CN110935329A - Preparation method of silver/alumina composite hollow fiber oxygen permeable membrane microreactor - Google Patents
Preparation method of silver/alumina composite hollow fiber oxygen permeable membrane microreactor Download PDFInfo
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Abstract
The invention provides a preparation method of a silver/alumina composite hollow fiber oxygen permeable membrane microreactor, which comprises the following steps: preparation of Al2O3A hollow fiber ceramic membrane support; II, secondly: for Al2O3Washing and pretreating the hollow fiber ceramic membrane; thirdly, the method comprises the following steps: for Al2O3Carrying out sensitization and activation treatment on the hollow fiber ceramic membrane; fourthly, the method comprises the following steps: preparing silver/aluminum oxide composite hollow fiber oxygen permeable membrane by chemical plating method, wherein metal Ag is in Al2O3The finger-shaped holes and the outer surface of the hollow fiber ceramic membrane form a cross-linking structure, so that the structure has the advantage of a microreactor structure on one hand, and the stability of the Ag metal membrane can be remarkably improved on the other hand; fifthly: a tubular silver/alumina composite hollow fiber oxygen permeable membrane microreactor is constructed, a tubular silver/alumina composite hollow fiber oxygen permeable membrane is transversely arranged in the microreactor, and both sides of the microreactor are hermetically connected with the inner wall of the microreactor through graphite gaskets. The silver/alumina composite hollow fiber oxygen permeable membrane microreactor prepared by the invention is O2High permselectivity, good stability, suitability for medium and low temperature environment, good chemical and thermal stability, and excellent reaction effect in oxygen-related reaction.
Description
Technical Field
The invention relates to a silver/alumina composite hollow fiber oxygen permeable membrane microreactor, and belongs to the technical field of inorganic membranes.
Background
Silver is a white bright, malleable and ductile metal. Silver has excellent thermal conductivity and electrical conductivity, is easy to polish, and has excellent light reflecting performance, welding performance and good bonding strength. Therefore, the optical waveguide has been widely used in the electronic industry, communication equipment, instruments and meters, airplanes, optical instruments, high-frequency components, waveguides and the like. Through continuous and intensive research and verification, the metallic silver is found to have selective permeability to oxygen. In 1986, Gryaznov et al, preschool university, discovered that metallic silver is selectively permeable to oxygen. In 1993, the research of Outlaw et al found that metallic silver has high oxygen permeation selectivity. In 2010, Bortoloto and the like design a novel double-membrane reactor by utilizing the selective permeability of silver to oxygen, oxygen is slowly introduced into a reaction area of a microreactor through a silver membrane to react with hydrogen, and then benzene is oxidized to directly prepare phenol, but the oxygen permeability is relatively low, so that the direct conversion production is not facilitated.
At present, the preparation method of the metal film mainly comprises a chemical vapor deposition method, a physical vapor deposition method, an electroplating method and chemical plating. Chemical plating is the most widely used method, mainly because there is no restriction on the shape of the material, the operation is simple and convenient, and the controllability is high. Compared with common ceramic tubes, the ceramic hollow fiber membrane prepared by the phase inversion method has the advantages of small diameter, short material transmission distance, thin tube wall, small permeation resistance, large flux and high separation efficiency, thereby being a good carrier of a metal membrane.
Compared with the common ceramic membrane, the finger-shaped holes of the hollow fiber ceramic membrane are equivalent to the micro-channels of the microreactor, and the hollow fiber ceramic membrane has the characteristic of microstructure. Compared with the traditional reactor, the micro-reactor has the unique properties of low energy consumption, high surface/volume ratio, short response time, good reaction controllability, excellent mass and heat transfer performance, uniform flow and temperature distribution, easy amplification and the like. However, the conventional method for preparing the membrane microreactor requires complex technology and expensive equipment, is high in cost, and moreover, is difficult to prepare the conventional ceramic membrane microreactor. Compared with the traditional microreactor, the hollow fiber ceramic membrane microreactor has the advantages that the practicability and operability are enhanced. Moreover, due to the existence of a large number of finger-shaped holes and the characteristic of thin tube wall, the resistance of the membrane body in diffusion is reduced, and the oxygen permeation rate of the membrane is effectively improved. Based on the structural advantages of the hollow fiber membrane, the invention mainly uses a phase inversion method to prepare the alumina hollow fiber membrane, and utilizes a chemical plating method to prepare the silver/alumina composite hollow fiber oxygen permeable membrane on the tubular alumina hollow fiber membrane, so that the oxygen permeable rate is high, the stability is good, the silver/alumina composite hollow fiber oxygen permeable membrane can be suitable for the medium-low temperature environment, and the silver/alumina composite hollow fiber oxygen permeable membrane has the advantages of good chemical and thermal stability and the like.
Disclosure of Invention
The present invention has been made to solve the problems occurring in the prior art, and has an object to,
a preparation method of a silver/alumina composite hollow fiber oxygen permeable membrane microreactor comprises the following steps:
the method comprises the following steps: preparation of Al2O3A hollow fiber ceramic membrane support;
step two: for Al2O3Washing and pretreating the hollow fiber ceramic membrane;
step three: for Al2O3Carrying out sensitization and activation treatment on the hollow fiber ceramic membrane;
step four: preparing a silver/aluminum oxide composite hollow fiber oxygen permeable membrane by adopting a chemical plating method;
step five: constructing a silver/alumina composite hollow fiber oxygen permeable membrane microreactor.
Preference is given toOf the Al2O3The preparation method of the hollow fiber ceramic membrane comprises the following steps:
preparation of Al by phase inversion-sintering technique2O3The hollow fiber ceramic membrane is prepared by uniformly mixing polyether sulfone, N-methyl pyrrolidone and polyvinylpyrrolidone in a mass ratio of 1:4:0.5 under an electric stirrer, and adding Al in batches2O3Adding powder in an amount which is 8 times of the mass of the polyether sulfone, and mixing and stirring for 48 hours to obtain a uniform membrane casting solution; transferring the casting solution into a stainless steel storage tank for vacuum defoaming for 90min, connecting with spinning equipment, extruding the casting solution through a spinning nozzle by using a gas pushing method, and allowing the extruded casting solution to enter an external coagulating bath for solidification and forming, thereby forming Al2O3A hollow fiber membrane precursor; the internal coagulation bath was a mixed solution of 70wt% NMP +30wt% EtOH, Al2O3Solidifying the hollow fiber precursor in water for 24h, fixing the hollow fiber precursor on a flat plate, naturally airing, and then vertically putting the hollow fiber precursor into a tubular resistance furnace to calcine for 4h at 1550 ℃ to obtain the porous Al with certain mechanical strength2O3A hollow fiber ceramic membrane.
Preferably, the Al is2O3The method for pretreating the hollow fiber ceramic membrane comprises the following steps: repeatedly cleaning with ethanol and deionized water in ultrasonic processor to remove Al2O3The deposit on the hollow fiber ceramic membrane was then dried at 100 ℃ for 12 hours.
Preferably, the Al is2O3The method for carrying out sensitization and activation treatment on the hollow fiber ceramic membrane comprises the following steps:
a. at 2g/L SnCl2Hydrochloric acid solution as sensitizing solution, adding Al2O3Soaking hollow fiber ceramic membrane in sensitizing solution for 4min to remove Al2O3Carrying out sensitization treatment on the hollow fiber ceramic membrane;
b. sensitizing Al by deionized water2O3Fully washing the hollow fiber ceramic membrane to remove the residual sensitizing solution on the surface;
c. in 0.2g/L of PdCl2Hydrochloric acid solution is used as activating solution to wash Al2O3Hollow fiber ceramic membraneSoaking in activating solution for 4min to remove Al2O3Activating the hollow fiber ceramic membrane;
d. after activation, Al was also treated with deionized water2O3Fully washing the hollow fiber ceramic membrane to remove the residual activating agent on the surface;
e. repeating the steps a to d until Al2O3Stopping when the surface of the hollow fiber ceramic membrane presents uniform black brown;
f. sensitizing and activating the finished Al2O3The hollow fiber ceramic membrane was dried at 100 ℃ for 12 hours.
Preferably, the method for preparing the silver/aluminum oxide composite hollow fiber oxygen permeable membrane by adopting the chemical plating method in the fourth step comprises the following steps:
with AgNO3Adjusting pH of the plating solution to 8-9 with ammonia water as a film forming material of silver, using disodium ethylene diamine tetraacetate as a complexing agent and hydrazine hydrate as a reducing agent, controlling the water bath temperature at 45 ℃, adding the reducing agent into a plating bottle every 30min, keeping the reaction time for 4h, and after the reaction is finished, adding Al loaded with a silver film2O3The hollow fiber ceramic membrane is repeatedly washed by absolute ethyl alcohol and deionized water, and then is dried at 100 ℃.
Preferably, the silver/alumina composite hollow fiber oxygen permeable membrane microreactor in the fifth step is cylindrical, one end of the silver/alumina composite hollow fiber oxygen permeable membrane microreactor is open and the other end of the silver/alumina composite hollow fiber oxygen permeable membrane microreactor is closed, an air inlet pipe is connected to the cylindrical body, an air outlet pipe is connected to the open end of the silver/alumina composite hollow fiber oxygen permeable membrane microreactor, a tubular silver/alumina composite hollow fiber oxygen permeable membrane is transversely installed in the silver/alumina composite hollow fiber oxygen permeable membrane microreactor, two sides of the silver/alumina composite hollow fiber oxygen permeable membrane microreactor are connected with the inner wall of the silver/alumina composite hollow fiber oxygen permeable membrane microreactor through graphite gaskets for sealing.
The silver/alumina composite hollow fiber oxygen permeable membrane microreactor prepared by the invention has high oxygen permeable rate and good stability, can be suitable for medium and low temperature environments, and has good chemical and thermal stability.
Drawings
FIG. 1 is a schematic structural diagram of a silver/alumina composite hollow fiber oxygen permeable membrane microreactor.
FIG. 2 is a schematic structural diagram of a testing device of a silver/alumina composite hollow fiber oxygen permeable membrane microreactor.
Fig. 3 is a cross-sectional view of the resistance furnace of the test apparatus of fig. 2.
In the figure:
1. a silver/alumina composite hollow fiber oxygen permeable membrane microreactor; 2. an air inlet pipe; 3. an air outlet pipe; 4. silver/alumina composite hollow fiber oxygen permeable membranes; 5. a graphite gasket; 6. a resistance furnace; 7. a pipeline; 8. a nitrogen gas cylinder; 9. an oxygen cylinder; 10. a pressure regulator; 11. a gas flow meter. A
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in figures 1-3, a preparation method of a silver/alumina composite hollow fiber oxygen permeable membrane microreactor comprises the following steps:
the method comprises the following steps: preparation of Al2O3Hollow fiber ceramic membrane support, Al2O3The preparation method of the hollow fiber ceramic membrane comprises the following steps: preparation of Al by phase inversion-sintering technique2O3A hollow fiber ceramic membrane. Firstly, polyether sulfone (PESf), N-methyl pyrrolidone (NMP) and polyvinylpyrrolidone (PVP) are uniformly mixed in a mass ratio of 1:4:0.5 under an electric stirrer, and then Al is added in batches2O3And mixing and stirring the powder (the addition amount is 8 times of the mass of the PESf) for 48 hours to obtain a uniform membrane casting solution. Transferring the casting solution into a stainless steel storage tank for vacuum defoaming for 90min, connecting with spinning equipment, extruding the casting solution through a spinning nozzle by using a gas pushing method, and allowing the casting solution to enter an external coagulation bath (tap water) for solidificationChemical molding to form Al2O3A hollow fiber membrane precursor. The internal coagulating bath is a mixed solution of 70wt.% of NMP and 30wt.% of EtOH, the hollow fiber precursor is solidified in water for 24 hours, fixed on a flat plate and naturally dried, and then vertically placed into a tubular resistance furnace to be calcined for 4 hours at 1550 ℃ to obtain porous Al with certain mechanical strength2O3A hollow fiber ceramic membrane.
Step two: for Al2O3Washing the hollow fiber ceramic membrane for pretreatment, repeatedly cleaning the hollow fiber ceramic membrane with ethanol and deionized water in an ultrasonic processor respectively to remove Al2O3The deposit on the hollow fiber ceramic membrane was then dried at 100 ℃ for 12 hours.
Step three: for Al2O3Carrying out sensitization and activation treatment on the hollow fiber ceramic membrane; at 2g/L SnCl2Hydrochloric acid solution as sensitizing solution, 0.2g/L PdCl2Hydrochloric acid solution as activating solution to Al2O3Hollow fiber ceramic membrane sensitization activation (Sn)2++ Pd2+→Sn4++ Pd0). The specific operation steps are as follows:
a. mixing Al2O3Placing the hollow fiber ceramic membrane into a container containing SnCl2Is immersed in the sensitizing solution for 4min to treat Al2O3Carrying out sensitization treatment on the hollow fiber ceramic membrane;
b. sensitizing Al by deionized water2O3Fully washing the hollow fiber ceramic membrane to remove the residual sensitizing solution on the surface;
c. al after washing2O3Putting hollow fiber ceramic membrane containing PdCl2By immersing in the activating solution for 4min, to Al2O3Activating the hollow fiber ceramic membrane;
d. after activation, Al was also treated with deionized water2O3And fully washing the hollow fiber ceramic membrane to remove the residual activating agent on the surface.
e. Repeating the steps a to d until Al2O3Stopping when the surface of the hollow fiber ceramic membrane presents uniform black brown;
f. sensitizing and activating the finished Al2O3The hollow fiber ceramic membrane was dried at 100 ℃ for 12 hours.
For Al2O3The hollow fiber ceramic membrane is sensitized and activated according to the following principle:
sensitization of metallic tin ions to Al2O3Divalent tin ions are adsorbed on the surface of the hollow fiber ceramic membrane carrier, and the hydrolysate of the hollow fiber ceramic membrane carrier has reducibility. The activation step is the most critical step in the pretreatment, and the quality of the activation step is directly related to whether the plating layer is uniform, the binding force between the plating layer and the carrier and the like. The main component of the common activating solution is PdCl2. The principle of activation is as follows: pd on activation2+As oxidant by Sn2+Reduction, Pd deposited on Al in the form of nanoparticles2O3Surface of hollow fiber ceramic membrane carrier, so that Al2O3The surface of the hollow fiber ceramic membrane carrier has stronger catalytic activity, Pd becomes a catalytic center in the subsequent chemical silver plating process, and the formation of a chemical silver plating layer is promoted through the transverse and longitudinal growth of silver particles at the catalytic center.
Step four: preparing silver/aluminum oxide composite hollow fiber oxygen permeable membrane by chemical plating method, wherein Ag membrane is loaded on Al2O3Hollow fiber ceramic membrane outer surface with AgNO3As a film forming material for silver, ammonia (NH) was used3·H2O) adjusting the pH value of the plating solution to 8-9, taking ethylene diamine tetraacetic acid (EDTA-2 Na) as a complexing agent, and hydrazine hydrate (N)2H4·H2O) is a reducing agent. Controlling the temperature of the water bath at 45 ℃, and adding a reducing agent N into the plating bottle every 30min2H4·H2O, reaction time lasts for 4 h. The chemical reaction equation of the process is as follows: 4Ag++N2H4+4OH-→4Ag+4H2O+N2×) @. After the reaction is finished, repeatedly washing the carrier loaded with the silver film by using absolute ethyl alcohol and deionized water, and then drying the carrier at 100 ℃ for later use. Metal Ag in Al2O3The finger-shaped holes and the outer surface of the hollow fiber ceramic membrane form a cross-linking structure, so that the hollow fiber ceramic membrane has the advantages of a microreactor structure on one hand and can display the advantages of a microreactor structure on the other handThe stability of the Ag metal film is improved.
Step five: the method comprises the steps of constructing a silver/alumina composite hollow fiber oxygen permeable membrane microreactor 1, wherein the silver/alumina composite hollow fiber oxygen permeable membrane microreactor 1 is cylindrical, one end of the silver/alumina composite hollow fiber oxygen permeable membrane microreactor 1 is open and the other end of the silver/alumina composite hollow fiber oxygen permeable membrane microreactor is closed, an air inlet pipe 2 is connected to the cylinder, an air outlet pipe 3 is connected to the open end of the silver/alumina composite hollow fiber oxygen permeable membrane microreactor 1, a tubular silver/alumina composite hollow fiber oxygen permeable membrane 4 is transversely installed in the silver/alumina composite hollow fiber oxygen permeable membrane microreactor 1, two sides of the silver/alumina composite hollow fiber oxygen permeable membrane microreactor are connected with the inner wall of the silver/alumina composite hollow fiber oxygen permeable membrane microreactor.
The oxygen permeation mechanism of the silver/aluminum oxide composite hollow fiber oxygen permeation membrane is as follows:
the silver metal has a special selective permeability to oxygen, so that the silver composite film is widely applied to oxygen purification and various reactions related to oxygen. The permeation mechanism of silver films follows the "dissolution-diffusion" principle. The infiltration process can be divided into the following steps:
(1) oxygen molecules on one side with high osmotic pressure diffuse to the surface of the silver film and are dissociated into high-activity oxygen atoms;
(2) the high active oxygen atoms gradually permeate into the silver film and are dissolved in the silver atom crystal lattice;
(3) the active oxygen atoms in the silver crystal lattice are diffused from one side of the film to the other side of the film in a gradient way;
(4) the active oxygen atoms diffused to the surface are gathered at the surface of the silver film and recombined into oxygen molecules which are desorbed from the surface of the silver film and diffused to the bulk phase at the other side.
A testing device for a silver/alumina composite hollow fiber oxygen permeation membrane microreactor comprises a silver/alumina composite hollow fiber oxygen permeation membrane microreactor 1, wherein the silver/alumina composite hollow fiber oxygen permeation membrane microreactor 1 is installed in a resistance furnace 6, and an air inlet pipe 2 and an air outlet pipe 3 both penetrate through the resistance furnace 6. The air inlet pipe 2 is connected with an oxygen gas storage bottle 9 and a nitrogen gas storage bottle 8 through a pipeline 7, the oxygen gas storage bottle 9 and the nitrogen gas storage bottle 8 are arranged in parallel, and a pressure regulator 10 which comprises a mass flow meter and a pressure gauge is arranged on the pipeline 7 and is used for regulating air inlet pressure; the gas outlet pipe 3 is connected with a gas flowmeter 11 and used for detecting flow. The test conditions of the test device of the composite hollow fiber membrane microreactor are as follows: the testing temperature is 200 ℃ and 500 ℃, the pressure range is 0.025-0.125MPa, the flow of all the raw material gases is controlled by a mass flow meter, the gas pressure difference is controlled by a precision pressure gauge, and the testing temperature is controlled by a resistance furnace.
After the silver/alumina composite hollow fiber oxygen permeable membrane 4 is manufactured, a tightness test needs to be carried out at normal temperature, and the tightness of the silver/alumina composite hollow fiber oxygen permeable membrane 4 is measured by adopting a self-made tightness test device. As shown in figure 2, a silver/alumina composite hollow fiber oxygen permeable membrane 4 is placed in a silver/alumina composite hollow fiber oxygen permeable membrane microreactor 1, a valve of a nitrogen gas storage cylinder 8 is opened, the pressure range is controlled to be 0.025-0.125MPa through a pressure regulator 10, nitrogen gas enters a gap between the silver/alumina composite hollow fiber oxygen permeable membrane microreactor 1 and the silver/alumina composite hollow fiber oxygen permeable membrane 4, and the gas flow is detected through a gas flow meter 11 connected with a gas outlet pipe 3. The calculation formula is expressed by the following formula:
wherein J represents a nitrogen permeation amount, mol.m-2•s-1•Pa-1(ii) a n represents the amount of substance, mol; s represents the surface area of the Ag film, m2(ii) a P represents a pressure difference, Pa; t represents time, s.
The formula for calculating the amount of substance is:
wherein P is0Represents atmospheric pressure, Pa; v represents the flow rate of nitrogen, L; r represents an Avogastron constant; t represents temperature, K.
After the prepared silver/alumina composite hollow fiber oxygen permeable membrane 4 is qualified through detection at normal temperature, then oxygen permeability performance test is carried out, before the oxygen permeability performance test is carried out, an air tightness test is still required to be carried out under the temperature condition corresponding to the oxygen permeability performance test, the test method is the same as the test method at normal temperature, nitrogen gas is firstly carried out, the test temperature is only required to be set between 200 ℃ and 500 ℃ through a resistance furnace 6, after the air tightness test meets the requirement, the air tightness of the silver/alumina composite hollow fiber oxygen permeable membrane 4 between 200 ℃ and 500 ℃ is proved to meet the requirement, then the oxygen permeability performance test is further carried out, firstly, a valve of a nitrogen gas storage bottle 8 is closed, a valve of an oxygen gas storage bottle 9 is opened, the pressure is regulated through a pressure regulator 10 to be always kept at 0.025-0.125MPa, after oxygen enters a gap between a silver/alumina composite hollow fiber oxygen permeable membrane microreactor 1 and the silver/alumina composite hollow fiber oxygen, the silver/aluminum oxide composite hollow fiber oxygen permeable membrane 4 selectively permeates oxygen, oxygen molecules diffuse to the surface of the silver membrane and are dissociated into high-activity oxygen atoms, the high-activity oxygen atoms gradually permeate into the silver membrane and are dissolved in silver atom lattices, the active oxygen atoms in the silver lattices are diffused to the opposite side of the membrane from one side of the silver membrane in a gradient manner, the active oxygen atoms diffused to the surface are gathered on the surface of the silver membrane and recombined to form the oxygen molecules, the oxygen molecules are desorbed from the surface of the silver membrane and diffused into the silver/aluminum oxide composite hollow fiber oxygen permeable membrane 4, and then the oxygen molecules are discharged through the air outlet pipe 3 and enter the gas flowmeter 11 to test the oxygen permeability.
In the invention, Al2O3The surface of the hollow fiber ceramic membrane is loaded with metallic silver, and the metallic silver is opposite to O2Has selective permeability, and the prepared silver/alumina composite hollow fiber oxygen permeable membrane 4 is used as O2Can realize O2The separation is efficient. Al (Al)2O3The hollow fiber ceramic membrane has small diameter, small transmission distance, thin tube wall, small permeation resistance, large flux and high separation efficiency, can be used as a good carrier of a metal membrane, and reduces the difficulty of preparing the silver membrane. Preparation of Al by phase inversion2O3Hollow fiber ceramic membrane, chemical plating method of Al on tubular2O3The preparation of the silver membrane on the hollow fiber ceramic membrane simplifies the preparation process and improves the stability of the membrane. The silver/alumina composite hollow fiber oxygen permeable membrane 4 has good chemical and thermal stability and can be appliedUnder the environment of medium and low temperature, the limit of high temperature condition is overcome, the energy consumption is reduced, the energy utilization rate is improved, and the practicability is increased. The silver/alumina composite hollow fiber oxygen permeable membrane 4 has mild preparation conditions, simple preparation process and low cost. The silver/alumina composite hollow fiber oxygen permeable membrane 4 can be used as a membrane separation material and can construct a high-efficiency medium-low temperature silver/alumina composite hollow fiber oxygen permeable membrane microreactor 1, so that the practical efficiency is further improved.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.
Claims (6)
1. A preparation method of a silver/alumina composite hollow fiber oxygen permeable membrane microreactor is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: preparation of Al2O3A hollow fiber ceramic membrane support;
step two: for Al2O3Washing and pretreating the hollow fiber ceramic membrane;
step three: for Al2O3Carrying out sensitization and activation treatment on the hollow fiber ceramic membrane;
step four: preparing a silver/aluminum oxide composite hollow fiber oxygen permeable membrane by adopting a chemical plating method;
step five: constructing a silver/alumina composite hollow fiber oxygen permeable membrane microreactor.
2. The preparation method of the silver/alumina composite hollow fiber oxygen permeable membrane microreactor according to claim 1 is characterized in that: the Al is2O3The preparation method of the hollow fiber ceramic membrane comprises the following steps:
preparation of Al by phase inversion-sintering technique2O3The hollow fiber ceramic membrane is prepared by mixing polyether sulfone, N-methyl pyrrolidone,Uniformly mixing polyvinylpyrrolidone in a mass ratio of 1:4:0.5 under an electric stirrer, and adding Al in batches2O3Adding powder in an amount which is 8 times of the mass of the polyether sulfone, and mixing and stirring for 48 hours to obtain a uniform membrane casting solution; transferring the casting solution into a stainless steel storage tank for vacuum defoaming for 90min, connecting with spinning equipment, extruding the casting solution through a spinning nozzle by using a gas pushing method, and allowing the extruded casting solution to enter an external coagulating bath for solidification and forming, thereby forming Al2O3A hollow fiber membrane precursor; the internal coagulation bath was a mixed solution of 70wt% NMP +30wt% EtOH, Al2O3Solidifying the hollow fiber precursor in water for 24h, fixing the hollow fiber precursor on a flat plate, naturally airing, and then vertically putting the hollow fiber precursor into a tubular resistance furnace to calcine for 4h at 1550 ℃ to obtain the porous Al with certain mechanical strength2O3A hollow fiber ceramic membrane.
3. The preparation method of the silver/alumina composite hollow fiber oxygen permeable membrane microreactor according to claim 1 is characterized in that: the Al is2O3The method for washing and pretreating the hollow fiber ceramic membrane comprises the following steps: repeatedly cleaning with ethanol and deionized water in ultrasonic processor to remove Al2O3The deposit on the hollow fiber ceramic membrane was then dried at 100 ℃ for 12 hours.
4. The preparation method of the silver/alumina composite hollow fiber oxygen permeable membrane microreactor according to claim 1 is characterized in that: the Al is2O3The method for carrying out sensitization and activation treatment on the hollow fiber ceramic membrane comprises the following steps:
a. at 2g/L SnCl2Hydrochloric acid solution as sensitizing solution, adding Al2O3Soaking hollow fiber ceramic membrane in sensitizing solution for 4min to remove Al2O3Carrying out sensitization treatment on the hollow fiber ceramic membrane;
b. sensitizing Al by deionized water2O3Fully washing the hollow fiber ceramic membrane to remove the residual sensitizing solution on the surface;
c. in 0.2g/L of PdCl2Preparation of hydrochloric acid solutionUsing the washed Al as an activating solution2O3Soaking hollow fiber ceramic membrane in activating solution for 4min to remove Al2O3Activating the hollow fiber ceramic membrane;
d. after activation, Al was also treated with deionized water2O3Fully washing the hollow fiber ceramic membrane to remove the residual activating agent on the surface;
e. repeating the steps a to d until Al2O3Stopping when the surface of the hollow fiber ceramic membrane presents uniform black brown;
f. sensitizing and activating the finished Al2O3The hollow fiber ceramic membrane was dried at 100 ℃ for 12 hours.
5. The preparation method of the silver/alumina composite hollow fiber oxygen permeable membrane microreactor according to claim 1 is characterized in that: the method for preparing the silver/aluminum oxide composite hollow fiber oxygen permeable membrane by adopting the chemical plating method comprises the following steps:
with AgNO3Adjusting pH of the plating solution to 8-9 with ammonia water as a film forming material of silver, using disodium ethylene diamine tetraacetate as a complexing agent and hydrazine hydrate as a reducing agent, controlling the water bath temperature at 45 ℃, adding the reducing agent into a plating bottle every 30min, keeping the reaction time for 4h, and after the reaction is finished, adding Al loaded with a silver film2O3The hollow fiber ceramic membrane is repeatedly washed by absolute ethyl alcohol and deionized water, and then is dried at 100 ℃.
6. The preparation method of the silver/alumina composite hollow fiber oxygen permeable membrane microreactor according to claim 1 is characterized in that: the silver/alumina composite hollow fiber oxygen permeable membrane microreactor in the fifth step is cylindrical, one end of the silver/alumina composite hollow fiber oxygen permeable membrane microreactor is open and the other end of the silver/alumina composite hollow fiber oxygen permeable membrane microreactor is closed, an air inlet pipe is connected to the cylinder, the open end of the silver/alumina composite hollow fiber oxygen permeable membrane microreactor is connected with an air outlet pipe, the silver/alumina composite hollow fiber oxygen permeable membrane microreactor is internally and transversely provided with a tubular silver/alumina composite hollow fiber oxygen permeable membrane, two sides of the silver/alumina composite hollow fiber oxygen permeable membrane microreactor are connected with the inner wall of the silver/alumina composite hollow fiber oxygen permeable membrane microreactor through graphite gaskets.
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| CN111686586A (en) * | 2020-06-29 | 2020-09-22 | 山东理工大学 | Vacuum flow chemical plating method for preparing palladium membrane on inner surface of alumina hollow fiber membrane |
| CN114774895A (en) * | 2022-03-31 | 2022-07-22 | 莫纶(珠海)新材料科技有限公司 | Al2O3Composite functional fiber and its prepn |
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