CN108970417B - Method for preparing metal hollow fiber membrane - Google Patents
Method for preparing metal hollow fiber membrane Download PDFInfo
- Publication number
- CN108970417B CN108970417B CN201810571597.3A CN201810571597A CN108970417B CN 108970417 B CN108970417 B CN 108970417B CN 201810571597 A CN201810571597 A CN 201810571597A CN 108970417 B CN108970417 B CN 108970417B
- Authority
- CN
- China
- Prior art keywords
- hollow fiber
- fiber membrane
- metal hollow
- tube
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- B01D71/022—Metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0076—Pretreatment of inorganic membrane material prior to membrane formation, e.g. coating of metal powder
-
- 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
Abstract
The invention relates to a method for directly preparing an ultrathin, superfine and smooth-outer-surface metal hollow fiber membrane, which comprises the following steps: carrying out coating pretreatment on the inner wall of the dense tube by using an organic solvent A; mixing and stirring metal powder and an organic solvent B in proportion for 24 hours, and then vacuumizing and defoaming to prepare a suspension; and (3) uniformly coating the newly prepared suspension on the inner wall of the compact tube, drying, putting into a sintering furnace for high-temperature sintering and degreasing, and obtaining the metal hollow fiber membrane with a thin membrane layer. The method has simple preparation process and low cost. Can be widely applied to the fields of petrochemical industry, biological medicine, food and beverage, water treatment and the like.
Description
Technical Field
The invention relates to a production method for preparing a metal hollow fiber membrane, belonging to the technical field of membranes.
Technical Field
The application range of the porous metal film is very wide, and with the further development of the filtration technology, the application field of the porous metal film is gradually expanded from the fields of petrifaction, pharmacy and the like to the high-technology fields of aerospace, seawater desalination, military and the like. The methods commonly used at present are a dry/wet spinning method and a thermally induced phase separation method for preparing a metal hollow fiber membrane. The dry/wet spinning method is to extrude the casting solution with high powder concentration through a spinning nozzle under the action of pressure and then to sinter the casting solution. However, since the metal film is extruded through a spinneret, it is difficult to control the thickness of the film to be 100 μm or less, and the film thickness is large, and finger-like voids are formed inside the film, thereby affecting the performance of the film. Meanwhile, in the dry/wet spinning method, the content of organic matters in the membrane casting solution is high, so that the content of residual carbon in the hollow fiber is high in the sintering process, and the toughness of the hollow fiber membrane is reduced.
Patent CN103386486A provides a method for preparing an unsupported porous metal film, which comprises the steps of uniformly mixing an organic solvent and metal powder, coating the mixture on the surface of a substrate, drying, peeling to obtain a blank, and finally placing a ceramic filler and the blank into a sintering mold to be sintered together to obtain the planar unsupported porous metal film. By the method, the blank is easy to damage in the process of stripping the porous metal film blank, and the operation difficulty is high; meanwhile, the organic matter content of the slurry is higher, so that the toughness of the metal film is easy to deteriorate in the sintering process; most importantly, the method can only produce a planar porous metal membrane, cannot directly prepare the tubular metal hollow fiber membrane, and has large application limitation.
Chinese patent application No. 201510009024.8 discloses a method for preparing a seamless metal tube, which comprises preparing metal powder into a suspension, placing the suspension in a mold of a porous ceramic tube, coating the metal powder inside the ceramic tube by filtration or impregnation, utilizing the capillary action of the three-dimensional pore channels of the porous ceramic tube and the permeability of fluid, drying, and sintering integrally. The process is simple, and the porous metal tube can be prepared, but the coating is directly carried out on the porous base material by the method, and partial metal powder can enter the pore channel of the porous base material, so that the prepared porous metal has high surface roughness and more defects; on the other hand, the use of fine-porous ceramics or ceramics coated with a film is not suitable for industrial use because the mold itself is expensive.
The chinese patent application No. 201110168259.3 discloses an isostatic pressing method for preparing porous tube, which comprises preparing a ceramic coating on the inner surface of a rigid outer mold, adding metal powder into the cavities of the rigid outer mold and the elastic inner mold, and co-firing after isostatic pressing to obtain the porous ceramic-metal composite membrane. When the ceramic coating is prepared by a dipping method or a spin-coating method, a blocking agent is not used for blocking between the ceramic powder and the outer die, so that the ceramic coating is broken and even cannot fall off in the demoulding process.
Disclosure of Invention
The invention provides a method for preparing an ultrathin metal hollow fiber membrane, which comprises the steps of uniformly coating a suspension on the inner wall of a compact tube, drying and sintering to obtain the ultrathin metal hollow fiber membrane.
The invention aims to solve the problems of large pipe diameter limitation, more internal defects of a film layer, complex preparation process and the like of the prepared hollow fiber film existing in the conventional preparation method of the hollow fiber film, and provides a method for preparing a metal hollow fiber film, in particular a preparation method which has good internal uniformity of the film layer, is ultrathin and has no size limitation on the pipe diameter of a film pipe.
The invention adopts the following technical scheme: the method comprises the following steps: (1) carrying out coating pretreatment on the inner wall of the compact tube by using an organic solvent A, (2) mixing and stirring metal powder and an organic solvent B in proportion for 24h, then vacuumizing and defoaming to prepare a suspension, (3) uniformly coating the newly prepared suspension on the inner wall of the compact tube, drying, then putting into a sintering furnace for degreasing and high-temperature sintering, and obtaining the metal hollow fiber membrane with a thin membrane layer after shedding.
The compact tube is made of stainless steel, tungsten steel, nickel-based alloy or ceramic, and the inner diameter of the tube is 0.1-10 mm.
The compact pipe is a straight pipe or a reducing pipe.
The organic solvent A is a silane coupling agent such as 1, 2-diethoxysilane (BTSE), gamma-aminopropylsilane (gamma-APS) or vinyl trimethoxy silane.
The organic solvent B is methyl cellulose, polyvinyl alcohol or polyvinyl butyral.
The metal powder is an alloy or a single metal with the average grain diameter of 0.05-20 mu m. Wherein the alloy is preferably stainless steel, titanium alloy, nickel-based alloy or copper alloy; the single metal is preferably iron, copper, titanium or nickel.
The casting solution comprises an organic solvent A in a mass ratio: the metal powder is 1: 1.0-1: 2.0.
The sintering temperature conditions can be divided into: (1) heating-heat preservation stage: heating to 300 ℃ at the temperature of 0 ℃, heating at the rate of 3-5 ℃/min, and then preserving heat for 3-5 h; heating to the temperature of 750 ℃ and 900 ℃ at the heating rate of 1-2 ℃/min at the temperature of 300 ℃, and then preserving heat for 4-6 h; (2) and (3) cooling: the temperature of 900 ℃ is reduced to 0 ℃ at the temperature of 750 ℃ and the rate of temperature reduction is 5-10 ℃/min.
The sintering is carried out in a hydrogen atmosphere, a nitrogen atmosphere, a hydrogen-nitrogen mixed atmosphere, an argon atmosphere or under a vacuum condition.
The film thickness of the metal hollow fiber membrane is 5-1000 μm.
Advantageous effects
The method for directly preparing the ultrathin, superfine and smooth-outer-surface metal hollow fiber membrane simplifies experimental operation and experimental equipment and greatly reduces production cost. The silane coupling agent can prevent element diffusion in the sintering process and is beneficial to complete falling of the metal hollow fiber membrane. Meanwhile, the invention can directly prepare the tubular membrane. In addition, the wall thickness of the prepared metal hollow fiber membrane can reach below 80 μm, the organic matter content of the metal membrane is obviously reduced, and the toughness is improved. Moreover, the metal hollow fiber membrane produced by the invention has small diameter and large length-diameter ratio, and can meet the cross flow requirement.
Drawings
Fig. 1 is a photograph of an ultra-thin stainless steel hollow fiber membrane prepared in example 1.
Fig. 2 is a surface SEM photograph of the ultra-thin stainless steel hollow fiber membrane prepared in example 1.
Fig. 3 is a cross-sectional SEM photograph of the ultra-thin stainless steel hollow fiber membrane prepared in example 1.
Detailed description of the invention
The method for preparing the metal hollow fiber membrane of the present invention is further illustrated by the following examples, which are only for illustrating the present invention and are not limited thereto.
Example 1
(1) A stainless steel compact tube with the inner diameter of 1mm and the wall thickness of 1mm is selected as the straight tube. The stainless steel compact tube is dip-coated in a fresh 0.3% 1, 2-diethoxysilyl ethane solution for 2min, then dried by compressed air, dried and stored for 24 h.
(2) 15g of 316L of stainless steel powder having an average particle size of 3 μm were mixed with 10ml of a 1.5% strength solution of polymethyl cellulose and stirred for 24 hours to form a suspension, and after the freshly prepared suspension was uniformly applied to a dense tube, accelerated drying was carried out by purging with 0.6L/min of nitrogen carrier gas at 30 ℃.
(3) And (3) carrying out high-temperature sintering: heating the stainless steel tube to 300 ℃ at the speed of 3 ℃/min under the hydrogen atmosphere, and preserving the heat for 3h to remove various organic additives. Then heating to 850 ℃ at the speed of 1 ℃/min, preserving heat for 4h, and finally cooling to room temperature at the speed of 5 ℃/min. Thus obtaining the stainless steel hollow fiber membrane.
(4) The SEM micrograph of the cross section of the surface is flat, the pore diameter distribution is uniform and the surface defects are few as shown in figure 1; the SEM micrograph of the cross section is shown in FIG. 2, and the thickness of the film is about 30 μm and the film thickness distribution is uniform. The average pore diameter of the stainless steel membrane was 0.5 μm as measured by bubble pressure method.
Example 2
(1) A ceramic compact tube with the inner diameter of 2mm and the wall thickness of 1mm is selected as the straight tube. The same procedure as in step (1) of example 1 was conducted, except that the solution was a freshly prepared 0.3% solution of γ -aminopropylsilane.
(2) 25g of 316L stainless steel powder having an average particle size of 5 μm were mixed with 20ml of a 1.5% strength solution of polymethyl cellulose and stirred for 24 hours to form a suspension, and after the freshly prepared suspension was uniformly applied to a dense tube, accelerated drying was carried out by purging with 1.4L/min of nitrogen carrier gas at 30 ℃.
(3) Same as step (3) of embodiment 1
(4) The membrane layer was about 50 μm thick and had an average pore diameter of 1 μm.
Embodiment 3
(1) A spiral tube with the inner diameter of 4mm and the wall thickness of 2mm is selected from a tungsten steel compact tube. Same as in step (1) of embodiment 1.
(2) 30g of spherical nickel powder with the average particle size of 5 mu m and 20ml of 2% polymethyl cellulose solution are mixed and stirred for 24h to form suspension, and after the newly prepared suspension is uniformly coated on a compact tube, nitrogen carrier gas purging is carried out at 40 ℃ by 3L/min to accelerate drying.
(3) The same procedure as in step (3) of example 1 was carried out, except that the temperature was raised to 900 ℃.
(4) The thickness of the membrane layer was about 60 μm and the average pore diameter was 1.2. mu.m.
Example 4
(1) A stainless steel dense tube with the inner diameter of 1mm and the wall thickness of 1mm is selected as a spiral tube. The same procedure as in (1) in example 1 was repeated, except that the concentration of the freshly prepared 1, 2-diethoxysilylethane solution was 0.5%.
(2) 30g of spherical nickel powder with the average particle size of 3 mu m is mixed with 20ml of 1.4 percent polymethyl cellulose solution and stirred for 24 hours to form suspension, and after the newly prepared suspension is uniformly coated on a compact tube, nitrogen carrier gas with the concentration of 0.6L/min and the temperature of 30 ℃ is used for blowing and accelerating the drying.
(3) The same procedure as in step (3) of example 1 was carried out, except that the temperature was raised to 900 ℃.
(4) The thickness of the membrane layer was about 50 μm and the average pore diameter was 0.4. mu.m.
Claims (4)
1. A method of making a metal hollow fiber membrane comprising: (1) carrying out coating pretreatment on the inner wall of the dense tube by using an organic solvent A, wherein the organic solvent A is 1, 2-diethoxysilane (BTSE), gamma-aminopropylsilane (gamma-APS) or vinyl trimethoxy silane solution; (2) mixing and stirring metal powder and an organic solvent B in proportion for 24 hours, and then vacuumizing and defoaming to prepare a suspension; wherein the organic solvent B is methyl cellulose, polyvinyl alcohol or polyvinyl butyral solution; wherein the metal powder is an alloy or a monometal having an average particle diameter of 0.05 to 20 μm; the alloy is stainless steel, titanium alloy, nickel-based alloy or copper alloy, and the single metal is iron, copper, titanium or nickel; (3) and uniformly coating the newly prepared suspension on the inner wall of the compact tube, drying, then placing into a sintering furnace for degreasing and high-temperature sintering, and obtaining the metal hollow fiber membrane with a thin membrane layer after shedding, wherein the membrane thickness of the metal hollow fiber membrane is 5-1000 mu m.
2. The method of producing a metal hollow fiber membrane according to claim 1, characterized in that: the compact tube is made of stainless steel, tungsten steel, nickel-based alloy or ceramic, and the inner diameter of the tube is 0.1-10 mm.
3. The method of producing a metal hollow fiber membrane according to claim 1, characterized in that: the compact pipe is a straight pipe or a reducing pipe.
4. The method of producing a metal hollow fiber membrane according to claim 1, characterized in that: the sintering is carried out in a hydrogen atmosphere, a nitrogen atmosphere, a hydrogen-nitrogen mixed atmosphere, an argon atmosphere or under a vacuum condition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810571597.3A CN108970417B (en) | 2018-06-01 | 2018-06-01 | Method for preparing metal hollow fiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810571597.3A CN108970417B (en) | 2018-06-01 | 2018-06-01 | Method for preparing metal hollow fiber membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108970417A CN108970417A (en) | 2018-12-11 |
| CN108970417B true CN108970417B (en) | 2021-03-30 |
Family
ID=64540698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810571597.3A Active CN108970417B (en) | 2018-06-01 | 2018-06-01 | Method for preparing metal hollow fiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108970417B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109745870A (en) * | 2019-02-28 | 2019-05-14 | 西部宝德科技股份有限公司 | A kind of preparation method of porous metal film |
| CN117695869B (en) * | 2024-02-02 | 2024-04-19 | 天津工业大学 | Iron-based alloy hollow fiber membrane for hydrogen separation and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103657435A (en) * | 2013-12-10 | 2014-03-26 | 南京工业大学 | Porous metal hollow fibrous membrane and preparation method |
| CN105013338A (en) * | 2014-04-22 | 2015-11-04 | 中国科学院上海高等研究院 | Once-formed preparation method of ceramic metal double-layer hollow fiber film |
| CN105307758A (en) * | 2013-06-27 | 2016-02-03 | 曼·胡默尔有限公司 | Ceramic whole blood hollow fiber membrane filter medium and use thereof for separating blood plasma / serum from whole blood |
| WO2016168140A1 (en) * | 2015-04-17 | 2016-10-20 | Arkema Inc. | Production system for composite porous solid articles |
-
2018
- 2018-06-01 CN CN201810571597.3A patent/CN108970417B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105307758A (en) * | 2013-06-27 | 2016-02-03 | 曼·胡默尔有限公司 | Ceramic whole blood hollow fiber membrane filter medium and use thereof for separating blood plasma / serum from whole blood |
| CN103657435A (en) * | 2013-12-10 | 2014-03-26 | 南京工业大学 | Porous metal hollow fibrous membrane and preparation method |
| CN105013338A (en) * | 2014-04-22 | 2015-11-04 | 中国科学院上海高等研究院 | Once-formed preparation method of ceramic metal double-layer hollow fiber film |
| WO2016168140A1 (en) * | 2015-04-17 | 2016-10-20 | Arkema Inc. | Production system for composite porous solid articles |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108970417A (en) | 2018-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tan et al. | Preparation and characterization of inorganic hollow fiber membranes | |
| JP3203252B2 (en) | Method for producing ceramic hollow fibers, especially hollow fiber membranes for microfiltration, ultrafiltration and gas separation | |
| CN110922204B (en) | Preparation method of low-temperature sintered alumina ceramic membrane | |
| CN103691330B (en) | A kind of preparation technology of porous stainless steel membrane | |
| CN108970417B (en) | Method for preparing metal hollow fiber membrane | |
| CN103657435A (en) | Porous metal hollow fibrous membrane and preparation method | |
| CN114538950A (en) | Porous silicon carbide ceramic skeleton based on biomass powder as carbon source and preparation method thereof | |
| Nakahira et al. | Green fabrication of porous ceramics using an aqueous electrophoretic deposition process | |
| CN109454231B (en) | Preparation method of iron-aluminum-copper alloy microporous filter material | |
| CN111825448B (en) | Method for preparing straight-through-hole zirconia ceramic with compact hole wall by wet spinning dipping method | |
| CN106631044A (en) | Method for shaping gradient-straight-hole double-layer asymmetric ceramic oxygen separation membrane | |
| CN111548183B (en) | Method for preparing graded porous silicon carbide ceramic by gel casting and carbothermic reduction | |
| US11918958B2 (en) | Fe-Al-based metal porous membrane and preparation method thereof | |
| CN110899703B (en) | Preparation method of high-porosity metal film | |
| CN115594514B (en) | Three-dimensional SiC framework reinforced SiC high-density ceramic and preparation method thereof | |
| CN111620698A (en) | Hierarchical pore ceramic sponge material with low-thermal-conductivity nanofiber framework and preparation method thereof | |
| JP2008156170A (en) | Method for manufacturing high-strength macro-porous ceramics and its porous body | |
| CN110981453A (en) | Preparation method of light ceramic filtering membrane | |
| CN111230118A (en) | FeAlSi intermetallic compound porous material and preparation method and application thereof | |
| CN112828280B (en) | Preparation method of metal membrane with gradient pore diameter structure | |
| KR100395036B1 (en) | manufacture method of open-cell type matal preform | |
| Ohzawa et al. | Preparation of SiC-based cellular substrate by pressure-pulsed chemical vapor infiltration into honeycomb-shaped paper preforms | |
| CN107619284A (en) | A kind of preparation method of SiBNC ceramic foams | |
| CN109020566B (en) | Preparation method of special foamed ceramic for filtering aluminum melt | |
| JPH01133988A (en) | Production of reticular silica whisker-porous ceramic composite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 210009 Nanjing University of Technology, 30 Puzhu South Road, Pukou District, Nanjing, Jiangsu Province Applicant after: Nanjing University of Technology Address before: 210009 Nanjing University of Technology, No. 5 New Model Road, Gulou District, Nanjing City, Jiangsu Province Applicant before: Nanjing University of Technology |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |