Abstract
The invention relates to a method for promoting a transfer membrane to separate oxygen and nitrogen by using axial chlorine type metalloporphyrin as an oxygen carrier, belonging to the technical field of gas separation. The transfer promotion membrane is prepared by axial chlorine-containing metalloporphyrin and a polymer on a support substrate, and the metalloporphyrin and the polymer form an effective thin layer. By axially introducing electron-withdrawing groups-Cl into the metal at the center of the metalloporphyrin, the density of electron clouds of the metal at the center and the affinity to oxygen are reduced, the desorption rate of oxygen on the metalloporphyrin is improved, the transfer and transportation of oxygen molecules in the membrane are effectively promoted, and the oxygen-nitrogen separation performance of the membrane is improved. The method can prepare the transfer-promoting membrane with uniform and thin effective layer thickness, no defect and high oxygen-nitrogen separation performance, the separation process is easy to operate, the flow is simple, the environment is friendly, and the transfer-promoting membrane can be used for producing oxygen-enriched air and nitrogen-enriched air and is applied to aspects of oxygen-enriched combustion, medical oxygen, air purification, food preservation, fire prevention and the like.
Description
Technical Field
The invention belongs to the technical field of gas separation, and particularly relates to a method for promoting a transfer membrane to separate oxygen and nitrogen by using metalloporphyrin as an oxygen carrier.
Background
The oxygen-enriched air obtained by air separation can be used for aspects of oxygen-enriched combustion, medical oxygen utilization, air purification and the like; the obtained nitrogen-enriched air can be used for food storage and the like. The main methods for air separation include cryogenic separation, pressure swing adsorption separation and membrane separation. Cryogenic separation is performed according to different boiling points of oxygen and nitrogen, and as a mature oxygen-nitrogen separation method, the method can produce high-purity oxygen and nitrogen in a large scale, but the method has high energy consumption and cost and complicated flow. Pressure swing adsorption separation is performed according to different interaction strengths of oxygen, nitrogen and an adsorption material, and oxygen prepared by the method has high purity, is not suitable for large-scale preparation and has high cost.
The membrane method for separating oxygen and nitrogen has the advantages of low energy consumption and production cost, easy operation and the like, and is a gas separation method with a very promising prospect. Meanwhile, the thinning of the effective layer of the membrane can reduce the mass transfer resistance of the gas and improve the permeation rate of the gas, which has important significance for the actual industrial production process. However, in the case of the conventional polymer membrane conforming to the dissolution-diffusion mechanism, the oxygen permeability and the oxygen/nitrogen selectivity are mutually restricted, i.e., the permeability and the selectivity are difficult to be simultaneously improved.
Metalloporphyrin has the advantages of easy synthesis, designable structure and the like, is used for oxygen-nitrogen membrane separation and achieves good separation effect, and part of reports is that electron-attracting groups (such as-Cl, -F and the like) are introduced into benzene rings of porphyrin ligand to improve the oxygen-nitrogen separation performance of the membrane (Polymer,2008,49(26): 5659:. 5664; Chemistry of Materials,2000,12(9): 2693:. 2697.) Chinese patent CN 1059736A discloses an oxygen-permeable Polymer film containing meso-cobalt porphyrin, wherein the porphyrin ligand has three α ortho-position substituents and one β ortho-position substituent to provide space for the adsorption and desorption of oxygen molecules, the metal porphyrin can selectively and rapidly adsorb oxygen molecules and has good stability, Chinese patent CN1059737A discloses a Polymer film containing meso-cobalt porphyrin, wherein the porphyrin ligand has four ortho-substituted aromatic amine α, and can simultaneously complex aromatic amine with an ortho-coordination center to make the aromatic porphyrin complex with an aromatic metal amide.
Based on the analysis and the combination of the advantages of the metalloporphyrin containing the electron-withdrawing group, the invention provides a method for promoting the oxygen and nitrogen separation of a transfer membrane by using axial chlorine-containing metalloporphyrin as an oxygen carrier. The method for directly introducing the-Cl electron-withdrawing group into the metalloporphyrin central metal has the advantages that: 1) the axial electron-withdrawing group-Cl can directly reduce the electron cloud density of the central metal, reduce the affinity with oxygen, improve the desorption rate of oxygen on the central metal and promote the transfer of oxygen in the membrane so as to increase the permeability and oxygen/nitrogen selectivity of oxygen; 2) in the process of complexing different central metals with oxygen, the bond length between the central metal and electron-withdrawing group-Cl can be correspondingly changed, so that the action strength of the central metal and oxygen can be adjusted, the action strength of oxygen and metalloporphyrin is moderate, and reversible complexing of metalloporphyrin and oxygen is favorably realized. By designing the structure of the metalloporphyrin and adopting a specific film preparation method, the compatibility of the metalloporphyrin and the polymer can be effectively improved, the thickness of an effective layer can be reduced, and the oxygen-nitrogen separation performance can be improved. The method has the advantages of high oxygen permeability and oxygen/nitrogen selectivity, simple operation, continuous production, environmental friendliness and the like in the process of separating oxygen and nitrogen, is an oxygen and nitrogen separation technology with application prospect, is suitable for producing oxygen-enriched air and nitrogen-enriched air, and is applied to aspects of oxygen-enriched combustion, medical oxygen, air purification, food preservation and the like.
Disclosure of Invention
The invention aims to provide a method for separating oxygen and nitrogen by utilizing a transport-promoting film taking axial chlorine-containing metalloporphyrin as an oxygen carrier.
The transfer-promoting membrane is prepared by preparing axial chlorine-containing metalloporphyrin and a polymer on a support substrate, wherein the metalloporphyrin and the polymer form an effective thin layer, and oxygen selectively permeates from one side of the membrane to the other side through reversible complexation of the metalloporphyrin and the oxygen, so that high permeability and high selectivity separation of the oxygen are realized.
The metalloporphyrin has the following structural formula:
wherein M is Co, Mn or Fe; when R is1Or R2Or R3is-OCH3、-OH、-CH3H, -Cl or-NO2Accordingly R2And R3Or R1And R3Or R1And R2Is H.
The polymer of the invention is a polyether amide block copolymer (Pebax) or a polymer with micropores (PIMs).
The mass percentage of the metalloporphyrin is 0.001-20% of the polymer.
The support substrate of the present invention is polyvinylidene fluoride (PVDF), Polyacrylonitrile (PAN), or Polyethersulfone (PES).
The promoting transfer membrane is suitable for producing oxygen-enriched air and nitrogen-enriched air, the produced oxygen-enriched air can be applied to oxygen-enriched combustion, medical oxygen and air purification, and the produced nitrogen-enriched air can be applied to food preservation and fire prevention.
Compared with the prior art, the axial chlorine-containing metalloporphyrin can selectively and reversibly complex oxygen, has high oxygen desorption rate, can effectively promote the transfer of oxygen in the membrane, and ensures that the transfer-promoting membrane has high oxygen-nitrogen separation performance. The oxygen and nitrogen separation promoting transfer membrane adopting the axial chlorine type metalloporphyrin as the oxygen carrier has the advantages of high separation efficiency, mild condition and easy operation, and provides a new membrane material for oxygen and nitrogen separation.
Detailed Description
The technical solutions of the present invention will be described in more detail below with reference to specific examples, but the present invention is not limited to the following examples, and various modifications and implementations are included in the technical scope of the present invention without departing from the scope described before and after.
Example 1
(1) Adding 20m L propionic acid, 10m L acetic acid and 10m L o-nitrotoluene into a three-neck flask, heating to 130 ℃, adding 10mmol p-methoxybenzaldehyde, uniformly stirring, adding 10m L o-nitrotoluene solution containing 10mmol pyrrole, reacting for 1h, adding 30m L anhydrous methanol into the system after the reaction is finished, standing for 3h, performing suction filtration, fully washing with deionized water, and performing vacuum drying to prepare the tetra (p-methoxyphenyl) porphyrin ligand.
(2) Adding 0.2mmol of tetra (p-methoxyphenyl) porphyrin ligand, 30m L DMF and 3m L acetic acid into a three-neck flask, heating to 150 ℃, refluxing for 30min, adding 1.2mmol of cobalt chloride, reacting for 5h, adding 40m L hydrochloric acid solution after the reaction is finished, standing overnight, performing suction filtration, and drying to prepare the tetra (p-methoxyphenyl) cobalt porphyrin chloride.
(3) Dissolving Pebax-2533 polymer particles in absolute ethyl alcohol at the temperature of 80 ℃ to prepare a Pebax-2533 ethanol solution with the mass fraction of 2 wt%, adding tetra (p-methoxyphenyl) cobalt porphyrin chloride into the solution to enable the mass fraction of the tetra (p-methoxyphenyl) cobalt porphyrin to be 0.6 wt% of the polymer, and fully stirring at the temperature of 40 ℃. Pouring the prepared membrane liquid into a glass tank, vertically soaking the PVDF substrate in the membrane liquid for about 20s, taking out, airing under natural conditions, and then vacuumizing and drying at 60 ℃ for 2 h.
The membrane prepared above was sealed in a membrane cell, and the oxygen and nitrogen gas permeability test was performed on the prepared membrane at room temperature, with the permeation side pressure being normal pressure and the permeation side pressure being 0.005MPa, to obtain an oxygen permeability and an oxygen/nitrogen selectivity of 21.2GPU and 13.1, respectively, under these conditions. The films were characterized using an electron microscope and the effective layer film thickness was 1 μm.
Example 2
(1) Adding 20m L propionic acid, 10m L acetic acid and 10m L o-nitrotoluene into a three-neck flask, heating to 130 ℃, adding 10mmol p-chlorobenzaldehyde, uniformly stirring, adding 10m L o-nitrotoluene solution containing 10mmol pyrrole, reacting for 1h, after the reaction is finished, adding 30m L anhydrous methanol into the system, standing for 3h, performing suction filtration, fully washing with deionized water, and performing vacuum drying to prepare the tetra (p-chlorophenyl) porphyrin ligand.
(2) Adding 0.2mmol of tetra (p-chlorophenyl) porphyrin ligand, 30m L DMF and 3m L acetic acid into a three-neck flask, heating to 150 ℃, refluxing for 30min, adding 1.2mmol of ferrous chloride, reacting for 5h, adding 40m L hydrochloric acid solution after the reaction is finished, standing overnight, performing suction filtration, and drying to prepare the tetra (p-chlorophenyl) ferriporphyrin chloride.
(3) The PIM-1 polymer was dissolved in chloroform to prepare a chloroform solution of PIM-1 with a mass fraction of 0.5 wt%, tetrakis (p-chlorophenyl) ferriporphyrin chloride was added to the solution so that the mass fraction thereof was 0.2 wt% of the polymer, and the mixture was sufficiently stirred at room temperature. Pouring the prepared membrane liquid into a glass tank, vertically dipping the PAN substrate in the membrane liquid for 10s, taking out, vertically inverting for 180 degrees, vertically dipping for 10s, naturally drying, and then vacuumizing and drying for 1h at 30 ℃.
The membrane prepared above was sealed in a membrane cell, and the oxygen and nitrogen gas permeability test was performed on the prepared membrane at room temperature, with the permeation side pressure being normal pressure and the permeation side pressure being 0.04MPa, to obtain an oxygen permeability and an oxygen/nitrogen selectivity of 1165.7GPU and 5.6, respectively, under these conditions. The films were characterized using an electron microscope and the effective layer film thickness was 1 μm.
Example 3
(1) Adding 20m L propionic acid, 10m L acetic acid and 10m L o-nitrotoluene into a three-neck flask, heating to 130 ℃, adding 10mmol o-nitrobenzaldehyde, uniformly stirring, adding 10m L o-nitrotoluene solution containing 10mmol pyrrole, reacting for 1h, adding 30m L anhydrous methanol into the system after the reaction is finished, standing for 3h, performing suction filtration, fully washing with deionized water, and performing vacuum drying to prepare the tetra (o-nitrophenyl) porphyrin ligand.
(2) Adding 0.2mmol of tetra (o-nitrophenyl) porphyrin ligand, 30m L DMF and 3m L acetic acid into a three-neck flask, heating to 150 ℃, refluxing for 30min, adding 1.2mmol of manganese chloride, reacting for 5h, adding 40m L hydrochloric acid solution after the reaction is finished, standing overnight, performing suction filtration, and drying to prepare the tetra (o-nitrophenyl) manganese porphyrin chloride.
(3) The Pebax-1657 polymer particles are dissolved in a mixture of 80 ℃ ethanol water (ethanol: water: 70:30, w/w) to prepare a membrane liquid of the Pebax-1657 with the mass fraction of 1 wt%, the tetra (o-nitrophenyl) manganoporphyrin chloride is added into the solution to enable the mass fraction of the tetra (o-nitrophenyl) manganoporphyrin to be 5 wt% of the polymer, and the mixture is fully stirred at room temperature. Pouring the prepared membrane liquid into a glass tank, vertically soaking the PES substrate in the glass tank for 20s, taking out, airing under natural conditions, and then vacuumizing and drying at 60 ℃ for 4 h.
And sealing the prepared membrane in a membrane pool, and carrying out an oxygen-nitrogen gas permeability test on the prepared membrane at room temperature, wherein the pressure of a permeation side is normal pressure, and the pressure of a permeation side is 0.035MPa, so that the oxygen permeability and the oxygen/nitrogen selectivity under the conditions are respectively 17.3GPU and 8.0. The films were characterized using an electron microscope and had a film thickness of 600 nm.
Example 4
(1) Adding 20m L propionic acid, 10m L acetic acid and 10m L o-nitrotoluene into a three-neck flask, heating to 130 ℃, adding 10mmol benzaldehyde, stirring uniformly, adding 10m L o-nitrotoluene solution containing 10mmol pyrrole, reacting for 1h, adding 30m L anhydrous methanol into the system after the reaction is finished, standing for 3h, performing suction filtration, fully washing with deionized water, and performing vacuum-pumping drying to prepare the tetraphenylporphyrin ligand.
(2) Adding 0.2mmol of tetraphenylporphyrin ligand, 30m L DMF and 3m L acetic acid into a three-neck flask, heating to 150 ℃, refluxing for 30min, adding 1.2mmol of ferrous chloride, reacting for 5h, adding 40m L hydrochloric acid solution after the reaction is finished, standing overnight, carrying out suction filtration, and drying to prepare the tetraphenylporphyrin chloride.
(3) Dissolving Pebax-2533 polymer particles in absolute ethyl alcohol at 80 ℃ to prepare a Pebax-2533 ethanol solution with the mass fraction of 3 wt%, adding tetraphenyl ferriporphyrin chloride into the solution to enable the mass fraction of the tetraphenyl ferriporphyrin chloride to be 0.1 wt% of the polymer, and fully stirring at 40 ℃. Pouring the prepared membrane liquid into a glass tank, vertically soaking the PVDF substrate in the membrane liquid for about 20s, taking out, airing under natural conditions, and then vacuumizing and drying at 60 ℃ for 3 h.
And sealing the prepared membrane in a membrane pool, and carrying out an oxygen-nitrogen gas permeability test on the prepared membrane at room temperature, wherein the pressure of a permeation side is normal pressure, and the pressure of a permeation side is 0.3MPa, so that the oxygen permeability and the oxygen/nitrogen selectivity under the conditions are respectively 14.1GPU and 3.9. The films were characterized using an electron microscope and the effective layer film thickness was 2 μm.
Example 5
(1) Adding 20m L propionic acid, 10m L acetic acid and 10m L o-nitrotoluene into a three-neck flask, heating to 130 ℃, adding 10mmol m hydroxybenzaldehyde, uniformly stirring, adding 10m L o-nitrotoluene solution containing 10mmol pyrrole, reacting for 1h, adding 30m L anhydrous methanol into the system after the reaction is finished, standing for 3h, performing suction filtration, fully washing with deionized water, and performing vacuum drying to prepare the tetra (m-hydroxyphenyl) porphyrin ligand.
(2) Adding 0.2mmol of tetra (m-hydroxyphenyl) porphyrin ligand, 30m L DMF and 3m L acetic acid into a three-neck flask, heating to 150 ℃, refluxing for 30min, adding 1.2mmol of cobalt chloride, reacting for 5h, adding 40m L hydrochloric acid solution after the reaction is finished, standing overnight, performing suction filtration, and drying to prepare the tetra (m-hydroxyphenyl) cobalt porphyrin chloride.
(3) The PIM-1 polymer is dissolved in chloroform to prepare a chloroform solution of PIM-1 with the mass fraction of 1 wt%, tetra (m-hydroxyphenyl) cobalt porphyrin chloride is added into the solution to enable the mass fraction of the solution to be 0.8 wt% of the polymer, and the solution is fully stirred at room temperature. Pouring the prepared membrane liquid into a glass tank, vertically dipping the PAN substrate in the membrane liquid for 10s, taking out, vertically inverting for 180 degrees, vertically dipping for 10s, naturally drying, and then vacuumizing and drying for 1h at 30 ℃.
The membrane prepared above was sealed in a membrane cell, and the oxygen and nitrogen gas permeability test was performed on the prepared membrane at room temperature, with the permeate-side pressure being normal pressure and the permeate-side pressure being 0.1MPa, to obtain an oxygen permeability and an oxygen/nitrogen selectivity of 679.2GPU and 4.1, respectively, under these conditions. The films were characterized using an electron microscope and the effective layer film thickness was 2 μm.
Example 6
(1) Adding 20m of L propionic acid, 10m of L acetic acid and 10m of L o-nitrotoluene into a three-neck flask, heating to 130 ℃, adding 10mmol of p-tolualdehyde, uniformly stirring, adding 10m of L o-nitrotoluene solution containing 10mmol of pyrrole, reacting for 1h, adding 30m of L anhydrous methanol into the system after the reaction is finished, standing for 3h, performing suction filtration, fully washing with deionized water, and performing vacuum drying to prepare the tetra (p-methylphenyl) porphyrin ligand.
(2) Adding 0.2mmol of tetra (p-methylphenyl) porphyrin ligand, 30m L DMF and 3m L acetic acid into a three-neck flask, heating to 150 ℃, refluxing for 30min, adding 1.2mmol of cobalt chloride, reacting for 5h, adding 40m L hydrochloric acid solution after the reaction is finished, standing overnight, performing suction filtration, and drying to prepare the tetra (p-methylphenyl) cobalt porphyrin chloride.
(3) Dissolving Pebax-2533 polymer particles in absolute ethyl alcohol at 80 ℃ to prepare a Pebax-2533 ethanol solution with the mass fraction of 2 wt%, adding tetra (p-methylphenyl) cobalt porphyrin chloride into the solution to enable the mass fraction of the tetra (p-methylphenyl) cobalt porphyrin to be 10 wt% of the polymer, and fully stirring at 40 ℃. Pouring the prepared membrane liquid into a glass tank, vertically soaking the PVDF substrate in the membrane liquid for about 20s, taking out, airing under natural conditions, and then vacuumizing and drying at 60 ℃ for 2 h.
The membrane prepared above was sealed in a membrane cell, and the oxygen and nitrogen gas permeability test was performed on the prepared membrane at room temperature, with the permeation side pressure being normal pressure and the permeation side pressure being 0.5MPa, to obtain an oxygen permeability and an oxygen/nitrogen selectivity under these conditions of 29.1GPU and 5.7, respectively. The films were characterized using an electron microscope and the effective layer film thickness was 1 μm.
Claims (6)
1. A method for separating oxygen and nitrogen by using a transfer-promoting membrane taking axial chlorine-containing metalloporphyrin as an oxygen carrier is characterized in that the transfer-promoting membrane is prepared by using axial chlorine-containing metalloporphyrin and a polymer on a supporting substrate, the metalloporphyrin and the polymer form an effective thin layer, and oxygen selectively permeates from one side of the membrane to the other side of the membrane through the reversible complexation of the metalloporphyrin and the oxygen, so that high-permeability and high-selectivity separation of the oxygen is realized.
2. The method of claim 1, wherein the metalloporphyrin has the formula:
wherein M is Co, Mn or Fe; when R is1Or R2Or R3is-OCH3、-OH、-CH3H, -Cl or-NO2Accordingly R2And R3Or R1And R3Or R1And R2Is H.
3. The method according to claim 1, wherein the polymer is a polyetheramide block copolymer (Pebax) or a polymer with intrinsic microporosity (PIMs).
4. The method of claim 1, wherein the metalloporphyrin is present in an amount of 0.001-20% by weight of the polymer.
5. The method according to claim 1, characterized in that the supporting substrate is polyvinylidene fluoride (PVDF), Polyacrylonitrile (PAN) or Polyethersulfone (PES).
6. The method of claim 1, wherein the facilitated transfer membrane is adapted to produce oxygen-enriched air and nitrogen-enriched air, the produced oxygen-enriched air is applicable to oxygen-enriched combustion, medical oxygen and air purification, and the produced nitrogen-enriched air is applicable to food preservation and fire prevention.
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