CN114682101A - Carbon hollow fiber membrane and preparation method thereof - Google Patents
Carbon hollow fiber membrane and preparation method thereof Download PDFInfo
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- CN114682101A CN114682101A CN202011599541.2A CN202011599541A CN114682101A CN 114682101 A CN114682101 A CN 114682101A CN 202011599541 A CN202011599541 A CN 202011599541A CN 114682101 A CN114682101 A CN 114682101A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000012528 membrane Substances 0.000 title claims abstract description 108
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 75
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 47
- 238000009987 spinning Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 51
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 17
- 239000002033 PVDF binder Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 150000001879 copper Chemical class 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- -1 alcohol amine Chemical class 0.000 claims description 6
- 230000001112 coagulating effect Effects 0.000 claims description 6
- 230000004907 flux Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 238000005345 coagulation Methods 0.000 claims description 3
- 230000015271 coagulation Effects 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 229920001955 polyphenylene ether Polymers 0.000 claims 1
- 238000005087 graphitization Methods 0.000 abstract description 8
- 230000035699 permeability Effects 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- 238000003763 carbonization Methods 0.000 description 9
- 230000001965 increasing effect Effects 0.000 description 7
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- 230000000052 comparative effect Effects 0.000 description 5
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- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- 239000010410 layer Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
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- 239000003054 catalyst Substances 0.000 description 2
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- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
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Images
Classifications
-
- 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
-
- 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
- B01D67/0067—Inorganic membrane manufacture by carbonisation or pyrolysis
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
- B01D69/087—Details relating to the spinning process
-
- 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
- B01D71/021—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/26—Electrical properties
Abstract
The invention discloses a carbon hollow fiber membrane and a preparation method thereof. The method comprises the following steps: (1) preparing a pore-forming agent dispersion liquid; (2) uniformly ultrasonically dispersing graphene oxide in a solvent, mixing the graphene oxide with a pore-forming agent dispersion solution, and mixing the graphene oxide with an organic membrane material to prepare a spinning solution; (3) spinning by using a spinning head of a spinning machine by using the spinning solution as a shell solution and water as a core solution to obtain a hollow fiber membrane precursor; (4) and roasting the hollow fiber membrane precursor for 1-4 h at the temperature of 700-1500 ℃ in an inert atmosphere, then soaking the roasted product in dilute nitric acid, and washing and drying to obtain the carbon hollow fiber membrane. The method is beneficial to reducing the graphitization temperature of the carbon hollow fiber membrane and enhancing the permeability and mechanical strength of the membrane.
Description
Technical Field
The invention belongs to the technical field of membranes, and relates to a carbon hollow fiber membrane and a preparation method thereof.
Background
Among many inorganic membrane materials, carbon materials are attracting attention because of their advantages such as good thermal stability, chemical stability, resistance to organic solvents, acid, alkali and microbial corrosion, and low cost. The traditional carbon material separation membrane is usually prepared by loading an organic precursor on a support and performing high-temperature carbonization. However, the great difference in thermal conductivity between the carbon layer and the support causes the carbon layer to crack due to uneven heating, which affects the film forming quality. The carbon hollow fiber membrane is used as a self-supporting membrane, and the problem can be effectively avoided. At present, organic polymer hollow fiber membranes such as Polyacrylonitrile (PAN) hollow fiber membranes, Cellulose (CA) hollow fiber membranes, Polyimide (PI) hollow fiber membranes, and the like are used as precursors in the prior art, and carbon hollow fiber membranes are prepared by a carbonization process. The carbon hollow fiber membrane prepared by the process has the defects of poor mechanical strength and permeability. The main reason for this result is that the carbon material composing the carbon hollow fiber membrane is mainly amorphous carbon, which has poor mechanical strength, and the membrane pore path formed by amorphous carbon is long and tortuous, and has large permeation resistance, so that the carbon hollow fiber membrane has poor permeability, is often used for gas separation and purification, and is difficult to apply in the large-scale water treatment field in the market.
Researches show that the conversion of amorphous carbon to graphitized carbon can be realized by high-temperature carbonization (more than 3000 ℃), the graphitized carbon material has higher mechanical strength and smaller mass transfer resistance, and is beneficial to improving the mechanical strength and the permeability of the carbon hollow fiber membrane, but the high-temperature carbonization has high requirements on equipment and materials, so that the production cost is greatly increased, and the application of the carbon hollow fiber membrane is not facilitated. Therefore, the preparation method of the novel carbon hollow fiber membrane is developed, the mechanical strength and the permeability of the membrane are improved, and the membrane has important research value and market value.
Disclosure of Invention
Aiming at the defects of the existing carbon hollow fiber membrane preparation process, the preparation method of the carbon hollow fiber membrane and the carbon hollow fiber membrane obtained by the method are provided. The method is beneficial to reducing the graphitization temperature of the carbon hollow fiber membrane and enhancing the permeability and mechanical strength of the membrane.
The first aspect of the present invention provides a method for producing a carbon hollow fiber membrane, comprising:
(1) uniformly mixing the copper salt solution and the alcohol amine solution, and standing for 1-7 days to obtain a pore-forming agent dispersion liquid;
(2) uniformly ultrasonically dispersing graphene oxide in a solvent, and then mixing the graphene oxide with a pore-forming agent dispersion liquid to obtain a mixture; adding an organic membrane material into the mixture under the condition of stirring and heating to prepare a spinning solution;
(3) taking the spinning solution as shell solution and water as core solution, and simultaneously passing through a spinning head of a spinning machine, wherein the ratio of the volume flow rate of the shell solution to the volume flow rate of the core solution is 0.5-5: spinning into a coagulating bath at the speed of 1, and naturally drying to obtain a hollow fiber membrane precursor;
(4) and roasting the hollow fiber membrane precursor for 1-4 h at the temperature of 700-1500 ℃ in an inert atmosphere, then soaking the roasted product in dilute nitric acid, and washing and drying to obtain the carbon hollow fiber membrane.
In the above technical solution, in the step (1), the copper salt may be a soluble copper salt, such as at least one of copper nitrate and copper chloride. The concentration of the copper salt solution is 1-20 mmol/L.
In the above technical solution, in the step (1), the alcohol amine is at least one selected from monoethanolamine, diethanolamine and triethanolamine. The concentration of the alcohol amine solution is 1-10 mmol/L.
In the above technical solution, the pore-forming agent dispersion prepared in step (1) contains Cu (OH) with a diameter of 3-100 nm2A nanowire.
In the above technical solution, in the step (2), the graphene oxide may be at least one selected from a single-layer graphene oxide and a multi-layer graphene oxide.
In the above technical solution, in the step (2), the solvent is at least one selected from N-N dimethylformamide, N-methylpyrrolidone, and dimethylsulfoxide. The addition amount of the graphene oxide accounts for 0.1-10% of the mass of the organic membrane material.
In the above technical scheme, in the step (2), the organic film material is selected from polyacrylonitrile, polyvinylidene fluoride, cellulose acetate, polyimide, polyetherimide or polyphenylene oxide. The addition amount of the organic membrane material accounts for 10-20% of the mass of the spinning solution.
In the technical scheme, in the step (2), the adding amount of the pore-forming agent accounts for 10-50% of the mass of the organic membrane material.
In the above technical scheme, in the step (2), the specific process of sequentially adding the organic film material to the mixture under the condition of stirring and heating is as follows: the stirring speed is 300-800 rpm, the heating rate is 1-2 ℃/min, and the temperature is 40-60 ℃.
In the above technical scheme, in the step (3), the spinning head is a coaxial spinning head with a concentric circle structure.
In the above technical solution, in the step (3), the coagulating bath is water. The temperature of the coagulating bath is 0-40 ℃.
In the above technical solution, in the step (4), the inert atmosphere may be at least one of nitrogen and argon.
In the above technical scheme, in the step (4), the concentration of the dilute nitric acid is 0.1 mol/L-1 mol/L.
In the above technical scheme, in the step (4), the calcination is carried out at 1500 ℃ of 700-.
In the above technical scheme, in the step (4), the time for soaking the roasted product in dilute nitric acid is 0.5-2 days.
In the above technical solution, in the step (4), the washing may be deionized washing. The drying conditions were as follows: the drying temperature is 40-80 deg.C, and the drying time is 4-12 h.
In the technical scheme, the aperture of the carbon hollow fiber membrane obtained in the step (4) is 1-100 nm, and the membrane flux is 10-100 L.m-2·bar-1·h-1. The carbon hollow fiber membrane is an ultrafiltration membrane and can be used for removing bacteria and turbidity.
The invention has the following beneficial effects:
1. in the method of the present invention, sp will be possessed2Adding the structural graphene oxide into an organic membrane material, adding a specific pore-forming agent, and preparing the hollow fiber membrane precursor containing the graphene oxide by a wet spinning technology. The carbonization temperature of the hollow fiber membrane precursor is controlled, so that the graphene oxide plays a role in catalyzing the graphitization of the carbon material, the graphitization conversion temperature (below 1500 ℃) of the amorphous carbon material is reduced, the graphitization conversion at a lower temperature is realized, and the obtained carbon hollow fiber membrane has good permeability and mechanical strength and certain conductivity.
2. Compared with the traditional high-temperature carbonization method, the method has the advantages of low preparation cost, no need of expensive high-temperature-resistant equipment and high preparation efficiency.
Drawings
Fig. 1 is a scanning electron microscope picture of a carbon hollow fiber membrane added with 10% graphene oxide prepared in example 2 of the present invention;
fig. 2 is a scanning electron microscope picture of the membrane pores of a hollow carbon fiber membrane (a) prepared in comparative example 1 without adding graphene oxide and a carbon hollow fiber membrane (b) prepared in example 2 with 10% graphene oxide added according to the present invention;
fig. 3 is a raman test graph of a carbon hollow fiber membrane without addition of graphene oxide prepared in comparative example 1, a carbon hollow fiber membrane with addition of 1% graphene oxide prepared in example 3, and a carbon hollow fiber membrane with addition of 5% graphene oxide prepared in example 1 according to the present invention;
fig. 4 is a graph showing changes in (a) flexural strength of a carbon hollow fiber membrane prepared in comparative example 1 to which no graphene oxide is added, a carbon hollow fiber membrane prepared in example 3 to which 1% graphene oxide is added, a carbon hollow fiber membrane prepared in example 1 to which 5% graphene oxide is added, and a carbon hollow fiber membrane prepared in example 2 to which 10% graphene oxide is added, according to the present invention;
fig. 5 is a graph showing changes in (b) tensile strength of the carbon hollow fiber membrane without graphene oxide prepared in comparative example 1, the carbon hollow fiber membrane with 1% graphene oxide prepared in example 3, the carbon hollow fiber membrane with 5% graphene oxide prepared in example 1, and the carbon hollow fiber membrane with 10% graphene oxide prepared in example 2 according to the present invention.
Detailed Description
The embodiments of the present invention will be described below with reference to the drawings, but the present invention is not limited to the following embodiments.
In the invention, the Raman test is characterized by adopting a DRS type Raman tester of Thermo Fisher company;
in the invention, the tensile strength and the bending strength are represented by a 3345 type universal tester of Instron company;
in the invention, a scanning electron microscope image is characterized by adopting a Hitachi S-4800 type scanning electron microscope;
in the invention, the membrane flux is measured by an external pressure method, and the membrane aperture is represented by an aperture tester.
Example 1 a carbon hollow fiber membrane with 5% graphene oxide added was prepared.
The preparation method comprises the following steps of preparing the carbon hollow fiber membrane by using graphene oxide as a catalyst and polyacrylonitrile as a membrane material:
(1) preparing a pore-forming agent: preparing 4 mmol/L copper nitrate solution, adding 1.6mmol/L ethanolamine solution, stirring strongly, and standing for 1 day to obtain pore-forming agent dispersion solution;
(2) preparing a spinning solution of a carbon nano material containing graphene oxide: and uniformly dispersing the graphene oxide in an N-N dimethylformamide solvent to prepare slurry with the mass fraction of 0.5%. Then, polyacrylonitrile is added into the graphene oxide solution one by one under the conditions of rotating speed of 300 rpm and heating at 60 ℃, so that the amount of the graphene oxide is 5 percent of the mass of the polyacrylonitrile, and a pore-forming agent dispersion solution accounting for 20 percent of the mass of the polyacrylonitrile is added to prepare a spinning solution with the mass concentration of the polyacrylonitrile being 10 percent;
(3) and (3) wet spinning: spinning the spinning solution serving as shell solution and water serving as core solution into a water coagulation bath at the shell solution volumetric flow rate of the spinning head with a concentric structure and the core solution volumetric flow rate =0.5:1, and then taking out and drying to obtain a polyacrylonitrile hollow fiber membrane;
(4) anaerobic carbonization: carbonizing a polyacrylonitrile precursor hollow fiber membrane for 2 hours at 1000 ℃, cooling, soaking for one day by using 0.1 mol/L dilute nitric acid, taking out, cleaning, and drying for 4 hours at 60 ℃ to obtain the carbon hollow fiber membrane.
As a result: the obtained carbon hollow fiber membrane has a pore diameter of about 20nm, belongs to ultrafiltration membrane, and has a membrane flux of 50 L.m-2·bar-1·h-1。
Example 2 a carbon hollow fiber membrane to which 10% graphene oxide was added was prepared.
The preparation method comprises the following steps of preparing the carbon hollow fiber membrane by using graphene oxide as a catalyst and polyvinylidene fluoride as a membrane material:
(1) preparing a pore-forming agent: preparing 10 mmol/L copper nitrate solution, adding 1.6mmol/L ethanolamine solution, stirring strongly, and standing for 7 days to obtain the pore-forming agent dispersion.
(2) Preparing a spinning solution of a carbon nano material containing graphene oxide: graphene oxide is uniformly dispersed in an N-N dimethylformamide solvent to prepare slurry with the concentration of 1%. Then, polyvinylidene fluoride is sequentially added into the graphene oxide solution under the conditions of rotating speed of 300 rpm and heating at 40 ℃, the amount of graphene oxide is 10% of the mass of polyvinylidene fluoride, and a pore-forming agent dispersion liquid accounting for 40% of the mass of polyvinylidene fluoride is added to prepare a spinning solution with the concentration of polyvinylidene fluoride of 10%.
(3) And (3) wet spinning: spinning the spinning solution serving as shell solution and water serving as core solution into a water coagulation bath at the shell solution volumetric flow rate and core solution volumetric flow rate =1:1 by using a spinning head with a concentric circle structure, and taking out and drying to obtain the polyvinylidene fluoride hollow fiber membrane.
(4) Anaerobic carbonization: because the polyvinylidene fluoride material has a low melting point and cannot be pre-oxidized, the polyvinylidene fluoride precursor hollow fiber membrane is directly carbonized for 2 hours at 1200 ℃, is naturally cooled, is soaked in 0.1 mol/L dilute nitric acid for one day, is taken out for cleaning, and is dried for 4 hours at 60 ℃ to obtain the carbon hollow fiber membrane.
As a result: the aperture of the obtained carbon hollow fiber membrane is about 50 nm according to the measurement of an aperture tester, belonging to the technical field of carbon hollow fiber membranesThe ultrafiltration membrane has a flux of 100 L.m-2·bar-1·h-1 。
Example 3 a carbon hollow fiber membrane with 1% graphene oxide added was prepared.
The difference from example 1 is that 1% of graphene oxide was added to make a carbon hollow fiber membrane in an amount of 1% by mass of polyacrylonitrile.
Comparative example 1
(1) Preparing a spinning solution without graphene oxide: sequentially adding polyacrylonitrile into an N-N dimethylformamide solvent under the conditions of rotating speed of 300 rpm and heating at 60 ℃, and then adding a polyvinylpyrrolidone pore-forming agent (the mass ratio of the polyvinylpyrrolidone pore-forming agent to the polyacrylonitrile is 1:4) to prepare a spinning solution with the polyacrylonitrile concentration of 10%;
(2) and (3) wet spinning: spinning the spinning solution serving as shell liquid and water serving as core liquid into a coagulating bath at the speed of shell liquid volumetric flow rate and core liquid volumetric flow rate =1:1 by using a spinning head with a concentric circle structure, and taking out and drying to obtain the polyacrylonitrile hollow fiber membrane.
(3) Anaerobic carbonization: carbonizing a polyacrylonitrile hollow fiber membrane at 1000 ℃ for 2 h, naturally cooling, soaking in 0.1 mol/L dilute nitric acid for one day, taking out, cleaning, and drying at 60 ℃ for 4 h to obtain the carbon hollow fiber membrane.
As a result: according to the measurement of a pore diameter tester, the pore diameter of the obtained carbon hollow fiber membrane is less than 5 nm, and the membrane flux is less than 1 L.m-2·bar-1·h-1 。
According to the invention shown in fig. 3, when the addition amount of graphene oxide is increased from 0 to 5%, raman test I of the prepared carbon hollow fiber membrane is performedD/IGBy increasing from about 0.8 by about 1.2, the degree of graphitization of the material is significantly increased. The increase in the degree of graphitization brings about an increase in the mechanical strength of the carbon hollow fiber membrane.
According to the present invention, as shown in fig. 4 and 5, when the amount of graphene oxide added is increased from 0 to 10%, the bending strength and the tensile strength of the carbon hollow fiber membrane are increased by 2.0 to 4.8 times and 4.3 to 16.0 times, respectively, as the amount of graphene added is increased. Meanwhile, according to the change of the membrane pores in fig. 2, it can be seen that the membrane pores become smooth and compact due to the increase of the graphitization degree, which is beneficial to enhancing the permeability of the membrane.
The above-mentioned embodiments are only specific embodiments of the present invention, and should not be construed as limiting the invention, so that obvious modifications and other modifications without departing from the spirit of the present invention are included in the scope of the present invention.
Claims (12)
1. A method of making a carbon hollow fiber membrane, comprising:
(1) uniformly mixing the copper salt solution and the alcohol amine solution, and standing for 1-7 days to obtain a pore-forming agent dispersion liquid;
(2) uniformly ultrasonically dispersing graphene oxide in a solvent, and then mixing the graphene oxide with a pore-forming agent dispersion liquid to obtain a mixture; adding an organic membrane material into the mixture under the condition of stirring and heating to prepare a spinning solution;
(3) taking the spinning solution as shell solution and water as core solution, and simultaneously passing through a spinning head of a spinning machine, wherein the ratio of the volume flow rate of the shell solution to the volume flow rate of the core solution is 0.5-5: spinning into a coagulating bath at the speed of 1, and naturally drying to obtain a hollow fiber membrane precursor;
(4) and roasting the hollow fiber membrane precursor for 1-4 h at the temperature of 700-1500 ℃ in an inert atmosphere, then soaking the roasted product in dilute nitric acid, and washing and drying to obtain the carbon hollow fiber membrane.
2. The method according to claim 1, wherein in the step (1), the copper salt is at least one of copper nitrate and copper chloride; the concentration of the copper salt solution is 1-20 mmol/L; the alcohol amine is selected from at least one of monoethanolamine, diethanolamine and triethanolamine; the concentration of the alcohol amine solution is 1-10 mmol/L.
3. The method according to claim 1, wherein in the step (2), the solvent is at least one selected from the group consisting of N-N dimethylformamide, N-methylpyrrolidone, and dimethylsulfoxide; the addition amount of the graphene oxide accounts for 0.1-10% of the mass of the organic membrane material.
4. The method according to claim 1, wherein in step (2), the organic film material is selected from polyacrylonitrile, polyvinylidene fluoride, cellulose acetate, polyimide, polyetherimide or polyphenylene ether; the addition amount of the organic film material accounts for 10-20% of the mass of the spinning solution.
5. The method of claim 1 wherein in step (2), the pore former dispersion is added in an amount of 10% to 50% by mass of the organic membrane material.
6. The method according to claim 1, wherein in step (2), the organic film material is added to the mixture under heating with stirring by the following specific process: the stirring speed is 300-800 rpm, the heating rate is 1-2 ℃/min, and the temperature is 40-60 ℃.
7. The method according to claim 1, wherein in step (3), the coagulation bath is water; the temperature of the coagulating bath is 0-40 ℃.
8. The method of claim 1, wherein in step (4), the dilute nitric acid has a concentration of 0.1 mol/L to 1 mol/L.
9. The method as claimed in claim 1, wherein in the step (4), the calcination is carried out at 800-1300 ℃ for 1-4 h.
10. The method according to claim 1, wherein in the step (4), the roasted product is soaked in the dilute nitric acid for 0.5-2 days; the drying conditions were as follows: the drying temperature is 40-80 deg.C, and the drying time is 4-12 h.
11. A carbon hollow fiber membrane produced by the production method according to any one of claims 1 to 10.
12. The carbon hollow fiber membrane according to claim 11, wherein the carbon hollow fiber membrane has a pore diameter of 1nm to 100nm and a membrane flux of 10 to 100L · m-2·bar-1·h-1。
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