CN104907052A - Composite nanofiber membrane and making method thereof - Google Patents
Composite nanofiber membrane and making method thereof Download PDFInfo
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- CN104907052A CN104907052A CN201410088644.0A CN201410088644A CN104907052A CN 104907052 A CN104907052 A CN 104907052A CN 201410088644 A CN201410088644 A CN 201410088644A CN 104907052 A CN104907052 A CN 104907052A
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Abstract
The invention discloses a composite nanofiber membrane and a making method thereof. The making method of the composite nanofiber membrane comprises the following steps: 1, making a polymer nanofiber membrane through adopting an electrostatic spinning technology; 2, immersing the polymer nanofiber membrane in a Mg<2+> solution, adding ammonia water, and carrying out hydrothermal treatment; and 3, repeatedly washing by using deionized water, and drying at 60DEG C to obtain the composite nanofiber membrane. The making method has the advantages of simple production process and low production cost, and the composite nanofiber membrane made in the invention has the advantages of large specific surface area, high adsorption efficiency, easy removal from water, no secondary pollution to water, and very good cyclic utilization performances.
Description
Technical field
The present invention relates to field of environment protection, particularly relate to a kind of composite nano-fiber membrane and preparation method thereof.
Background technology
Heavy metal refers to that relative density is greater than the metal of 4.5g/cm3.As copper, lead, zinc, tin, nickel, cobalt, antimony, mercury, cadmium and bismuth etc.All containing heavy metal in air, earth, even food and water.The threat of heavy metal pollution is that it can not be decomposed by the microorganisms, and contrary organism can enriching heavy metal, and some heavy metal can be converted into the stronger metallo-organic compound of toxicity.The toxicity of major part heavy metal ion is further serious with concentration and the growth of action time.
Developing rapidly in recent years along with modern industry, pollution of chromium problem also becomes outstanding day by day.Industrial as plating, plumbous platform refining, intermetallic composite coating, the making of ceramic material, the production of glass etc. all can produce a large amount of chromium.Pollution of chromium can bring many health problems, as human body dehydration, stomach pain, Nausea and vomiting can be caused, feel dizzy, belly distending pain, lung's function sustain damage, serious meeting causes death.The method of heavy-metal ion removal traditional at present comprises chemical precipitation method, ion-exchange, solvent extraction, absorption method etc.But the processing method of traditional process heavy metal ion have a lot of shortcoming as: complicated operation, cost is higher, and treatment effeciency is low, recycles ability etc.Therefore, researching and developing novel reproducible adsorbent is the emphasis that process heavy metal wastewater thereby technology should be paid close attention to.
Nano material causes the extensive concern of people day by day in recent years, and the nano material of numerous species is used to the removal of heavy metal ion, as: active carbon, Fe
3o
4, AlOOH, Mg (OH)
2deng, the adsorbent specific area compared with traditional adsorbent with nanostructured is large, and adsorption efficiency is high.But also there is certain defect due to nano-powder itself, and as: easily reunite, be difficult to Separation of Solid and Liquid, easily secondary pollution etc. is caused to water body, its application is limited by very large.In recent years along with the development of electrostatic spinning technique, electrostatic spinning nano fiber film gradually for the removal of heavy metal ion as chitosan nano fiber membrane.Because most of electrostatic spinning nano fiber film does not have the ability of heavy-metal ion removal, the ability therefore making it have Adsorption of Heavy Metal Ions by carrying out modification to nano fibrous membrane becomes the emphasis of people's research gradually.
Summary of the invention
The present invention is directed to the problems referred to above, propose a kind of composite nano-fiber membrane and preparation method thereof.
The invention provides a kind of preparation method of composite nano-fiber membrane, described method comprises the steps:
(1) method of electrostatic spinning is adopted to prepare polymer nanofibre film;
(2) described polymer nanofibre film is immersed in Mg
2+in solution, add ammoniacal liquor, hydrothermal treatment consists;
(3) repeatedly rinse by deionized water, dry at 60 DEG C, obtain composite nano-fiber membrane.
In described step (1), the polymer prepared selected by described polymer nanofibre film have can with Mg (OH)
2there is the functional group of chelatropic reaction.
Further, described can with Mg (OH)
2there is the functional group of chelatropic reaction, comprising: > C=O ,-CN, OC-N, or-NH
2.
Further, described polymer comprises: polyamide 6 (PA6), polyacrylonitrile (PAN) or thermoplastic polyester elastomer (TPEE).
In described step (2), described Mg
2+solution comprises: MgSO
4solution, MgCl
2solution, or Mg (NO
3)
2solution.
Wherein, the molecular weight of described polymer is greater than 10
5.
In described step (1), the solvent dissolving described polymer used has volatility; The mass fraction of spinning solution is 10-40%; Spinning voltage is 16-24KV; Needle diameter used is 0.6-1.0mm; Receiving range is 10-20cm; Receiver is aluminium foil, and the spinning time is 4-12h.
In described step (2), described Mg
2+the mass fraction of solution is 5-30%; It is 1-5ml that institute adds ammoniacal liquor;
Hydrothermal temperature is 20-80 DEG C; Hydro-thermal time 1-5h.
In described step (3), dry 1h at 60 DEG C, obtains described composite nano-fiber membrane.
In addition, present invention also offers a kind of composite nano-fiber membrane adopting above-mentioned preparation method to obtain.
Composite nano-fiber membrane of the present invention and preparation method thereof, compared with traditional adsorbent, has production technology simple, and specific area is large, high to the removal efficiency of Cr (VI), is easy to Separation of Solid and Liquid, cyclic utilization rate advantages of higher.
Accompanying drawing explanation
Below with reference to accompanying drawings specific embodiments of the invention are described, wherein:
Fig. 1 is Inventive polymers@Mg (OH)
2the preparation flow schematic diagram of composite nano-fiber membrane;
Fig. 2 is Inventive polymers@Mg (OH)
2the schematic diagram of composite nano-fiber membrane;
Fig. 3 is for using the schematic diagram of Cr (VI) solion before and after composite nano-fiber membrane of the present invention absorption.
Detailed description of the invention
The invention provides one and have the magnesium system composite nano-fiber membrane efficiently removing Cr (VI) ability, the preparation method of this composite nano-fiber membrane is roughly described below: first prepare polymer nanofibre film by the method for electrostatic spinning; Then polymer nanofibre film is immersed in Mg
2+in solution, add ammoniacal liquor, hydrothermal treatment consists, make magnesium hydroxide crystal grow the surface on nano fibrous membrane, and then obtain polymer@Mg (OH)
2composite nano-fiber membrane.
With PA6@Mg (OH)
2composite nano-fiber membrane is example, and one provided by the invention is renewable has the magnesium system composite nano-fiber membrane efficiently removing Cr (VI), and its preparation method comprises following key step:
(1) method of electrostatic spinning is used to prepare PA6 nano fibrous membrane;
(2) PA6 nano fibrous membrane is immersed in Mg
2+in solution, add ammoniacal liquor, hydrothermal treatment consists (preferred 1-5h);
(3) repeatedly rinse by deionized water, dry 1h at 60 DEG C, can obtain having the PA6 Mg (OH) efficiently removing Cr (VI)
2composite nano-fiber membrane.
Wherein, above-mentioned steps (1), adopts the method for electrostatic spinning to prepare PA6 nano fibrous membrane and belongs to technology known in the art, be only illustrated the configuration main points of spinning solution and electrostatic spinning apparatus herein, no longer repeat electrospinning process.
The molecular weight of PA6 described above is 1.8-2 ten thousand, and the mass fraction of spinning solution PA6 is 10-40% (being preferably 12-20%), and the relevant parameter configuration of electrostatic spinning apparatus is as follows: spinning voltage is 16-24KV, and needle diameter used is 0.6-1.0mm; Receiving range is 10-20cm; Receiver is aluminium foil, and the spinning time is 4-12h.Mg joins in institute
2+liquid quality fraction is 5-30%, and added ammoniacal liquor is 1-5ml, and hydrothermal temperature is 20-80 DEG C, hydro-thermal time 1-5h.
In order to make technical scheme of the present invention and advantage clearly understand, below in conjunction with accompanying drawing and some exemplary embodiments, the enforcement to technical solution of the present invention is described in further detail.
Embodiment 1
Get 1.6g PA6 (molecular weight is 1.8-2.0 ten thousand), add 10ml formic acid and dissolve, stir 12h, stand-by.
Spinning solution is injected electrostatic spinning apparatus, adjustment spinning parameter is as follows: spinning nozzle is 15cm to the distance of gathering-device (Collector in Fig. 1), spinning solution flow velocity is 1.8mL/h, cathode voltage 20KV, cathode voltage-2KV, drum rotation speed is 100r/min, spinning temperature room temperature, spinning time 11h.Take 1g anhydrous magnesium sulfate, put into the beaker of a certain amount of deionized water, stirring and dissolving.Add the PA6 nano fibrous membrane of certain mass, after nano fibrous membrane is separated with aluminium foil, aluminium foil is taken out.In solution, slowly drip 3ml ammoniacal liquor again, preservative film seals, 40 DEG C of water bath with thermostatic control 2h.Film is taken out, deionized water rinsing, 60 DEG C of oven dry.
Get the composite nano-fiber membrane (also can be called compound adsorbent) of the efficient reusable edible of above-mentioned preparation, be placed in 250ml beaker, add 100ml Cr
2o
7 2-(40mg/L) solution, within 7 days, measure the concentration of chromium ion, experimental result shows, the maximal absorptive capacity of this composite nano-fiber membrane to Cr (VI) reaches 158.2mg/g later.
Embodiment 2
Get 1.6g PA6 (molecular weight is 1.8-2.0 ten thousand), add 10ml formic acid and dissolve, stir 12h, stand-by.
Spinning solution is injected electrostatic spinning apparatus, regulates spinning parameter as follows: spinning nozzle is 15cm to the distance of gathering-device, and spinning solution flow velocity is 1.8mm/h, cathode voltage 20KV, cathode voltage-2KV, drum rotation speed is 100r/min, spinning temperature room temperature, spinning time 11h.Take 1g anhydrous magnesium sulfate, put into the beaker of a certain amount of deionized water, stirring and dissolving.Add the PA6 nano fibrous membrane of certain mass, after nano fibrous membrane is separated with aluminium foil, aluminium foil is taken out.In solution, slowly drip 3ml ammoniacal liquor again, preservative film seals, 40 DEG C of water bath with thermostatic control 2h.Film is taken out, deionized water rinsing, 60 DEG C of oven dry.
Get the compound adsorbent of the efficient reusable edible of above-mentioned preparation, be placed in 250ml beaker, add 100ml Cr
2o
7 2-(60mg/L) solution, within 7 days, measure the concentration of chromium ion, experimental result shows, the maximal absorptive capacity of this composite nano-fiber membrane to Cr (VI) reaches 195.2mg/g later.
Embodiment 3
Get 1.6g PA6 (molecular weight is 1.8-2.0 ten thousand), add 10ml formic acid and dissolve, stir 12h, stand-by.
Spinning solution is injected electrostatic spinning apparatus, regulates spinning parameter as follows: spinning nozzle is 15cm to the distance of gathering-device, and spinning solution flow velocity is 1.8mm/h, cathode voltage 20KV, cathode voltage-2KV, drum rotation speed is 100r/min, spinning temperature room temperature, spinning time 11h.Take 1g anhydrous magnesium sulfate, put into the beaker of a certain amount of deionized water, stirring and dissolving.Add the PA6 nano fibrous membrane of certain mass, after nano fibrous membrane is separated with aluminium foil, aluminium foil is taken out.In solution, slowly drip 3ml ammoniacal liquor again, preservative film seals, 40 DEG C of water bath with thermostatic control 2h.Film is taken out, deionized water rinsing, 60 DEG C of oven dry.
Get the compound adsorbent of the efficient reusable edible of above-mentioned preparation, be placed in 250ml beaker, add 100ml Cr
2o
7 2-(80mg/L) solution, within 7 days, measure the concentration of chromium ion, experimental result shows, the maximal absorptive capacity of this composite nano-fiber membrane to Cr (VI) reaches 225.4mg/g later.
Embodiment 4
Get 1.6g PA6 (molecular weight is 1.8-2.0 ten thousand), add 10ml formic acid and dissolve, stir 12h, stand-by.
Spinning solution is injected electrostatic spinning apparatus, regulates spinning parameter as follows: spinning nozzle is 15cm to the distance of gathering-device, and spinning solution flow velocity is 1.8mm/h, cathode voltage 20KV, cathode voltage-2KV, drum rotation speed is 100r/min, spinning temperature room temperature, spinning time 11h.Take 1g anhydrous magnesium sulfate, put into the beaker of a certain amount of deionized water, stirring and dissolving.Add the PA6 nano fibrous membrane of certain mass, after nano fibrous membrane is separated with aluminium foil, aluminium foil is taken out.In solution, slowly drip 3ml ammoniacal liquor again, preservative film seals, 40 DEG C of water bath with thermostatic control 2h.Film is taken out, washes in deionized water, 60 DEG C of oven dry.
Get the compound adsorbent of the efficient reusable edible of above-mentioned preparation, be placed in 250ml beaker, add 100ml Cr
2o
7 2-(100mg/L) solution, within 3 days, measure the concentration of chromium ion, experimental result shows, the maximal absorptive capacity of this composite nano-fiber membrane to Cr (VI) reaches 260.4mg/g later.
Embodiment 5
Get 1.6g PA6 (molecular weight is 1.8-2.0 ten thousand), add 10ml formic acid and dissolve, stir 12h, stand-by.
Spinning solution is injected electrostatic spinning apparatus, regulates spinning parameter as follows: spinning nozzle is 15cm to the distance of gathering-device, and spinning solution flow velocity is 1.8mm/h, cathode voltage 20KV, cathode voltage-2KV, drum rotation speed is 100r/min, spinning temperature room temperature, spinning time 11h.Take 1g anhydrous magnesium sulfate, put into the beaker of a certain amount of deionized water, stirring and dissolving.Add the PA6 nano fibrous membrane of certain mass, after nano fibrous membrane is separated with aluminium foil, aluminium foil is taken out.In solution, slowly drip 3ml ammoniacal liquor again, preservative film seals, 40 DEG C of water bath with thermostatic control 2h.Film is taken out, deionized water rinsing, 60 DEG C of oven dry.
Get the compound adsorbent of the efficient reusable edible of above-mentioned preparation, be placed in 250ml beaker, add 100ml Cr
2o
7 2-(120mg/L) solution, within 3 days, measure the concentration of chromium ion, experimental result shows, the maximal absorptive capacity of this composite nano-fiber membrane to Cr (VI) reaches 282.6mg/g later.
Composite nano-fiber membrane provided by the invention, compared with traditional adsorbent, has that porosity is high, specific area is large, strong to the removal ability of Cr (VI), takes out and can not cause secondary pollution to water body, cyclic utilization rate advantages of higher in Yi Shui.
Be noted that for the person of ordinary skill of the art, under the premise without departing from the principles of the invention, without the need to the other technologies feature just can associated through creative work, some modification and improvement can also be made.The technology scope is not limited to the content on description, must determine its technical scope according to interest field.
Claims (10)
1. a preparation method for composite nano-fiber membrane, is characterized in that, described method comprises the steps:
(1) method of electrostatic spinning is adopted to prepare polymer nanofibre film;
(2) described polymer nanofibre film is immersed in Mg
2+in solution, add ammoniacal liquor, hydrothermal treatment consists;
(3) repeatedly rinse by deionized water, dry at 60 DEG C, obtain composite nano-fiber membrane.
2. the method for claim 1, is characterized in that, in described step (1), the polymer prepared selected by described polymer nanofibre film have can with Mg (OH)
2there is the functional group of chelatropic reaction.
3. method as claimed in claim 2, is characterized in that, described can with Mg (OH)
2there is the functional group of chelatropic reaction, comprising: > C=O ,-CN, OC-N, or-NH
2.
4. the method as described in claim 1 or 2 or 3, it is characterized in that, described polymer comprises: polyamide 6 (PA6), polyacrylonitrile (PAN) or thermoplastic polyester elastomer (TPEE).
5. method as claimed in claim 4, is characterized in that, in described step (2), and described Mg
2+solution comprises: MgSO
4solution, MgCl
2solution, or Mg (NO
3)
2solution.
6. method as claimed in claim 5, it is characterized in that, the molecular weight of described polymer is greater than 10
5.
7. method as claimed in claim 6, it is characterized in that, in described step (1), the solvent dissolving described polymer used has volatility; The mass fraction of spinning solution is 10-40%; Spinning voltage is 16-24KV; Needle diameter used is 0.6-1.0mm; Receiving range is 10-20cm; Receiver is aluminium foil, and the spinning time is 4-12h.
8. method as claimed in claim 7, is characterized in that, in described step (2), and described Mg
2+the mass fraction of solution is 5-30%; It is 1-5ml that institute adds ammoniacal liquor; Hydrothermal temperature is 20-80 DEG C; Hydro-thermal time 1-5h.
9. method as claimed in claim 8, it is characterized in that, in described step (3), dry 1h at 60 DEG C, obtains described composite nano-fiber membrane.
10. the composite nano-fiber membrane adopting the preparation method as described in arbitrary claim of claim 1 to 9 to obtain.
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|---|---|---|---|
| CN201410088644.0A CN104907052A (en) | 2014-03-12 | 2014-03-12 | Composite nanofiber membrane and making method thereof |
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|---|---|---|---|
| CN201410088644.0A CN104907052A (en) | 2014-03-12 | 2014-03-12 | Composite nanofiber membrane and making method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333873A (en) * | 2020-04-13 | 2020-06-26 | 广东荷花新材料科技有限公司 | Preparation method of nanofiber solution and preparation method of nanofibers |
| CN115006998A (en) * | 2022-06-16 | 2022-09-06 | 浙江理工大学 | Composite nanofiber membrane for heavy metal sewage treatment and preparation method and application thereof |
-
2014
- 2014-03-12 CN CN201410088644.0A patent/CN104907052A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333873A (en) * | 2020-04-13 | 2020-06-26 | 广东荷花新材料科技有限公司 | Preparation method of nanofiber solution and preparation method of nanofibers |
| CN115006998A (en) * | 2022-06-16 | 2022-09-06 | 浙江理工大学 | Composite nanofiber membrane for heavy metal sewage treatment and preparation method and application thereof |
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