CN107159157A - Contain heavy metal ion blotting cross-linked chitosan nano fibrous membrane and preparation method thereof - Google Patents
Contain heavy metal ion blotting cross-linked chitosan nano fibrous membrane and preparation method thereof Download PDFInfo
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- CN107159157A CN107159157A CN201710321085.7A CN201710321085A CN107159157A CN 107159157 A CN107159157 A CN 107159157A CN 201710321085 A CN201710321085 A CN 201710321085A CN 107159157 A CN107159157 A CN 107159157A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
- B01J20/28038—Membranes or mats made from fibers or filaments
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The present invention relates to containing heavy metal ion blotting cross-linked chitosan nano fibrous membrane and preparation method thereof, preparation method comprises the following steps：(1) the chitosan spinning solution containing contents of many kinds of heavy metal ion is prepared；(2) electrostatic spinning is carried out, the chitosan nano fiber membrane containing contents of many kinds of heavy metal ion is prepared；(3) above-mentioned chitosan nano fiber membrane is used into glutaraldehyde cross-linking at room temperature, obtained containing contents of many kinds of heavy metal ion cross-linked chitosan nano fibrous membrane；(4) it is placed in above-mentioned containing contents of many kinds of heavy metal ion cross-linked chitosan nano fibrous membrane in dilute acid soln, removes the contents of many kinds of heavy metal ion of chelating, the cross-linked chitosan nano fibrous membrane of contents of many kinds of heavy metal ion trace is dried to obtain after washing.Compared with prior art, chitosan nano fiber membrane of the present invention has excellent adsorptive selectivity, high absorption capacity and high stability, can effectively adsorb the contents of many kinds of heavy metal ion in waste water, and can repeatedly use, simple to operate, is widely used.
Description
Technical field
The invention belongs to heavy metal ion adsorbing material technical field, it is related to a kind of containing heavy metal ion blotting crosslinking shell
Glycan nano fibrous membrane and preparation method thereof.
Background technology
In recent years, with the development of industrial or agricultural, pollution of the heavy metal ion to water environment is increasingly severe.Due to heavy metal
With enriching, and it is difficult in water body to be degraded, toxicity is big, and can in vivo accumulates again and participate in biosphere and follow
Ring, the mankind are further through drinking-water and food chain, and final intake heavy metal enters in body, and then various organs are caused with damage and disease
Become.Therefore, effectively remove heavy metal ions in wastewater has turned into current urgent task.At present, the suction in physical treatment process
Attached method is a kind of generally acknowledged and cost-effective method.In numerous sorbing materials, chitosan is due to containing largely can be with gold
Belong to the active amino and hydroxy functional group of ion chelating, and wide material sources, it is cheap, therefore often made heavy metal ion suction
Attached dose.However, the chemical stability and heat endurance of chitosan are poor, chelation group utilization rate is not high, and adsorption capacity is poor, limit
The high efficiency absorption of heavy metal ion is made.
Chitosan be used for heavy metal ions in wastewater absorption report document it is more, but chitosan be typically with sheet or
The form of grain is adsorbed, and adsorbance is small.Such as when adsorbing Pb (II), sheet chitosan and graininess chitosan maximum adsorption are full
It is 12.6mg/g (Bassi R, Prasher SO, Simpson BK.Removal of selected metal respectively with amount
ions from aqueous solutions using chitosan flakes.Separation Science and
Technology,2000,35:547-560) with 100.1mg/g (Chen AH, Yang CY, Chen CY, Chen CY, Chen
CW.The chemically crosslinked metal-complexed chitosans for comparative
adsorptions of Cu(II),Zn(II),Ni(II)and Pb(II)ions in aqueous medium.Journal
of Hazardous Materials,2009,163:1068-1075), and electrostatic spinning chitosan nano fiber can reach
263.2mg/g(Haider S,Park SY.Preparation of the electrospun chitosan nanofibers
and their applications to the adsorption of Cu(II)and Pb(II)ions from an
aqueous solution.Journal of Membrane Science,2009,328:90-96).Exist to improve chitosan
Stability in acid solution, chitosan generally requires to be crosslinked, and the result of crosslinking causes absorption property to reduce, ion blotting
The problem of introducing of technology solves excessively crosslinking and too low adsorption efficiency well (Chen AH, Yang CY, Chen CY,
Chen CY,Chen CW.The chemically crosslinked metal-complexed chitosans for
comparative adsorptions of Cu(II),Zn(II),Ni(II)and Pb(II)ions in aqueous
medium.Journal of Hazardous Materials 2009；163:1068-75).Up to the present, relevant trace shell
Glycan sorbing material is only limitted to the trace of single ionic, and with chitosan particle (Sun Shengling, Ma Ning, king's love duty copper mold plates in the majority
The Study on adsorption properties ion exchanges of metal ion by cross-linked chitosan and absorption, 2004,20 (3):193-198), shell is had no
The multiple trace of glycan Electrospun nano-fibers is used for the application in terms of heavy metal ion adsorbing material.
The Chinese invention patent of Application No. 201110146164.1 discloses a kind of chitosan nano fiber membrane adsorption material
Material and preparation method thereof, the preparation method of the sorbing material comprises the following steps：Chitosan spinning solution is added into Static Spinning
Silk equipment prepares chitosan nano fiber membrane with method of electrostatic spinning；By obtained chitosan nano fiber membrane in alkaline solution
After immersion, cleaned and drying process obtains chitosan nano fibrous membrane adsorbing material.Constitute the Nanowire of the sorbing material
The average diameter of dimension is 100-600nm, and the porosity of the sorbing material is 15-60%.Different from above-mentioned contrast patent, this hair
The stability of the chitosan Electrospun nano-fibers film sorbing material of bright preparation in the solution is good, better than existing sorbing material,
And with good biocompatibility, cost is low, raw material sources are wide, it is reusable the characteristics of.Especially it is noted that the present invention
The sorbing material can be with the heavy metal ion in simultaneous selection adsorbent solution, and adsorbance is big, such as simultaneously to Pb2+、Cd2+
And Cu2+Adsorbance up to 552mg/g, 332mg/g and 313mg/g.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind has absorption selection
Property, high absorption capacity, high stability and can adsorb simultaneously contents of many kinds of heavy metal ion containing heavy metal ion blotting crosslinking shell gather
Sugared nano fibrous membrane.
Another object of the present invention is just to provide above-mentioned containing heavy metal ion blotting cross-linked chitosan nano fibrous membrane
Preparation method.
The purpose of the present invention can be achieved through the following technical solutions：
Preparation method containing heavy metal ion blotting cross-linked chitosan nano fibrous membrane, this method specifically includes following step
Suddenly：
Step (1)：Chitosan and more than at least two heavy metallic salt are dissolved in the mixed of trifluoroacetic acid and dichloromethane
In bonding solvent, stir at room temperature, until chitosan, heavy metallic salt are completely dissolved, the chitosan containing heavy metal ion is made
Solution；
Step (2)：Chitosan solution containing heavy metal ion is transferred in electrospinning device, passes through electrostatic spinning
Be made contain heavy metal ion chitosan nano fiber membrane, after be placed in drying in oven, to remove residual solvent；
Step (3)：By being placed in containing heavy metal ion chitosan nano fiber membrane containing glutaraldehyde steam after drying
In closed container, cross-linking reaction is carried out at room temperature, is made and is contained heavy metal ion cross-linked chitosan nano fibrous membrane；
Step (4)：Rinsed repeatedly using diluted acid containing heavy metal ion cross-linked chitosan nano fibrous membrane, until in solution
Untill no longer detecting heavy metal ion, by drying, that is, it is made and contains heavy metal ion blotting cross-linked chitosan nanofiber
Film.
Chitosan described in step (1) is the chitosan that deacetylation is 85-95%.
The weight/mass percentage composition of chitosan is 1-5% in the described chitosan solution containing heavy metal ion.
Heavy metallic salt described in step (1) include lead chloride, caddy, chromium chloride, plumbi nitras, chromic nitrate, chromic nitrate,
Two or more in lead sulfate, chromium sulfate or cadmium sulfate.
The gross mass percentage composition of heavy metal ion is 0.01- in the described chitosan solution containing heavy metal ion
1%.
The ratio between volume of trifluoroacetic acid and dichloromethane described in step (1) is 1:5~5:1.
The process conditions of electrostatic spinning described in step (2) are：Application voltage is 10-30KV, and propulsion speed is 0.1-
1mL/h, it is 10-20cm to receive distance, and oven temperature is set to 40-70 DEG C.
The time of cross-linking reaction described in step (3) is 10-24h.
The volumetric concentration of glutaraldehyde steam described in step (3) is 0.63-1.05mg/m3。
Aldehyde radical on amino and glutaraldehyde molecules in chitosan molecule occurs for cross-linking reaction, and the two happens is that Schiff
Alkali, the crosslinking of different chitosan molecule chains is got up.
Diluted acid described in step (4) includes one kind in watery hydrochloric acid, dilute sulfuric acid or dust technology.
Contain heavy metal ion blotting cross-linked chitosan nano fibrous membrane, the Nanowire using what the above method was prepared from
The average diameter for tieing up the nanofiber in film is 80-500nm.
It is produced by the present invention that there is excellent absorption selection containing heavy metal ion blotting cross-linked chitosan nano fibrous membrane
The chitosan sorbing material of property, high absorption capacity and high stability, can effectively adsorb the contents of many kinds of heavy metal ion in waste water,
And can repeatedly use, it is simple to operate, it is widely used.
Compared with prior art, the invention has the characteristics that：
1) it is produced by the present invention to have specific surface area high containing heavy metal ion blotting cross-linked chitosan nano fibrous membrane
Up to 200m2The features such as/g, porosity may be up to 70%, internal void is more, can increase the contact area with metal ion, increase
Adsorbance, shortens the time (about 8-12 hours) for reaching adsorption equilibrium, by being combined with multiple ion trace, with more
Metal ion binding site, effectively adsorbs the contents of many kinds of heavy metal ion in waste water；
2) in preparation process, nano fibrous membrane heat decomposition temperature is improved after crosslinking, residual qualities increase, heat
Stability is improved；
3) preparation process is simple, and controllability is good, and raw material sources are wide, and economic and practical is good, it is easy to carries out industrialization and expands life
Production, environmental protection, with good application prospect.
Brief description of the drawings
Fig. 1 is the ESEM spectrogram containing heavy metal ion blotting cross-linked chitosan nano fibrous membrane in embodiment 1.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1：
Preparation method containing heavy metal ion blotting cross-linked chitosan nano fibrous membrane, this method specifically includes following step
Suddenly：
Step (1)：Chitosan and two heavy metal species salt are dissolved in the in the mixed solvent of trifluoroacetic acid and dichloromethane, in
Stir at room temperature, until chitosan, heavy metallic salt are completely dissolved, the chitosan solution containing heavy metal ion is made；
Step (2)：Chitosan solution containing heavy metal ion is transferred in electrospinning device, passes through electrostatic spinning
Be made contain heavy metal ion chitosan nano fiber membrane, after be placed in drying in oven, to remove residual solvent；
Step (3)：By being placed in containing heavy metal ion chitosan nano fiber membrane containing glutaraldehyde steam after drying
In closed container, cross-linking reaction is carried out at room temperature, is made and is contained heavy metal ion cross-linked chitosan nano fibrous membrane；
Step (4)：Rinsed repeatedly using watery hydrochloric acid containing heavy metal ion cross-linked chitosan nano fibrous membrane, until solution
In no longer detect heavy metal ion untill, by drying, that is, be made and contain heavy metal ion blotting cross-linked chitosan Nanowire
Tie up film.
Chitosan is the chitosan that deacetylation is 85% in step (1).In chitosan solution containing heavy metal ion
The weight/mass percentage composition of chitosan is 1.8%, and the gross mass percentage composition of heavy metal ion is 0.2%.Heavy metallic salt is PbCl2
And CdCl2, wherein, the concentration ratio 2 of lead ion/cadmium ion:1.The ratio between volume of trifluoroacetic acid and dichloromethane is 1/5.
The process conditions of electrostatic spinning are in step (2)：Application voltage be 19KV, propulsions speed be 0.9mL/h, reception away from
From for 12cm, oven temperature is set to 60 DEG C.
The time of cross-linking reaction is 24h in step (3).
As shown in figure 1, the present embodiment be prepared from contain heavy metal ion blotting cross-linked chitosan nano fibrous membrane, should
The average diameter of nanofiber in nano fibrous membrane is 110nm.
The present embodiment contains heavy metal ion blotting cross-linked chitosan nano fibrous membrane and is used for when adsorbing mixed ion solutions,
Lead ion maximal absorptive capacity reaches 552mg/g, and cadmium ion maximal absorptive capacity reaches 332mg/g, and copper ion maximal absorptive capacity reaches
313mg/g。
The present embodiment contains heavy metal ion blotting cross-linked chitosan nano fibrous membrane to contents of many kinds of heavy metal ion adsorbance
Test result it is as shown in table 1.
Table 1
Embodiment 2：
Preparation method containing heavy metal ion blotting cross-linked chitosan nano fibrous membrane, this method specifically includes following step
Suddenly：
Step (1)：Chitosan and two heavy metal species salt are dissolved in the in the mixed solvent of trifluoroacetic acid and dichloromethane, in
Stir at room temperature, until chitosan, heavy metallic salt are completely dissolved, the chitosan solution containing heavy metal ion is made；
Step (2)：Chitosan solution containing heavy metal ion is transferred in electrospinning device, passes through electrostatic spinning
Be made contain heavy metal ion chitosan nano fiber membrane, after be placed in drying in oven, to remove residual solvent；
Step (3)：By being placed in containing heavy metal ion chitosan nano fiber membrane containing glutaraldehyde steam (body after drying
Product concentration is 0.63mg/m3) closed container in, cross-linking reaction is carried out at room temperature, be made containing heavy metal ion be crosslinked shell
Glycan nano fibrous membrane；
Step (4)：Rinsed repeatedly using watery hydrochloric acid containing heavy metal ion cross-linked chitosan nano fibrous membrane, until solution
In no longer detect heavy metal ion untill, by drying, that is, be made and contain heavy metal ion blotting cross-linked chitosan Nanowire
Tie up film.
Chitosan is the chitosan that deacetylation is 95% in step (1).In chitosan solution containing heavy metal ion
The weight/mass percentage composition of chitosan is 2.0%, and the gross mass percentage composition of heavy metal ion is 0.3%.Heavy metallic salt is PbCl2
And CdCl2, wherein, the concentration ratio 1 of lead ion/cadmium ion:1.The ratio between volume of trifluoroacetic acid and dichloromethane is 2:3.
The process conditions of electrostatic spinning are in step (2)：Application voltage be 19KV, propulsions speed be 0.8mL/h, reception away from
From for 9cm, oven temperature is set to 65 DEG C.
The time of cross-linking reaction is 24h in step (3).
What the present embodiment was prepared from contains heavy metal ion blotting cross-linked chitosan nano fibrous membrane, the nano fibrous membrane
In nanofiber average diameter be 130nm.
The present embodiment contains heavy metal ion blotting cross-linked chitosan nano fibrous membrane and is used for when adsorbing mixed ion solutions,
Lead ion maximal absorptive capacity reaches 537mg/g, and cadmium ion maximal absorptive capacity reaches 327mg/g, and copper ion maximal absorptive capacity reaches
303mg/g。
Embodiment 3：
Preparation method containing heavy metal ion blotting cross-linked chitosan nano fibrous membrane, this method specifically includes following step
Suddenly：
Step (1)：Chitosan and two heavy metal species salt are dissolved in the in the mixed solvent of trifluoroacetic acid and dichloromethane, in
Stir at room temperature, until chitosan, heavy metallic salt are completely dissolved, the chitosan solution containing heavy metal ion is made；
Step (2)：Chitosan solution containing heavy metal ion is transferred in electrospinning device, passes through electrostatic spinning
Be made contain heavy metal ion chitosan nano fiber membrane, after be placed in drying in oven, to remove residual solvent；
Step (3)：By being placed in containing heavy metal ion chitosan nano fiber membrane containing glutaraldehyde steam (body after drying
Product concentration is 1.05mg/m3) closed container in, cross-linking reaction is carried out at room temperature, be made containing heavy metal ion be crosslinked shell
Glycan nano fibrous membrane；
Step (4)：Rinsed repeatedly using watery hydrochloric acid containing heavy metal ion cross-linked chitosan nano fibrous membrane, until solution
In no longer detect heavy metal ion untill, by drying, that is, be made and contain heavy metal ion blotting cross-linked chitosan Nanowire
Tie up film.
Chitosan is the chitosan that deacetylation is 90% in step (1).In chitosan solution containing heavy metal ion
The weight/mass percentage composition of chitosan is 1.9%, and the gross mass percentage composition of heavy metal ion is 0.4%.Heavy metallic salt is PbCl2
And CdCl2, wherein, the concentration ratio 4 of lead ion/cadmium ion:3.The ratio between volume of trifluoroacetic acid and dichloromethane is 5:1.
The process conditions of electrostatic spinning are in step (2)：Application voltage be 20KV, propulsions speed be 0.7mL/h, reception away from
From for 12cm, oven temperature is set to 65 DEG C.
The time of cross-linking reaction is 24h in step (3).
What the present embodiment was prepared from contains heavy metal ion blotting cross-linked chitosan nano fibrous membrane, the nano fibrous membrane
In nanofiber average diameter be 140nm.
The present embodiment contains heavy metal ion blotting cross-linked chitosan nano fibrous membrane and is used for when adsorbing mixed ion solutions,
Lead ion maximal absorptive capacity reaches 610mg/g, and cadmium ion maximal absorptive capacity reaches 311mg/g, and copper ion maximal absorptive capacity reaches
287mg/g。
Embodiment 4：
Preparation method containing heavy metal ion blotting cross-linked chitosan nano fibrous membrane, this method specifically includes following step
Suddenly：
Step (1)：Chitosan and three heavy metal species salt are dissolved in the in the mixed solvent of trifluoroacetic acid and dichloromethane, in
Stir at room temperature, until chitosan, heavy metallic salt are completely dissolved, the chitosan solution containing heavy metal ion is made；
Step (2)：Chitosan solution containing heavy metal ion is transferred in electrospinning device, passes through electrostatic spinning
Be made contain heavy metal ion chitosan nano fiber membrane, after be placed in drying in oven, to remove residual solvent；
Step (3)：By being placed in containing heavy metal ion chitosan nano fiber membrane containing glutaraldehyde steam (body after drying
Product concentration is 0.8mg/m3) closed container in, cross-linking reaction is carried out at room temperature, be made containing heavy metal ion crosslinking shell gather
Sugared nano fibrous membrane；
Step (4)：Rinsed repeatedly using watery hydrochloric acid containing heavy metal ion cross-linked chitosan nano fibrous membrane, until solution
In no longer detect heavy metal ion untill, by drying, that is, be made and contain heavy metal ion blotting cross-linked chitosan Nanowire
Tie up film.
Chitosan is the chitosan that deacetylation is 89% in step (1).In chitosan solution containing heavy metal ion
The weight/mass percentage composition of chitosan is 5%, and the gross mass percentage composition of heavy metal ion is 1%.Heavy metallic salt is lead chloride, chlorine
Cadmium, chromium chloride, wherein, the concentration ratio 2 of lead ion, cadmium ion and chromium ion:3:1.The body of trifluoroacetic acid and dichloromethane
The ratio between product is 3:2.
The process conditions of electrostatic spinning are in step (2)：Application voltage is 30KV, and propulsion speed is 1mL/h, receives distance
For 20cm, oven temperature is set to 70 DEG C.
The time of cross-linking reaction is 18h in step (3).
What the present embodiment was prepared from contains heavy metal ion blotting cross-linked chitosan nano fibrous membrane, the nano fibrous membrane
In nanofiber average diameter be 500nm.
Embodiment 5：
Preparation method containing heavy metal ion blotting cross-linked chitosan nano fibrous membrane, this method specifically includes following step
Suddenly：
Step (1)：Chitosan and three heavy metal species salt are dissolved in the in the mixed solvent of trifluoroacetic acid and dichloromethane, in
Stir at room temperature, until chitosan, heavy metallic salt are completely dissolved, the chitosan solution containing heavy metal ion is made；
Step (2)：Chitosan solution containing heavy metal ion is transferred in electrospinning device, passes through electrostatic spinning
Be made contain heavy metal ion chitosan nano fiber membrane, after be placed in drying in oven, to remove residual solvent；
Step (3)：By being placed in containing heavy metal ion chitosan nano fiber membrane containing glutaraldehyde steam (body after drying
Product concentration is 1.0mg/m3) closed container in, cross-linking reaction is carried out at room temperature, be made containing heavy metal ion crosslinking shell gather
Sugared nano fibrous membrane；
Step (4)：Rinsed repeatedly using watery hydrochloric acid containing heavy metal ion cross-linked chitosan nano fibrous membrane, until solution
In no longer detect heavy metal ion untill, by drying, that is, be made and contain heavy metal ion blotting cross-linked chitosan Nanowire
Tie up film.
Chitosan is the chitosan that deacetylation is 92% in step (1).In chitosan solution containing heavy metal ion
The weight/mass percentage composition of chitosan is 1%, and the gross mass percentage composition of heavy metal ion is 0.01%.Heavy metallic salt is nitric acid
Lead, caddy, chromic nitrate, wherein, the concentration ratio 1 of lead ion, cadmium ion and chromium ion:2:1.Trifluoroacetic acid and dichloromethane
The ratio between volume be 4:1.
The process conditions of electrostatic spinning are in step (2)：Application voltage be 10KV, propulsions speed be 0.1mL/h, reception away from
From for 10cm, oven temperature is set to 40 DEG C.
The time of cross-linking reaction is 10h in step (3).
What the present embodiment was prepared from contains heavy metal ion blotting cross-linked chitosan nano fibrous membrane, the nano fibrous membrane
In nanofiber average diameter be 80nm.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using invention.
Person skilled in the art obviously can easily make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without passing through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel are according to the announcement of the present invention, and not departing from improvement and modification that scope made all should be the present invention's
Within protection domain.
Claims (10)
1. the preparation method containing heavy metal ion blotting cross-linked chitosan nano fibrous membrane, it is characterised in that this method is specific
Comprise the following steps：
Step (1)：By chitosan with more than at least two heavy metallic salt be dissolved in trifluoroacetic acid and dichloromethane mixing it is molten
In agent, stir at room temperature, until chitosan, heavy metallic salt are completely dissolved, the chitosan solution containing heavy metal ion is made；
Step (2)：Chitosan solution containing heavy metal ion is transferred in electrospinning device, is made by electrostatic spinning
Containing heavy metal ion chitosan nano fiber membrane, after be placed in drying in oven, to remove residual solvent；
Step (3)：By being placed in containing heavy metal ion chitosan nano fiber membrane containing the closed of glutaraldehyde steam after drying
In container, cross-linking reaction is carried out at room temperature, is made and is contained heavy metal ion cross-linked chitosan nano fibrous membrane；
Step (4)：Rinsed repeatedly using diluted acid containing heavy metal ion cross-linked chitosan nano fibrous membrane, until in solution no longer
Untill detecting heavy metal ion, by drying, that is, it is made and contains heavy metal ion blotting cross-linked chitosan nano fibrous membrane.
2. the preparation method according to claim 1 containing heavy metal ion blotting cross-linked chitosan nano fibrous membrane, its
It is characterised by, the chitosan described in step (1) is the chitosan that deacetylation is 85-95%.
3. the preparation method according to claim 2 containing heavy metal ion blotting cross-linked chitosan nano fibrous membrane, its
It is characterised by, the weight/mass percentage composition of chitosan is 1-5% in the chitosan solution containing heavy metal ion.
4. the preparation method according to claim 1 containing heavy metal ion blotting cross-linked chitosan nano fibrous membrane, its
It is characterised by, the heavy metallic salt described in step (1) includes lead chloride, caddy, chromium chloride, plumbi nitras, chromic nitrate, nitric acid
Two or more in chromium, lead sulfate, chromium sulfate or cadmium sulfate.
5. the preparation method according to claim 4 containing heavy metal ion blotting cross-linked chitosan nano fibrous membrane, its
It is characterised by, the gross mass percentage composition of heavy metal ion is 0.01- in the chitosan solution containing heavy metal ion
1%.
6. the preparation method according to claim 1 containing heavy metal ion blotting cross-linked chitosan nano fibrous membrane, its
It is characterised by, the ratio between volume of trifluoroacetic acid and dichloromethane described in step (1) is 1:5~5:1.
7. the preparation method according to claim 1 containing heavy metal ion blotting cross-linked chitosan nano fibrous membrane, its
It is characterised by, the process conditions of the electrostatic spinning described in step (2) are：Application voltage is 10-30KV, and propulsion speed is 0.1-
1mL/h, it is 10-20cm to receive distance, and oven temperature is set to 40-70 DEG C.
8. the preparation method according to claim 1 containing heavy metal ion blotting cross-linked chitosan nano fibrous membrane, its
It is characterised by, the time of the cross-linking reaction described in step (3) is 10-24h.
9. the preparation method according to claim 1 containing heavy metal ion blotting cross-linked chitosan nano fibrous membrane, its
It is characterised by, the diluted acid described in step (4) includes one kind in watery hydrochloric acid, dilute sulfuric acid or dust technology.
10. contain heavy metal ion blotting cross-linked chitosan using what the method described in any one of claim 1 to 9 was prepared from
Nano fibrous membrane, it is characterised in that the average diameter of the nanofiber in the nano fibrous membrane is 80-500nm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110327902A (en) * | 2019-07-18 | 2019-10-15 | 晋江瑞碧科技有限公司 | A kind of preparation method of chitosan-based lead ion trace nanofiber |
| CN110639482A (en) * | 2019-10-24 | 2020-01-03 | 南京工程学院 | Preparation method of uranyl ion imprinted composite membrane with inverse opal structure |
| CN113529278A (en) * | 2021-06-21 | 2021-10-22 | 五邑大学 | Crosslinking type nanofiber membrane and preparation method and application thereof |
| CN113648984A (en) * | 2021-09-24 | 2021-11-16 | 长春工业大学 | temperature-pH response molecularly imprinted fiber membrane and preparation method thereof |
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| CN110639482A (en) * | 2019-10-24 | 2020-01-03 | 南京工程学院 | Preparation method of uranyl ion imprinted composite membrane with inverse opal structure |
| CN110639482B (en) * | 2019-10-24 | 2022-07-22 | 南京工程学院 | Preparation method of uranyl ion imprinted composite membrane with inverse opal structure |
| CN113529278A (en) * | 2021-06-21 | 2021-10-22 | 五邑大学 | Crosslinking type nanofiber membrane and preparation method and application thereof |
| CN113529278B (en) * | 2021-06-21 | 2022-06-21 | 五邑大学 | Crosslinking type nanofiber membrane and preparation method and application thereof |
| CN113648984A (en) * | 2021-09-24 | 2021-11-16 | 长春工业大学 | temperature-pH response molecularly imprinted fiber membrane and preparation method thereof |
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