CN107983177B - Preparation method of bi-component asymmetric hollow fiber ceramic membrane with petal-shaped cross section - Google Patents
Preparation method of bi-component asymmetric hollow fiber ceramic membrane with petal-shaped cross section Download PDFInfo
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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
- B01D71/02—Inorganic material
- B01D71/024—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
- B01D69/082—Hollow fibre membranes characterised by the cross-sectional shape of the fibre
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Abstract
The invention belongs to the technical field of inorganic membrane separation, and particularly relates to a preparation method of a bi-component asymmetric hollow fiber ceramic membrane with a petal-shaped cross section. The method comprises the steps of preparing a polymer solution, preparing a ceramic-polymer membrane casting solution, preparing a hollow fiber ceramic membrane blank, preparing a hollow fiber ceramic membrane matrix with a petal-shaped cross section, and preparing a bi-component asymmetric hollow fiber ceramic membrane with a petal-shaped cross section. The outer surface of the hollow fiber ceramic membrane substrate is not a smooth circular arc any more, but a curved surface with uniform height and undulation, so that the outer surface area of the hollow fiber ceramic membrane is increased; the porous structure of the novel hollow fiber ceramic membrane matrix improves the mass transfer rate. In addition, a selective permeability functional film layer is deposited on the outer surface of the hollow fiber ceramic membrane substrate, so that compared with the traditional hollow fiber ceramic membrane, the mass transfer rate is greatly improved, the surface reaction is promoted, and the cost is saved.
Description
Technical Field
The invention belongs to the technical field of inorganic membrane separation, and particularly relates to a preparation method of a bi-component asymmetric hollow fiber ceramic membrane with a petal-shaped cross section.
Background
The ceramic membrane is a membrane which is prepared by ceramic materials, has high selective permeability and plays a role in separation, has good chemical stability, can be used under the condition of high temperature and also has the capability of resisting microorganisms; and because of its high mechanical strength, high separation efficiency, long service life, etc., can be used in the separation and purification field and catalytic reaction field extensively, such as Chinese patent CN101733048A discloses a hollow fiber membrane reactor used for gas phase oxidation reaction and its preparation and application; chinese patent CN106630109A discloses a ceramic membrane and a preparation method thereof, a ceramic membrane component and a wastewater treatment system; chinese patent CN106316359A discloses a method for preparing a ceramic membrane support body by using purified water sludge and the prepared ceramic membrane support body; chinese patent CN202052474U discloses a high-efficiency high-strength corrugated ceramic membrane filter tube and a ceramic membrane ultrafilter; a ceramic membrane detection device disclosed in chinese patent CN 203750427U; chinese patent CN203007023U discloses a reciprocating rotary tubular ceramic membrane bioreactor; chinese patent CN1676198A discloses a ceramic hollow fiber membrane reactor for oxygen production by air separation, a preparation method and application thereof. The research of ceramic membrane technology has become one of the key research directions in the fields of materials and chemical industry at home and abroad at present.
The problems that the ratio of the surface area to the volume of a membrane is too small and the thickness of the membrane is relatively thick exist in the practical production application of a sheet-type or plate-type ceramic membrane adopted in the current laboratory research, so that the exchange area of surface reaction is relatively low and the separation efficiency is relatively low. In contrast, the hollow fiber ceramic membrane prepared by the developed phase inversion-sintering technology can achieve the advantages of reducing the membrane thickness and increasing the membrane area under the condition of the same strength requirement; meanwhile, compared with the traditional tubular ceramic membrane, the material consumption is less, and the specific surface area is larger; has high membrane area/volume ratio, and provides a new direction for reducing the cost of the ceramic membrane and realizing industrialization. Such as X.Tan, et al, Preparation of LSCF ceramic membranes for oxidative production by a phase-inversion/sintering technique, Ind.Eng.Chem.Res.,2005,44, 61; liu, et al, Oxygen selective ceramic fiber membranes, j.member.sci.,2005,246,103.
In recent years, in order to further improve the performance of hollow fiber ceramic membranes, various catalytic modifications of the membrane surfaces of the hollow fiber ceramic membranes are performed by various research institutes at home and abroad. For example, chinese patent CN106669440A discloses a method for modifying ceramic film and modified ceramic film; CN101302121A discloses a surface nano-coated modified ceramic oxygen permeable membrane and a preparation method thereof; CN101279205A discloses a ceramic hollow fiber oxygen permeable membrane with a surface loaded with a catalyst and a preparation method thereof; yacou, et, Palladium surface modified La0.6Sr0.4Co0.2Fe0.8O3-δhollow fibres for oxygen separation.,2011,380,223；K.Zhang,et al,Novel CO2-tolerant ion-transporting ceramic membranes with an external short circuit for oxygen separation atintermediate temperatures,Energy Environ.Sci.,2012,5,5257；N.Han,et al,Effectof enhanced oxygen reduction activity on oxygen permeation ofLa0.6Sr0.4Co0.2Fe0.8O3-δmembrane decorated by K2NiF4-type oxide,J Alloy Compd.,2016,654,280；K.Zhang,Robust ion-transporting ceramic membrane with aninternal short circuit for oxygen production,J.Mater.Chem.A.,2013,1,9150。
In order to apply the hollow fiber ceramic membrane to industrial production better, a great deal of research is made on the improvement of the ceramic membrane structure. For example, chinese patent CN101318106A discloses a plate-like ceramic membrane formed by connecting a plurality of hollow fiber ceramic membranes in parallel and a method for manufacturing the same; chinese patent CN102895886A discloses a hollow fiber ceramic oxygen permeable membrane with a double-composite asymmetric structure and a preparation method thereof; chinese patent CN105080359A discloses a preparation method of a ceramic hollow fiber oxygen permeable membrane bundle; chinese patent CN106431446A discloses a preparation method of a two-phase independent regularly distributed double-transport channel sheet-shaped ceramic membrane; chinese patent CN204352761U discloses a dish-shaped ceramic membrane filter element; chinese patent CN102172477A discloses a combined honeycomb ceramic membrane filter element; m.zuo, Ionic communication center-carbon phase recess fiber formulations for high temperature carbon dioxide separation, j.member.sci.,2014,458, 58; han, The effect of microstructure and surface resolution with K2NiF4-type oxide upon the oxygen permeability of perovskite-type La0.7Sr0.3FeO3-δhollow fiber membranes,RSC Adv.,2015,5,88602。
Chinese patent CN105854632A discloses a preparation method of a diatomite hollow fiber ceramic membrane, which takes diatomite as a raw material and adopts a phase inversion method and a dry-wet coating spinning technology combined with low-temperature sintering to prepare the diatomite hollow fiber ceramic membrane.
Chinese patent CN105536559A discloses a mullite ceramic hollow fiber membrane and a preparation method thereof. Adding medium ceramic powder into a polymer solution prepared from an organic polymer, an additive and a solvent to prepare casting film slurry; stirring to obtain uniformly dispersed casting film slurry; adding the fiber into a slurry tank on a spinning device, vacuumizing, introducing core liquid, adding nitrogen pressure to extrude the vacuumized casting film slurry into a spinning nozzle, immersing a wet fiber film extruded from the spinning nozzle into an external coagulating bath for gelling and curing through a dry spinning process of 0-20cm to form a ceramic hollow fiber film green body, naturally drying, and placing in a high-temperature furnace; heating to 700 ℃ to remove the organic polymer, heating to 800-1600 ℃ to sinter, cooling to 500 ℃ and naturally cooling to obtain the final product.
Compared with the traditional sheet-shaped and tubular membranes, the hollow fiber ceramic membrane prepared by the patent has great improvement in the aspects of membrane thickness, membrane area-volume ratio and the like, and if the external surface area of the membrane can be further increased on the basis, the separation and reaction performance of the membrane can be greatly improved. Therefore, it is necessary to develop a method for preparing a hollow fiber ceramic membrane having a large outer surface area.
Disclosure of Invention
The invention aims to provide a preparation method of a bi-component asymmetric hollow fiber ceramic membrane with a petal-shaped cross section, the prepared hollow fiber ceramic membrane has low cost, large external surface area and good reaction effect, the mass transfer rate of the hollow fiber ceramic membrane is greatly improved, and the separation efficiency is improved.
The preparation method of the double-component asymmetric hollow fiber ceramic membrane with the petal-shaped cross section comprises the following steps:
(1) preparation of Polymer solutions
Dissolving an organic polymer, an additive A and an additive B in an organic solvent to obtain a polymer solution;
(2) preparation of ceramic-Polymer casting solutions
Adding ceramic powder into the polymer solution obtained in the step (1), and uniformly stirring to form a ceramic-polymer membrane casting solution;
(3) preparing hollow fiber ceramic membrane blank with petal-shaped cross section
Vacuumizing the ceramic-polymer membrane casting solution obtained in the step (2), then placing the ceramic-polymer membrane casting solution into a spinning equipment tank, spinning the ceramic-polymer membrane casting solution into an outer coagulating liquid through a spinning nozzle, soaking the ceramic-polymer membrane casting solution into the outer coagulating liquid, and carrying out phase conversion and solidification under the combined action of the inner coagulating liquid and the outer coagulating liquid to obtain a hollow fiber ceramic membrane blank with a petal-shaped cross section;
(4) preparing a hollow fiber ceramic membrane matrix with petal-shaped cross section
Straightening, airing and sintering the hollow fiber ceramic membrane blank with the petal-shaped cross section obtained in the step (3) to obtain a hollow fiber ceramic membrane matrix with the petal-shaped cross section;
(5) preparation of double-component asymmetric hollow fiber ceramic membrane with petal-shaped cross section
And (4) depositing a selective permeability functional film layer on the hollow fiber ceramic membrane substrate with the petal-shaped cross section obtained in the step (4) to obtain the bi-component asymmetric hollow fiber ceramic membrane with the petal-shaped cross section.
Wherein:
in the step (1), the mass ratio of the organic polymer, the additive A, the additive B and the organic solvent is 12.5-25:0.1-5:0.5-25:50-100, preferably 12.5:0.1-3:0.5-10: 50;
the additive A is polyacrylamide (PAM, M)rAbout 150000), adding the additive A in the form of mixed solution, wherein the mass ratio of the additive A to water to alcohol in the mixed solution is 0.1-10:0.1-50:0.1-100, preferably 0.1-3:0.1-15: 5-40;
the alcohol is ethylene glycol or glycerol.
In the step (1), the organic polymer is polysulfone (M)r22000), polyether sulfone, polyacrylonitrile, polycarbonate, polyethylenimine (M)r10000), polyetherimide (melt index: 9g/min) or cellulose acetate (M)rApproximately equal to 50000).
In the step (1), the additive B is polyvinylpyrrolidone (PVP, M)r360000), polyvinyl butyral (PVB, viscosity (10% ethanol solution)>580 MPa.s), ammonium polymethacrylate, polyacrylate, gamma-butyrolactone, polymethyl methacrylate orOne or more of phosphate esters.
In the step (1), the organic solvent is N-methylpyrrolidone (NMP) and N, N-dimethylformamide-d7N, N-dimethylacetamide-d9Or dimethyl sulfoxide-d6One or more of (a).
In the selection of the organic polymer, the polymer with higher number average molecular weight and lower melt index in the homologous polymer is selected; and the additive A, the additive B and the organic solvent also select substances with larger molar mass and higher viscosity to improve the viscosity of the casting solution.
In the step (2), the ceramic powder is Al2O3、ZrO2、TiO2Or SiO2One or more of; the mass ratio of the ceramic powder to the polymer solution is 6-12:5, the average particle size of the ceramic powder is 0.02-10 μm, and the viscosity of the ceramic-polymer casting solution is 25000-55000 MPa.s.
In the step (3), the vacuumizing pressure is 0.01-0.1MPa, the vacuumizing time is 1-2h, and the spinning pressure is 0-0.25 MPa; the soaking temperature is 20-80 ℃, and the soaking time is 12-48 h.
In the step (3), the inner condensation liquid is N, N-dimethylformamide-d7N, N-dimethylacetamide-d9Dimethyl sulfoxide-d6One or more of water, ethanol, propanol or ethylene glycol; the external condensation liquid is water or ethanol.
In the step (4), the sintering: firstly, heating to 600-800 ℃ at the heating rate of 2-5 ℃/min, and roasting for 1-8 h; then raising the temperature to 1000-1600 ℃ at the temperature raising speed of 1-2 ℃/min, sintering for 1-10h, then lowering the temperature to 750-850 ℃ at the speed of 1-2 ℃/min, and finally lowering the temperature to room temperature.
In the step (5), the selectively permeable functional film layer is La0.6Sr0.4Co0.2Fe0.8O3-δThin film layer, Ba0.5Sr0.5Co0.8Fe0.2O3-δFilm layer, molecular sieve film layer, Al2O3Thin film layer, NiO thin film layer or Co3O4A film layer, said perm-selective functionalityThe thickness of the thin film layer is 1-20 μm.
Viscosity is a measure of the viscosity of a fluid and is a representation of the fluid flow forces versus internal friction phenomena, with greater viscosity indicating greater internal friction. Viscosity is essentially a property of a fluid to resist flow, and is a measure of the ability of the fluid to resist relative molecular motion due to molecular attraction, i.e., the internal resistance to fluid flow. The relationship between viscosity and shear force and shear rate is: viscosity is the shear force/shear rate. The higher the viscosity of the casting solution is, the larger the shearing force is, the larger the applied force is, and the lower the fluidity is; on the contrary, the lower the viscosity of the casting solution is, the smaller the shearing force is, the smaller the applied force is, and the better the fluidity is.
Along with the increase of the content of the ceramic powder in the casting solution or the reduction of the particle radius of the ceramic powder to a certain degree, the specific surface area is relatively increased, the polymer components on the outer surface of the ceramic powder are relatively increased, and the viscosity of the casting solution is increased. When the viscosity is higher, the pressure required in the spinning process of preparing the hollow fiber membrane blank by the membrane casting solution is higher, and the friction force acts in the spinning process, so that the prepared hollow fiber ceramic membrane is compact and loses the bulk phase pore structure. When the viscosity is too high, the fluidity of the casting solution is extremely poor, and a hollow fiber membrane blank cannot be formed even if a large pressure is applied in the spinning forming process. However, the hollow fiber ceramic membrane with a large external surface area can be prepared by increasing the viscosity of the casting solution, and therefore, the preparation of the casting solution with good fluidity and high viscosity is urgently needed.
The invention has the following beneficial effects:
in the invention, when PAM is added, the rotational viscosity of the system is greatly improved. Because PAM can be dispersed in water to form a stable system, then dispersed in glycol or glycerol and finally added into an organic solvent to form a water-in-oil uniform and stable PAM-organic solvent system, the viscosity of the casting solution is greatly improved by the solid-liquid mixed phase system. The resistance reduction effect of PAM can ensure the good fluidity of the casting solution system. Compared with the existing method for adjusting the viscosity of the casting solution, the method enables the high-viscosity casting solution to successfully spin the dual-component asymmetric hollow fiber ceramic membrane with the petal-shaped cross section under the synergistic action of the PAM and the additive B, and ensures the porous structure of the hollow fiber ceramic membrane.
On the premise of introducing PAM, the viscosity of the hollow fiber ceramic membrane is adjusted together with the additive B, so that the hollow fiber ceramic membrane is successfully spun under high viscosity. PAM is soluble in water, and a trace amount of PAM can reduce the frictional resistance of 50-80% in an aqueous solution system. PAM is partially soluble in ethylene glycol or glycerol and insoluble in N, N-dimethylformamide-d7N, N-dimethylacetamide-d9Or dimethyl sulfoxide-d6. The PAM is firstly dispersed in water, then added into glycol or glycerol to form a uniform and stable mixed solution, and then the mixed solution is added into an organic solvent system to form particles wrapped by water molecules/alcohol and is uniformly dispersed in the organic solvent system, so that the viscosity of the casting solution is greatly increased by the solid-liquid mixed system.
The outer surface of the hollow fiber ceramic membrane substrate is not a smooth circular arc any more, but a curved surface with uniform height and undulation, so that the outer surface area of the hollow fiber ceramic membrane is increased. In addition, a selective permeability functional film layer is deposited on the outer surface of the hollow fiber ceramic membrane substrate, so that compared with the traditional hollow fiber ceramic membrane, the mass transfer rate is greatly improved, the surface reaction is promoted, and the cost is saved.
Drawings
FIG. 1 is a schematic structural view of a hollow fiber ceramic membrane substrate having a petal-shaped cross section according to the present invention;
wherein 1: hollow fiber ceramic membrane matrix tube wall, 2: the hollow fiber ceramic membrane substrate inner cavity;
FIG. 2 is an electron magnifier drawing of a hollow fiber ceramic membrane substrate of the present invention having a petal-shaped cross section;
FIG. 3 is a scanning electron microscope image of a hollow fiber ceramic membrane substrate of the present invention having a petal-shaped cross section;
fig. 4 is a scanning electron microscope image of the bi-component asymmetric hollow fiber ceramic membrane of example 1 having a petal-shaped cross section.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The preparation method of the double-component asymmetric hollow fiber ceramic membrane with the petal-shaped cross section comprises the following steps:
(1) preparation of Polymer solutions
12.5g of polyethersulfone, 0.1g of polyacrylamide and 1g of polyvinylpyrrolidone were dissolved in 50g N, N-dimethylformamide-d7To obtain a polymer solution; wherein the polyacrylamide is added in the form of a mixed solution: 0.1g of polyacrylamide was dissolved in 3g of water, and then added to 10g of ethylene glycol to form a mixed solution.
(2) Preparation of ceramic-Polymer casting solutions
145g of Al2O3Adding the ceramic powder into 74.6g of the polymer solution obtained in the step (1), fully stirring for 24h to completely and uniformly disperse the ceramic powder in the polymer solution to form a ceramic-polymer casting solution, wherein the viscosity of the ceramic-polymer casting solution is 26000MPa & s; wherein the average grain size of the ceramic powder is 1 μm.
(3) Preparing hollow fiber ceramic membrane blank with petal-shaped cross section
Placing the ceramic-polymer membrane casting solution obtained in the step (2) under the condition of 0.08MPa, vacuumizing for 1.5h, then placing the ceramic-polymer membrane casting solution in a spinning equipment tank, spinning the ceramic-polymer membrane casting solution into a coagulating liquid at 25 ℃ through a spinning nozzle under the condition of 0.15MPa for soaking for 15h, and carrying out phase conversion and solidification under the combined action of the inner coagulating liquid and the outer coagulating liquid to obtain a hollow fiber ceramic membrane blank with a petal-shaped cross section; wherein the external condensate is water, and the internal condensate is water and N, N-dimethylformamide-d7The mass ratio of the two is 1: 4;
(4) preparing a hollow fiber ceramic membrane matrix with petal-shaped cross section
Straightening and airing the hollow fiber ceramic membrane blank with the cross section of the petal shape obtained in the step (3) for 36 hours at room temperature, then putting the blank into an electric furnace for sintering treatment by a program, raising the temperature to 800 ℃ in the air at a temperature raising speed of 5 ℃/min, roasting for 4 hours, and burning out organic matters in the blank; and then, the temperature is increased to 1450 ℃ at the temperature rise speed of 2 ℃/min for sintering for 8h, then the temperature is reduced to 800 ℃ at the speed of 2 ℃/min, and finally, the temperature is freely reduced to room temperature, so that the hollow fiber ceramic membrane substrate with the cross section being in a petal shape is obtained.
(5) Preparation of double-component asymmetric hollow fiber ceramic membrane with petal-shaped cross section
Depositing a layer of La with the thickness of 10 mu m on the hollow fiber ceramic membrane substrate with the petal-shaped cross section obtained in the step (4) by adopting an immersion method0.6Sr0.4Co0.2Fe0.8O3-δAnd (3) obtaining a bi-component asymmetric hollow fiber ceramic-oxygen permeable membrane with a petal-shaped cross section, wherein a scanning electron microscope image of the membrane is shown in figure 4.
From FIG. 4, it can be seen that the outer surface of the sheet was provided with a selectively permeable film layer having a thickness of about 10 μm by the dipping treatment.
Example 2
The preparation method of the double-component asymmetric hollow fiber ceramic membrane with the petal-shaped cross section comprises the following steps:
(1) preparation of Polymer solutions
12.5g of polyethyleneimine, 0.5g of polyacrylamide and 2g of polyvinyl butyral were dissolved in 50g N, N-dimethylformamide-d7To obtain a polymer solution; wherein the polyacrylamide is added in the form of a mixed solution: 0.5g of polyacrylamide was dissolved in 5g of water, and then added to 20g of ethylene glycol to form a mixed solution.
(2) Preparation of ceramic-Polymer casting solutions
145.5g of SiO2Adding the ceramic powder into 79g of the polymer solution obtained in the step (1), fully stirring for 30h to completely and uniformly disperse the ceramic powder in the polymer solution to form a ceramic-polymer casting solution, wherein the viscosity of the ceramic-polymer casting solution is 27400MPa & s; wherein the average grain size of the ceramic powder is 4 μm.
(3) Preparing hollow fiber ceramic membrane blank with petal-shaped cross section
Placing the ceramic-polymer membrane casting solution obtained in the step (2) under the condition of 0.05MPa, vacuumizing for 1.5h, then placing the ceramic-polymer membrane casting solution in a spinning equipment tank, spinning the ceramic-polymer membrane casting solution into 24 ℃ coagulating liquid through a spinning nozzle under the condition of 0.15MPa for soaking for 15h, and carrying out phase conversion and solidification under the combined action of the inner coagulating liquid and the outer coagulating liquid to obtain the cross sectionA hollow fiber ceramic membrane blank with a petal-shaped surface; wherein the external condensate is water, and the internal condensate is water and dimethyl sulfoxide-d6The mass ratio of the two is 1: 5;
(4) preparing a hollow fiber ceramic membrane matrix with petal-shaped cross section
Straightening and airing the hollow fiber ceramic membrane blank with the cross section of the petal shape obtained in the step (3) for 30h at room temperature, then putting the blank into an electric furnace for sintering treatment by a program, raising the temperature to 800 ℃ in the air at a temperature rise speed of 5 ℃/min, roasting for 4h, and burning out organic matters in the blank; and then, the temperature is increased to 1350 ℃ at the temperature rising speed of 2 ℃/min for sintering for 8h, then the temperature is reduced to 800 ℃ at the speed of 2 ℃/min, and finally, the temperature is freely reduced to room temperature, so that the hollow fiber ceramic membrane substrate with the cross section being in a petal shape is obtained.
(5) Preparation of double-component asymmetric hollow fiber ceramic membrane with petal-shaped cross section
Depositing a layer of Ba with the thickness of 5 mu m on the hollow fiber ceramic membrane substrate with the petal-shaped cross section obtained in the step (4) by adopting an immersion method0.5Sr0.5Co0.8Fe0.2O3-δAnd (3) a film layer, namely obtaining the bicomponent asymmetric hollow fiber ceramic-oxygen permeable membrane with the petal-shaped cross section.
Example 3
The preparation method of the double-component asymmetric hollow fiber ceramic membrane with the petal-shaped cross section comprises the following steps:
(1) preparation of Polymer solutions
12.5g of polysulfone, 0.5g of polyacrylamide and 4g of ammonium polymethacrylate were dissolved in 50g N, N-dimethylformamide-d7To obtain a polymer solution; wherein the polyacrylamide is added in the form of a mixed solution: 0.5g of polyacrylamide was dissolved in 5g of water, and then added to 25g of ethylene glycol to form a mixed solution.
(2) Preparation of ceramic-Polymer casting solutions
75g of Al2O3Ceramic powder and 75g TiO2Adding the ceramic powder into 96g of the polymer solution obtained in the step (1), and fully stirring for 30h to completely and uniformly disperse the ceramic powder in the polymer solutionForming ceramic-polymer casting solution in the polymer solution, wherein the viscosity of the ceramic-polymer casting solution is 27000MPa & s; wherein the average grain size of the ceramic powder is 5 μm.
(3) Preparing hollow fiber ceramic membrane blank with petal-shaped cross section
Placing the ceramic-polymer membrane casting solution obtained in the step (2) under the condition of 0.07MPa, vacuumizing for 1.5h, then placing the ceramic-polymer membrane casting solution in a spinning equipment tank, spinning the ceramic-polymer membrane casting solution into a coagulating liquid at 25 ℃ through a spinning nozzle under the condition of 0.2MPa for soaking for 20h, and carrying out phase conversion and solidification under the combined action of the inner coagulating liquid and the outer coagulating liquid to obtain a hollow fiber ceramic membrane blank with a petal-shaped cross section; wherein the external condensate is water, and the internal condensate is water and N, N-dimethylformamide-d7The mass ratio of the two is 1: 4;
(4) preparing a hollow fiber ceramic membrane matrix with petal-shaped cross section
Straightening and airing the hollow fiber ceramic membrane blank with the cross section of the petal shape obtained in the step (3) for 30h at room temperature, then putting the blank into an electric furnace for sintering treatment by a program, raising the temperature to 800 ℃ in the air at a temperature rise speed of 5 ℃/min, roasting for 4h, and burning out organic matters in the blank; and then, the temperature is increased to 1300 ℃ at the heating rate of 2 ℃/min for sintering for 8h, then the temperature is reduced to 800 ℃ at the heating rate of 2 ℃/min, and finally, the temperature is freely reduced to room temperature, so that the hollow fiber ceramic membrane substrate with the cross section being in a petal shape is obtained.
(5) Preparation of double-component asymmetric hollow fiber ceramic membrane with petal-shaped cross section
And (4) depositing and generating a molecular sieve film layer with the thickness of 15 mu m on the hollow fiber ceramic film substrate with the cross section of the petal shape obtained in the step (4) by adopting an impregnation method, and obtaining the bi-component asymmetric hollow fiber ceramic-molecular sieve film with the cross section of the petal shape.
Example 4
The preparation method of the double-component asymmetric hollow fiber ceramic membrane with the petal-shaped cross section comprises the following steps:
(1) preparation of Polymer solutions
12.5g of polyethersulfone, 0.5g of polyacrylamide and 5g of ammonium polymethacrylate were dissolved in 50g N, N-dimethylformamideAmine-d7To obtain a polymer solution; wherein the polyacrylamide is added in the form of a mixed solution: 0.5g of polyacrylamide was dissolved in 10g of water, and then added to 2g of glycerin to form a mixed solution.
(2) Preparation of ceramic-Polymer casting solutions
150g of ZrO2Adding the ceramic powder into 80g of the polymer solution obtained in the step (1), fully stirring for 24h to completely and uniformly disperse the ceramic powder in the polymer solution to form a ceramic-polymer casting solution, wherein the viscosity of the ceramic-polymer casting solution is 27500MPa & s; wherein the average grain size of the ceramic powder is 5 μm.
(3) Preparing hollow fiber ceramic membrane blank with petal-shaped cross section
Placing the ceramic-polymer membrane casting solution obtained in the step (2) under the condition of 0.1MPa, vacuumizing for 2h, then placing the ceramic-polymer membrane casting solution in a spinning equipment tank, spinning the ceramic-polymer membrane casting solution into a coagulating liquid at the temperature of 22 ℃ through a spinning nozzle under the condition of the spinning pressure of 0.15MPa, soaking for 15h, and carrying out phase conversion and solidification under the combined action of an inner coagulating liquid and an outer coagulating liquid to obtain a hollow fiber ceramic membrane blank with a petal-shaped cross section; wherein the external condensate is water, and the internal condensate is water and N, N-dimethylformamide-d7The mass ratio of the two is 1: 5;
(4) preparing a hollow fiber ceramic membrane matrix with petal-shaped cross section
Straightening and airing the hollow fiber ceramic membrane blank with the cross section of the petal shape obtained in the step (3) for 36 hours at room temperature, then putting the blank into an electric furnace for sintering treatment by a program, raising the temperature to 800 ℃ in the air at a temperature raising speed of 5 ℃/min, roasting for 4 hours, and burning out organic matters in the blank; and then, the temperature is increased to 1400 ℃ at the heating rate of 2 ℃/min for sintering for 8h, then the temperature is reduced to 800 ℃ at the speed of 2 ℃/min, and finally, the temperature is freely reduced to room temperature, so that the hollow fiber ceramic membrane substrate with the cross section being in a petal shape is obtained.
(5) Preparation of double-component asymmetric hollow fiber ceramic membrane with petal-shaped cross section
Depositing and generating a layer of Al with the thickness of 18 mu m on the hollow fiber ceramic membrane substrate with the petal-shaped cross section obtained in the step (4) by adopting an immersion method2O3Film layer of cross section ofPetal-shaped double-component asymmetric hollow fiber ceramic-oxide membrane.
Example 5
The preparation method of the double-component asymmetric hollow fiber ceramic membrane with the petal-shaped cross section comprises the following steps:
(1) preparation of Polymer solutions
12.5g of polysulfone, 1g of polyacrylamide, 2.5g of polyvinylpyrrolidone and 2.5g of polyvinyl butyral were dissolved in 50g of N, N-dimethylformamide-d7To obtain a polymer solution; wherein the polyacrylamide is added in the form of a mixed solution: 1g of polyacrylamide was dissolved in 10g of water, and then added to 20g of ethylene glycol to form a mixed solution.
(2) Preparation of ceramic-Polymer casting solutions
155g of Al2O3Ceramic powder and 25g ZrO2Adding the ceramic powder into 98.5g of the polymer solution obtained in the step (1), fully stirring for 24h to completely and uniformly disperse the ceramic powder in the polymer solution to form a ceramic-polymer casting solution, wherein the viscosity of the ceramic-polymer casting solution is 41000MPa & s; wherein the average grain size of the ceramic powder is 7 μm.
(3) Preparing hollow fiber ceramic membrane blank with petal-shaped cross section
Placing the ceramic-polymer membrane casting solution obtained in the step (2) under the condition of 0.02MPa, vacuumizing for 2h, then placing the ceramic-polymer membrane casting solution in a spinning equipment tank, spinning the ceramic-polymer membrane casting solution into a coagulating liquid at the temperature of 22 ℃ through a spinning nozzle under the condition of the spinning pressure of 0.25MPa, soaking for 20h, and carrying out phase conversion and solidification under the combined action of an inner coagulating liquid and an outer coagulating liquid to obtain a hollow fiber ceramic membrane blank with a petal-shaped cross section; wherein the external condensate is water, and the internal condensate is water and N, N-dimethylformamide-d7The mass ratio of the two is 1: 5;
(4) preparing a hollow fiber ceramic membrane matrix with petal-shaped cross section
Straightening and airing the hollow fiber ceramic membrane blank with the cross section of the petal shape obtained in the step (3) for 30h at room temperature, then putting the blank into an electric furnace for sintering treatment by a program, raising the temperature to 800 ℃ in the air at a temperature rise speed of 5 ℃/min, roasting for 4h, and burning out organic matters in the blank; and then, the temperature is increased to 1400 ℃ at the heating rate of 2 ℃/min for sintering for 8h, then the temperature is reduced to 800 ℃ at the speed of 2 ℃/min, and finally, the temperature is freely reduced to room temperature, so that the hollow fiber ceramic membrane substrate with the cross section being in a petal shape is obtained.
(5) Preparation of double-component asymmetric hollow fiber ceramic membrane with petal-shaped cross section
And (4) depositing and generating a NiO thin film layer with the thickness of 12 mu m on the hollow fiber ceramic membrane substrate with the petal-shaped cross section obtained in the step (4) by adopting an impregnation method to obtain the double-component asymmetric hollow fiber ceramic-oxide membrane with the petal-shaped cross section.
Example 6
The preparation method of the double-component asymmetric hollow fiber ceramic membrane with the petal-shaped cross section comprises the following steps:
(1) preparation of Polymer solutions
12.5g of polyvinyl nitrile, 0.5g of polyacrylamide and 2g of ammonium polymethacrylate were dissolved in 50g of dimethyl sulfoxide-d6To obtain a polymer solution; wherein the polyacrylamide is added in the form of a mixed solution: 0.5g of polyacrylamide was dissolved in 5g of water, and then added to 10g of ethylene glycol to form a mixed solution.
(2) Preparation of ceramic-Polymer casting solutions
145g of Al2O3Adding the ceramic powder into 78g of the polymer solution obtained in the step (1), fully stirring for 24h to completely and uniformly disperse the ceramic powder in the polymer solution to form a ceramic-polymer casting solution, wherein the viscosity of the ceramic-polymer casting solution is 26000MPa & s; wherein the average grain size of the ceramic powder is 3 μm.
(3) Preparing hollow fiber ceramic membrane blank with petal-shaped cross section
Placing the ceramic-polymer membrane casting solution obtained in the step (2) under the condition of 0.08MPa, vacuumizing for 2h, then placing the ceramic-polymer membrane casting solution in a spinning equipment tank, spinning the ceramic-polymer membrane casting solution into a coagulating liquid at 25 ℃ through a spinning nozzle under the condition of 0.2MPa for soaking for 12h, and carrying out phase conversion and solidification under the combined action of the inner coagulating liquid and the outer coagulating liquid to obtain a hollow fiber ceramic membrane blank with a petal-shaped cross section; wherein the external condensate is water, and the internal condensate is water and dimethyl sulfoxide-d6The mass ratio of the two is 1: 4;
(4) preparing a hollow fiber ceramic membrane matrix with petal-shaped cross section
Straightening and airing the hollow fiber ceramic membrane blank with the cross section of the petal shape obtained in the step (3) for 36 hours at room temperature, then putting the blank into an electric furnace for sintering treatment by a program, raising the temperature to 800 ℃ in the air at a temperature raising speed of 5 ℃/min, roasting for 4 hours, and burning out organic matters in the blank; and then, the temperature is increased to 1450 ℃ at the temperature rise speed of 2 ℃/min for sintering for 8h, then the temperature is reduced to 800 ℃ at the speed of 2 ℃/min, and finally, the temperature is freely reduced to room temperature, so that the hollow fiber ceramic membrane substrate with the cross section being in a petal shape is obtained.
(5) Preparation of double-component asymmetric hollow fiber ceramic membrane with petal-shaped cross section
Depositing a layer of Co with the thickness of 8 mu m on the hollow fiber ceramic membrane substrate with the petal-shaped cross section obtained in the step (4) by adopting an immersion method3O4And (3) obtaining a double-component asymmetric hollow fiber ceramic-oxide membrane with a petal-shaped cross section.
The structure of the hollow fiber ceramic membrane matrix with the petal-shaped cross section is shown in figure 1, the middle part is an inner cavity of the hollow fiber ceramic membrane matrix, the periphery of the inner cavity is a tube wall of the hollow fiber ceramic membrane matrix, and the distance from the petal-shaped top end of the tube wall to the inner cavity is 300-;
FIG. 2 is an electron magnifier view of a hollow fiber ceramic membrane substrate with petal-shaped cross section;
from fig. 3, it can be seen that the recessed portion of the outer surface of the hollow fiber ceramic membrane substrate corresponds to 30% to 35% of the entire sectional thickness of the ceramic membrane substrate.
Example 7
Polymer solutions were prepared from various additives, water, ethylene glycol, 12.5g polysulfone, 50g N-methyl pyrrolidone (NMP), and casting dope solutions were further prepared and tested for polymer solution viscosity and for casting dope viscosity as shown in Table 1.
TABLE 1 test data sheet
Note: experiments 7-9 are two-component experiments, experiment 7 with additive a being PVP and additive B being PVB, the remainder being performed according to the procedure of example 1; the procedure of experiment 8 was carried out with reference to the procedure of example 1; additive B in experiment 9 was PVB and the rest was carried out with reference to the procedure of example 1.
The external surface area of the two-component asymmetric hollow fiber ceramic membrane having a petal-shaped cross section obtained in examples 1 to 6 was measured, and the measurement results are shown in table 2.
TABLE 2 data determination Table
| Examples | 1 | 2 | 3 | 4 | 5 | 6 |
| External surface area (cm)2/cm) | 0.34 | 0.37 | 0.35 | 0.33 | 0.36 | 0.35 |
Claims (10)
1. A preparation method of a bi-component asymmetric hollow fiber ceramic membrane with a petal-shaped cross section is characterized by comprising the following steps:
(1) preparation of Polymer solutions
Dissolving an organic polymer, an additive A and an additive B in an organic solvent to obtain a polymer solution;
the additive A is polyacrylamide, the additive A is added in the form of mixed solution, and the mass ratio of the additive A to water to alcohol in the mixed solution is 0.1-10:0.1-50: 0.1-100; the alcohol is ethylene glycol or glycerol;
(2) preparation of ceramic-Polymer casting solutions
Adding ceramic powder into the polymer solution obtained in the step (1), and uniformly stirring to form a ceramic-polymer membrane casting solution;
(3) preparing hollow fiber ceramic membrane blank with petal-shaped cross section
Vacuumizing the ceramic-polymer membrane casting solution obtained in the step (2), then placing the ceramic-polymer membrane casting solution into a spinning equipment tank, spinning the ceramic-polymer membrane casting solution into an outer coagulating liquid through a spinning nozzle, soaking the ceramic-polymer membrane casting solution into the outer coagulating liquid, and carrying out phase conversion and solidification under the combined action of the inner coagulating liquid and the outer coagulating liquid to obtain a hollow fiber ceramic membrane blank with a petal-shaped cross section;
(4) preparing a hollow fiber ceramic membrane matrix with petal-shaped cross section
Straightening, airing and sintering the hollow fiber ceramic membrane blank with the petal-shaped cross section obtained in the step (3) to obtain a hollow fiber ceramic membrane matrix with the petal-shaped cross section;
(5) preparation of double-component asymmetric hollow fiber ceramic membrane with petal-shaped cross section
And (4) depositing a selective permeability functional film layer on the hollow fiber ceramic membrane substrate with the petal-shaped cross section obtained in the step (4) to obtain the bi-component asymmetric hollow fiber ceramic membrane with the petal-shaped cross section.
2. The method for preparing a bicomponent asymmetric hollow fiber ceramic membrane having a petal-shaped cross section according to claim 1, wherein the method comprises the steps of: in the step (1), the mass ratio of the organic polymer, the additive A, the additive B and the organic solvent is 12.5-25:0.1-5:0.5-25: 50-100.
3. The method for preparing a bicomponent asymmetric hollow fiber ceramic membrane having a petal-shaped cross section according to claim 1, wherein the method comprises the steps of: in the step (1), the organic polymer is one or more of polysulfone, polyethersulfone, polyacrylonitrile, polycarbonate, polyethyleneimine, polyetherimide or cellulose acetate.
4. The method for preparing a bicomponent asymmetric hollow fiber ceramic membrane having a petal-shaped cross section according to claim 1, wherein the method comprises the steps of: in the step (1), the additive B is one or more of polyvinylpyrrolidone, polyvinyl butyral, ammonium polymethacrylate, polyacrylate, gamma-butyrolactone, polymethyl methacrylate or phosphate.
5. The method for preparing a bicomponent asymmetric hollow fiber ceramic membrane having a petal-shaped cross section according to claim 1, wherein the method comprises the steps of: in the step (1), the organic solvent is N-methyl pyrrolidone or N, N-dimethyl formamide-d7N, N-dimethylacetamide-d9Or dimethyl sulfoxide-d6One or more of (a).
6. The method for preparing a bicomponent asymmetric hollow fiber ceramic membrane having a petal-shaped cross section according to claim 1, wherein the method comprises the steps of: in the step (2), the ceramic powder is Al2O3、ZrO2、TiO2Or SiO2One or more of; the mass ratio of the ceramic powder to the polymer solution is 6-12:5, the average particle size of the ceramic powder is 0.02-10 μm, and the viscosity of the ceramic-polymer casting solution is 25000-55000 MPa.s.
7. The method for preparing a bicomponent asymmetric hollow fiber ceramic membrane having a petal-shaped cross section according to claim 1, wherein the method comprises the steps of: in the step (3), the vacuumizing pressure is 0.01-0.1MPa, the vacuumizing time is 1-2h, the spinning pressure is 0-0.25MPa, the soaking temperature is 20-80 ℃, and the soaking time is 12-48 h.
8. The method for preparing a bicomponent asymmetric hollow fiber ceramic membrane having a petal-shaped cross section according to claim 1, wherein the method comprises the steps of: in the step (3), the inner condensation liquid is N, N-dimethylformamide-d7N, N-dimethylacetamide-d9Dimethyl sulfoxide-d6One or more of water, ethanol, propanol or ethylene glycol; the external condensation liquid is water or ethanol.
9. The method for preparing a bicomponent asymmetric hollow fiber ceramic membrane having a petal-shaped cross section according to claim 1, wherein the method comprises the steps of: in the step (4), the sintering: firstly, heating to 600 + 800 ℃ at a heating rate of 2-5 ℃ per min, and roasting for 1-8 h; and then raising the temperature to 1000 ℃ with a temperature raising speed of 1-2 ℃ per min, sintering for 1-10h, then lowering the temperature to 750 ℃ with a temperature raising speed of 1-2 ℃ per min, and finally lowering the temperature to room temperature.
10. The method for preparing a bicomponent asymmetric hollow fiber ceramic membrane having a petal-shaped cross section according to claim 1, wherein the method comprises the steps of: in the step (5), the selectively permeable functional film layer is La0.6Sr0.4Co0.2Fe0.8O3−δ Thin film layer, Ba0.5Sr0.5Co0.8Fe0.2O3−δ Film layer, molecular sieve film layer, Al2O3 Thin film layer, NiO thin film layer or Co3O4 And the thickness of the selective permeability functional film layer is 1-20 mu m.
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| EP0948827A1 (en) * | 1996-11-18 | 1999-10-13 | University Of Southern California | Novel polymer electrolyte membranes for use in fuel cells |
| CN102240508A (en) * | 2010-05-14 | 2011-11-16 | 韩国energy技术研究院 | Ba 0.5 Sr0.5 Co 0.8 Fe 0.2 O3- delta film coated by La 0.6 Sr0.4 Ti0.3 Fe 0.7 O3-delta for oxygen separation and preparing method thereof |
| CN103349918A (en) * | 2013-06-19 | 2013-10-16 | 南京工业大学 | Method for preparing multichannel ceramic hollow fiber membrane |
| CN105056771A (en) * | 2015-07-20 | 2015-11-18 | 胡萍 | Enhanced hollow fiber membrane and preparation method thereof |
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| EP0948827A1 (en) * | 1996-11-18 | 1999-10-13 | University Of Southern California | Novel polymer electrolyte membranes for use in fuel cells |
| CN102240508A (en) * | 2010-05-14 | 2011-11-16 | 韩国energy技术研究院 | Ba 0.5 Sr0.5 Co 0.8 Fe 0.2 O3- delta film coated by La 0.6 Sr0.4 Ti0.3 Fe 0.7 O3-delta for oxygen separation and preparing method thereof |
| CN103349918A (en) * | 2013-06-19 | 2013-10-16 | 南京工业大学 | Method for preparing multichannel ceramic hollow fiber membrane |
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