CN106311165A - Chitosan nanofiber composite film for adsorbing and separating heavy metal ions and preparation method and application thereof - Google Patents
Chitosan nanofiber composite film for adsorbing and separating heavy metal ions and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a chitosan nanofiber composite film for adsorbing and separating heavy metal ions and a preparation method and application thereof. The composite film is a chitosan electrospun nanofiber/non-woven fabric base composite film. The method for preparing the composite film comprises the following steps: performing electro-spinning on chitosan on a non-woven fabric base through an electrostatic spinning method, thereby obtaining a composite fiber film; and combining multiple composite fiber film layers in different manners, thereby preparing an adsorption and separation medium. The adsorption and separation medium is filled in a filter separator and can be used for dynamically adsorbing and filtering to remove heavy metal ions in water. The composite film disclosed by the invention is simple and convenient in preparation method, green, environmental-friendly, low in cost, easy to popularize and apply, high in heavy metal wastewater treatment efficiency and high in selectivity, can be used for purifying and treating heavy metals in industrial and domestic wastewater, and has important social and economical benefits.
Description
Technical field
The invention belongs to adsorbing material and fields of nano material application, be specifically related to a kind of chitosan nano fiber
Composite membrane and its preparation method and application, particularly relates to a kind of chitosan for adsorbing separation heavy metal ion
Nano-fiber composite film and its preparation method and application.
Background technology
Along with the fast development of China's economic society and the quickening of process of industrialization advance, a large amount of industrial wastewaters
Arbitrarily discharge, the heavy metal pollution causing water body is the most serious.In recent years, heavy metal-polluted water event frequency
Numerous generation.Such as, more than 5000 ton of industrial waste chromium slag of Qujing of Yunnan Luliang chemical industry Industrial Co., Ltd. in 2012
Illegal dumping causes polluting Upper Reaches of Pearl River event, causes and topples over 77, rural area domestic animal death near ground, fork bath
Storehouse 4 ten thousand stere water body and 3000 cubic metres of water bodys of neighbouring mountain valley with clumps of trees and bamboo ditch are contaminated, and produce the biggest environment danger
Evil, the water body safety of serious threat Pearl River Delta.
The existence of plurality of heavy metal ion in water body, can be enriched with and drink entrance human body, to people by food chain
The health of body causes serious harm.The absorption of excess heavy metal ion, may cause allergy, burst human body
Infections, spasm, DNA distort, and even make cell generation canceration.Therefore, in water, the heavy metal ion of excess must
Must remove.
Absorption method has been obtained for being widely applied as a kind of important method processing heavy metal wastewater thereby.Inhale
Attached method heavy-metal ion removal has the advantages such as easy and simple to handle, advantages of good adsorption effect, more comes in terms of water body purification
The most concerned.The high speed development of nanotechnology the most in recent years, nano material is big and superior due to specific surface area
Absorption property, obtained more concern.
Electrospinning process is a kind of important method preparing nanofiber.Static Spinning chitosan nano fiber has
Have the highest specific surface area so that more adsorption functional group is exposed to fiber surface, heavy metal from
Son has higher absorbability.CN102218300A discloses a kind of chitosan nano fibrous membrane adsorbing material
And preparation method thereof, it includes procedure below: join in electrospinning device by chitosan spinning solution,
Chitosan nano fiber membrane is prepared with method of electrostatic spinning；The chitosan nano fiber membrane that obtains is molten in alkalescence
After soaking in liquid, cleaned and dried obtains chitosan nano fibrous membrane adsorbing material.
CN103285819A disclose a kind of Static Spinning chitosan nano fiber membrane for Adsorption of Heavy Metal Ions and
Its preparation method, highlights the preparation process of electrostatic spinning chitin fiber, the heavy metal ion being directed to
Only include copper and two kinds of ions of lead.CN103801266A discloses a kind of chitosan nano fibrous membrane adsorbing material
And preparation method thereof, basically identical with disclosed in CN102218300A of its preparation process.
Although the most a lot of documents all disclose chitosan nano fiber membrane material, and use it for adsorbing separation
Heavy metal ion, but, these chitosan nano fiber membrane materials are homogenous material, and its mechanical property is relatively
Difference, thus limit its range；Simultaneously as these chitosan nano fiber membrane materials are all without friendship
Connection, limits its use in acid condition；Further, since the swelling action of chitosan, inhale in static state
In additive process, heavy metal ion hardly diffuses to the inside of material, thus causes adsorption effect on the low side, it is impossible to
Farthest play the advantage of chitosan nano fiber material.
Summary of the invention
The invention provides a kind of chitosan nano fiber composite membrane and its preparation method and application, particularly carry
Supply a kind of chitosan nano fiber composite membrane for adsorbing separation heavy metal ion and preparation method thereof and answered
With.The present invention has not only widened the actual application in terms of heavy metal adsorption of the electrostatic spinning nano material, and
It is high, cheap and make the features such as simple that composite film material prepared by the present invention has intensity,
Overcome the fraud that poor mechanical property and service efficiency during chitosan Electrospun nano-fibers directly uses are low
End.
For reaching this purpose, the present invention by the following technical solutions:
First aspect, the invention provides a kind of chitosan nano fiber for adsorbing separation heavy metal ion
Composite membrane, described composite membrane is formed by the bottom of chitosan nano fiber and nonwoven fabric base.
The present invention by by chitosan nano fiber electrospinning at the bottom of nonwoven fabric base, add chitosan nano fine
Dimension mechanical property in use, and, chitosan nano fiber can penetrate at the bottom of nonwoven fabric base
Hole in, thus increase the interface bond strength of bi-material, it is to avoid chitosan nano fiber is in nothing
Spin the suprabasil stripping of cloth to come off；Meanwhile, during dynamic adsorption heavy metal, heavy metal solution penetrates whole
Individual Filtration Adsorption medium, heavy metal ion can contact more fully with adsorbing material, increase adsorbing material
Adsorption area, thus improve the absorbability of material；It addition, by controlling spinning time and substrate
Select, aperture and the thickness size of composite can be controlled, such that it is able to obtain that there is big flux, low pressure
The material of power loss, reduces the energy loss in application process.
In the present invention, the content of described chitosan nano fiber is 0.5-4g/m2, such as, can be 0.5g/m2、
0.8g/m2、1g/m2、1.2g/m2、1.4g/m2、1.5g/m2、1.8g/m2、2g/m2、2.5g/m2、2.8g/m2、
3g/m2、3.2g/m2、3.4g/m2、3.5g/m2、3.8g/m2、4g/m2, preferably 1-3.5g/m2, further
It is preferably 2.5g/m2。
In the present invention, the deacetylation of described chitosan is 75-95%, can be such as 75%, 76%, 78%,
80%, 82%, 84%, 85%, 88%, 90%, 92%, 95%, preferably 80-90%, the most excellent
Elect 90% as.
In the present invention, the molecular weight of described chitosan is 15-30 ten thousand, such as, can be 150,000,160,000,17
Ten thousand, 180,000,190,000,200,000,210,000,220,000,230,000,240,000,250,000, preferably 18-25
Ten thousand, more preferably 200,000.
In the present invention, it is polyester fiber, polypropylene fibre, Fypro, poly-second at the bottom of described nonwoven fabric base
Any one in enol fiber, polyacrylonitrile fibre, cotton fiber, viscose rayon, flaxen fiber or glass fibre
Kind or the mixing of at least two, preferably polyester fiber, vinal or viscose rayon in any one
Plant or the mixing of at least two, more preferably polyester fiber.
Second aspect, present invention also offers the preparation method of a kind of composite membrane as described in relation to the first aspect, its
Comprise the following steps:
(1) preparation of chitosan nano fiber；
(2) use step (1) preparation method by chitosan nano fiber electrospinning at the bottom of nonwoven fabric base,
Obtain described chitosan nano fiber composite membrane.
In the present invention, the preparation method of step (1) described chitosan nano fiber is method of electrostatic spinning.
Method of electrostatic spinning of the present invention comprises the following steps: dissolved in a solvent by described chitosan, stirring
It is completely dissolved to chitosan, stands 2h deaeration, obtain chitosan solution；Wherein, the work of described electrostatic spinning
Skill is: voltage 15-30kV, receiving range 6-15cm, spinning liquid liquid supply rate 0.5-1.5mL/h.
Wherein, the voltage of described electrostatic spinning is 15-30kV, can be such as 15kV, 17kV, 18kV,
20kV、22kV、23kV、25kV、28kV、30kV；Receiving range is 6-15cm, the most permissible
It is 6cm, 8cm, 10cm, 11cm, 12cm, 13cm, 14cm, 15cm；Spinning liquid liquid supply rate
For 0.5-1.5mL/h, can be such as 0.5mL/h, 0.6mL/h, 0.8mL/h, 1.0mL/h, 1.2mL/h,
1.3mL/h、1.4mL/h、1.5mL/h。
Preferably, described solvent be trifluoroacetic acid or acetum, preferably mass concentration be the vinegar of 85-90%
Acid solution.
Preferably, the concentration of described chitosan solution is 3-5wt%, can be such as 3wt%, 3.1wt%,
3.2wt%, 3.5wt%, 3.7wt%, 3.8wt%, 4wt%, 4.2wt%, 4.5wt%, 4.6wt%, 4.7wt%,
4.9wt%, 5wt%, preferably 3.5-4wt%, more preferably 4wt%.
In the present invention, a diameter of 60-200nm of chitosan nano fiber prepared by step (1).
In the preparation method of chitosan nano fiber composite membrane of the present invention, it is also possible to comprise the following steps:
(3) chitosan nano fiber composite membrane step (2) prepared uses cross-linking agent to cross-link；
(4) by the described composite membrane combination of the different numbers of plies, obtain composite membrane and filter separating medium；
(5) described composite membrane filtration separating medium is installed in filter separator.
In the present invention, step (3) described cross-linking agent is in epoxychloropropane, formaldehyde, Biformyl or glutaraldehyde
Any one or the mixing of at least two, preferably formaldehyde or glutaraldehyde, more preferably glutaraldehyde.
Preferably, the compound mode of step (4) described composite membrane is superposing type and/or rolling；Preferably, institute
The number of plies stating composite membrane is 1-20 layer.
As preferred technical scheme, the preparation method of chitosan nano fiber composite membrane of the present invention includes
Following steps:
(1) method of electrostatic spinning is used to prepare chitosan nano fiber；
(2) preparation method of step (1) is used chitosan nano fiber electrospinning to be made at the bottom of nonwoven fabric base
Obtain chitosan nano fiber composite membrane；
(3) the chitosan nano fiber composite membrane prepared employing cross-linking agent is cross-linked；
(4) by the combination by different modes of the chitosan nano fiber composite membrane of the different numbers of plies, filtered
Separating medium；
(5) chitosan nano fiber composite membrane filtration separating medium is installed in filter separator, makes a huge sum of money
Belong to solution and penetrate filtration separating medium, Dynamic Adsorption of Heavy Metal Ions.
As further preferred technical scheme, the preparation side of chitosan nano fiber composite membrane of the present invention
Method can also comprise the following steps:
(1) preparation of chitosan nano fiber: described chitosan is dissolved in trifluoroacetic acid or mass concentration is
In the acetum of 85-90%, stirring and be completely dissolved to chitosan, stand 2h deaeration, obtaining mass fraction is
The uniform spinning liquid of 3-5wt%；Electrospinning process is utilized to prepare chitosan nano fiber, described electrostatic
The technique of spinning is: voltage 15-30kV, receiving range 6-15cm, spinning liquid liquid supply rate 0.5-1.5mL/h；
A diameter of 60-200nm of the described chitosan nano fiber prepared；
(2) use step (1) preparation method by chitosan nano fiber electrospinning at the bottom of nonwoven fabric base,
Obtain described chitosan nano fiber/nonwoven fabrics composite film；
(3) chitosan nano fiber composite membrane step (2) prepared uses cross-linking agent to cross-link, institute
Stating cross-linking agent is the mixed of any one or at least two in epoxychloropropane, formaldehyde, Biformyl or glutaraldehyde
Close；
(4) use superposing type and/or rolling to be combined the described composite membrane of 1-20 layer, obtain composite membrane
Filter separating medium；
(5) described composite membrane filtration separating medium is installed in filter separator, makes heavy metal solution penetrate
Filter separating medium, Dynamic Adsorption of Heavy Metal Ions.
The third aspect, present invention also offers composite membrane as described in relation to the first aspect adsorbing separation heavy metal from
Application in son.
In the present invention, described heavy metal ion is Pb2+、Cd2+、Cu2+、Zn2+、Ni2+Or Cr6+In appoint
Anticipate a kind of or the mixing of at least two, preferably Cr6+, more preferably in drinking water or industrial wastewater
Low concentration Cr6+。
Compared with prior art, the present invention at least has the advantages that
(1) present invention is by chitosan nano fiber electrospinning at the bottom of nonwoven fabric base, goes for dynamic filtration absorption
Except the heavy metal ion in water, solution easily penetrates whole adsorbing material, makes heavy metal ion and more absorption
Site contacts, and increases the adsorption area of adsorbing material, thus improves adsorption effect.
(2) present invention is by chitosan nano fiber electrospinning at the bottom of nonwoven fabric base, can penetrate into non-woven fabrics
In the hole of substrate, thus increase the interface bond strength of bi-material, it is to avoid chitosan nano fiber
Come off in the suprabasil stripping of non-woven fabrics, the problem overcoming the intensity difference of chitosan material own.
(3) composite prepared by the present invention, can control by controlling spinning time and the selection of substrate
The aperture of composite and thickness size, such that it is able to obtain that there is big flux, the material of low-pressure loss,
Reduce the energy loss in application process；Simultaneously as chitosan nano fiber have passed through crosslinking, permissible
Use the most in acid condition.
(4) preparation method that the present invention relates to and technique are simple, easy popularization and application.
Accompanying drawing explanation
Fig. 1 is the SEM Electronic Speculum figure of the chitosan nano fiber composite membrane of preparation in the embodiment of the present invention 1.
Fig. 2 is the breakthrough curve of the chitosan nano fiber composite membrane of preparation in the embodiment of the present invention 1.
Fig. 3 is the breakthrough curve of the chitosan nano fiber composite membrane of preparation in the embodiment of the present invention 2.
Fig. 4 is the breakthrough curve of the chitosan nano fiber composite membrane of preparation in the embodiment of the present invention 3.
Fig. 5 is the breakthrough curve of the chitosan nano fiber composite membrane of preparation in the embodiment of the present invention 4.
Fig. 6 is that the chitosan nano fiber composite membrane prepared in the embodiment of the present invention 5 is to contents of many kinds of heavy metal ion
The size of adsorbance compares.
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art it will be clearly understood that
The only help of described embodiment understands the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
1) be 90% by 3g deacetylation, molecular weight be 200,000 chitosan be dissolved in 57g mass fraction and be
In the acetum of 90%, stirring and dissolving 12h, obtain the uniform spinning liquid that mass fraction is 5%；Utilize
Electrospinning process prepares chitosan nano fiber, and wherein, the technique of electrostatic spinning is: voltage 23kV,
Spinning distance is 6cm, and liquid supply speed is 1mL/h；Employing grammes per square metre is 34g/m2Polyester non-woven fabric be substrate,
A diameter of 20 μm of polyester fiber, the pore size of non-woven fabrics is 114 μm；By chitosan nano fiber electrospinning
On at the bottom of nonwoven fabric base, obtain chitosan nano fiber/polyester non-woven fabric composite.The composite of preparation
The average diameter of middle chitin fiber is 60-120nm (as shown in Figure 1), and the grammes per square metre of chitin fiber is 2g/m2,
The aperture of composite is 0.56 μm；The composite of preparation is put into and fills the dry of 20mL glutaraldehyde solution
In dry device, glutaraldehyde vapor crosslinking 12h, obtain the chitosan nano fiber composite of crosslinking.
2) disk of the lower 10 a diameter of 47mm of cutting from composite, uses superposing type, by same
Direction stacks up, and makes Filtration Adsorption medium；Adsorbing medium is put in filter, obtain filter assemblies；
With peristaltic pump as power source, by the Cr VI (Cr that initial concentration is 1mg/L6+) solution is with 2mL/min's
Speed penetrates filter assemblies, collects the effluent after different time, and in detection effluent, hexavalent chromium is dense
Degree (Ct).With the time as abscissa, solution concentration is vertical coordinate, draw curve, obtain breakthrough curve (as
Shown in Fig. 2).
Figure it is seen that with outflow concentration reach 100 μ g/L for breakthrough point time, time of break-through is
160min, is 16.50mg/g by being calculated now adsorbance, and breakthrough curve rises mild.Approximately pass through
810min, the concentration of effluent reaches 800 μ g/L.
Embodiment 2
1) be 95% by 1.5g deacetylation, molecular weight be 150,000 chitosan be dissolved in 50g trifluoroacetic acid
In, stirring and dissolving 4h, obtain the uniform spinning liquid that mass fraction is 3%；Electrospinning process is utilized to prepare
Go out chitosan nano fiber；Wherein, the technique of electrostatic spinning is: voltage 15kV, and spinning distance is 10cm,
Liquid supply speed is 0.5mL/h；Employing grammes per square metre is 27g/m2Polypropylene fiber nonwoven cloth be substrate, shell is gathered
Sugar nanofiber electrospinning, in substrate, obtains chitosan/polypropylene non-woven fabric composite；The composite wood of preparation
In material, the average diameter of chitin fiber is 70-150nm, and the grammes per square metre of chitin fiber is 1g/m2, composite wood
The aperture of material is 1.03 μm；The composite of preparation is put in the exsiccator filling 20mL glyoxal solution,
Biformyl vapor crosslinking 12h, obtains the chitosan nano fiber composite of crosslinking.
2) disk of the lower 20 a diameter of 47mm of cutting from composite, uses superposing type, by same
Direction stacks up, and makes Filtration Adsorption medium；Adsorbing medium is put in filter, obtain filter assemblies；
With peristaltic pump as power source, by the Cr VI (Cr that initial concentration is 1mg/L6+) solution is with 2mL/min's
Speed penetrates filter assemblies, collects the effluent after different time, and in detection effluent, hexavalent chromium is dense
Degree (Ct).With the time as abscissa, solution concentration is vertical coordinate, draw curve, obtain breakthrough curve (as
Shown in Fig. 3).
From figure 3, it can be seen that with outflow concentration reach 100 μ g/L for breakthrough point time, time of break-through be about
95min, now adsorbance is 9.88mg/g, breakthrough curve steeper slope.Approximately pass through 825min, effluent
Concentration reach 800 μ g/L.
Embodiment 3
1) be 70% by 3g deacetylation, molecular weight be 300,000 chitosan be dissolved in 57g mass fraction and be
In the acetum of 85%, stir molten 12h, obtain the uniform spinning liquid that mass fraction is 5%；Utilize quiet
Electrical spinning method prepares chitosan nano fiber；Wherein, the technique of electrostatic spinning is: voltage 30kV, spins
Flight lead is from for 15cm, and liquid supply speed is 1.5ml/h；Employing grammes per square metre is 34g/m2Polyamide non-woven fabrics be base
The end, a diameter of 10 μm of Fypro, the pore size of non-woven fabrics is 68 μm；Chitosan nano is fine
Dimension electrospinning, in substrate, obtains chitosan nano fiber/polyamide non-woven fabric composite material；The composite wood of preparation
In material, the average diameter of chitin fiber is 70-200nm, and the grammes per square metre of chitin fiber is 0.5g/m2, composite wood
The aperture of material is 3.2 μm；The composite of preparation is put in the exsiccator filling 20mL formalin, first
Aldehyde vapor crosslinking 12h, obtains the chitosan nano fiber composite of crosslinking.
2) disk of the lower 5 a diameter of 47mm of cutting from composite, uses superposing type, by same side
To stacking up, make Filtration Adsorption medium；Adsorbing medium is put in filter, obtain filter assemblies；
With peristaltic pump as power source, the hexavalent chromium solution that initial concentration is 5mg/L is penetrated with the speed of 2mL/min
Filter assemblies, collects the effluent after different time, the concentration (C of hexavalent chromium in detection effluentt)。
With the time as abscissa, solution concentration is vertical coordinate, draws curve, obtains breakthrough curve (as shown in Figure 4).
During from fig. 4, it can be seen that initial concentration is 5mg/L, breakthrough curve reaches breakthrough point soon, bent
The steeper slope of line.In this composite, the content of chitosan nano fiber is less, thus causes material relatively
It is pierced in the short time.But actual application can improve absorption effect by the number of plies increasing material
Really.
Embodiment 4
1) preparation of spinning solution method such as embodiment 1, the technique of electrostatic spinning is: voltage 30kV, spinning distance
For 10cm, liquid supply speed is 0.1mm/min；Employing grammes per square metre is 100g/m2Glass fibre non-woven be base
The end, by chitosan nano fiber electrospinning in substrate, obtain chitosan/glass fibre non-woven composite；
In the composite of preparation, the average diameter of chitin fiber is 75nm, and the grammes per square metre of chitin fiber is 4g/m2,
The aperture of composite is 2.1 μm；The composite of preparation is put into and fills 20mL epoxychloropropane solution
In exsiccator, epoxychloropropane vapor crosslinking 12h, obtain the chitosan nano fiber composite of crosslinking.
2) disk of the lower 1 a diameter of 47mm of cutting from composite, makes Filtration Adsorption medium；Will
Adsorbing medium is put in filter, obtains filter assemblies；With peristaltic pump as power source, it is 2mg/L by initial concentration
Hexavalent chromium solution penetrate filter assemblies with the speed of 2mL/min, collect the effluent after different time, inspection
Survey the concentration (C of chromium ion in effluentt).With the time as abscissa, solution concentration is vertical coordinate, draws song
Line, obtains breakthrough curve (as shown in Figure 5).
From fig. 5, it can be seen that owing to the aperture of composite is relatively big, between adsorbent solution and composite
Insufficient contact, breakthrough curve reaches breakthrough point soon, and slope of a curve is steeper.
Embodiment 5
1) preparation of spinning solution method such as embodiment 2, the technique of electrostatic spinning is: voltage 20kV, spinning distance
For 8cm, liquid supply speed is 0.1mm/min；Employing grammes per square metre is 30g/m2Polyester fiber non-woven fabric be substrate,
By chitosan nano fiber electrospinning in substrate, obtain chitosan/polyester fabric nonwoven cloth composite；Preparation
Composite in the average diameter of chitin fiber be 75nm, the grammes per square metre of chitin fiber is 2g/m2, multiple
The aperture of condensation material is 0.7 μm.
2) preparation method of Filtration Adsorption medium such as embodiment 1, multiple containing 10 layers in the most each Filtration Adsorption medium
Condensation material, a diameter of 47mm；Prepare 6 Filtration Adsorption media, be respectively intended to adsorbing separation lead, cadmium, copper,
Zinc, nickel and Cr VI；The concentration of heavy metal ion is all 1mg/L；Adsorbing medium is put in filter,
To filter assemblies；With peristaltic pump as power source, by solution that initial concentration is 1mg/L with the speed of 2mL/min
Degree penetrates filter assemblies, collects the effluent after different time, the concentration of heavy metal ion in detection effluent
(Ct).With the time as abscissa, solution concentration is vertical coordinate, draws curve respectively, obtains breakthrough curve,
Trying to achieve 10% when penetrating from curve, composite is to the adsorbance of various heavy metal ion as shown in Figure 6.
From fig. 6, it can be seen that the absorbability size order of various heavy metal ion is by composite:
Cu>Cr>Ni>Cd>Pb.Especially best to copper and chromic adsorption effect, during breakthrough point, adsorbance is super
Cross 15mg/g.Composite has adsorption effect to contents of many kinds of heavy metal ion, can disposably remove in water
Contents of many kinds of heavy metal ion, have very important significance in actual applications.
Embodiment 6
1) preparation of spinning solution method, electrostatic spinning process and cross-linking method such as embodiment 1, obtaining size is
The composite films of 200mm*300mm.
2) preparation of rolling method is used to filter separating medium；By chitosan nano fiber composite membrane, around a diameter of
After the hollow reel of 15mm is closely wound, loads in the shell of a diameter of 20mm, two ends are carried out
Termination process, obtains wound fil-tration adsorbing medium；Adsorbing medium is put in filter, obtain filter assemblies；
With peristaltic pump as power source, the hexavalent chromium solution that initial concentration is 1mg/L is penetrated with the speed of 2mL/min
Filter assemblies, collects the effluent after different time, the concentration (C of hexavalent chromium in detection effluentt)；
After about 150 minutes, detect that the concentration of hexavalent chromium is 100 μ g/L.
Comparative example 1
Preparation does not contains the chitosan nano fibrous membrane adsorbing material at the bottom of nonwoven fabric base, comprises the following steps:
Be 90% by 3g deacetylation, molecular weight be 200,000 chitosan to be dissolved in 57g mass fraction be 90%
Acetum in, stirring and dissolving 12h, obtain the uniform spinning liquid that mass fraction is 5%；Utilize electrostatic
Spinning process prepares chitosan nano fiber membrane, and wherein, the technique of electrostatic spinning is: voltage 23kV, spins
Flight lead is from for 6cm, and liquid supply speed is 1mL/h；The chitosan nano fiber membrane obtained is soaked in alkaline solution
After bubble, cleaned and dried obtains chitosan nano fibrous membrane adsorbing material.
Comparative example 2
Directly use polyester non-woven fabric substrate as heavy-metal adsorption material.Use embodiment 1 step (2)
Method prepares filtration separating medium at the bottom of nonwoven fabric base.
Comparative example 3
Using the chitosan nano fibrous membrane adsorbing material of comparative example 1 as heavy-metal adsorption material, do not contain nothing
Spin cloth substrate, use glutaraldehyde to cross-link chitosan nano fibrous membrane adsorbing material.
Comparative example 4
Chitosan nano fiber/polyester non-woven fabric composite prepared by the step (1) of embodiment 1 is not used
Glutaraldehyde cross-links.
Adsorbing material above-described embodiment 1-4 and comparative example 1-4 prepared carries out following test:
By 0.05g adsorbing material, join 100mL prepare containing heavy metal ion Pb2+、Cd2+、
Cu2+、Ni2+And Cr6+Aqueous solution in (concentration of each heavy metal ion is 10mg/L), at constant temperature oscillator
Middle room temperature concussion 8h, the aqueous solution after pipetting l0mL concussion with pipet is in plastic tube and seal.Use
With the concentration of heavy metal ion in absorption rear solution before ICP test absorption, it is computed obtaining each adsorbing material pair
The adsorbance (mg/g) of various heavy metal ion is as shown in table 1.
Table 1
As it can be seen from table 1 after chitosan crosslinked, although partial adsorbates group is occupied, but due to quilt
The chitosan dissolved reduces, and adsorbance increases on the contrary.Polyester non-woven fabric substrate heavy metal ion does not adsorb
Effect, such that it is able to get rid of the substrate contribution to adsorption effect.Due to the existence at the bottom of nonwoven fabric base, chitosan
Fibrolaminar thickness reduces, and makes solution be easier to diffuse into the inside of fiber, thus causes the increasing of adsorbance
Add.Meanwhile, composite has adsorption effect to contents of many kinds of heavy metal ion, can disposably remove in water
Contents of many kinds of heavy metal ion, makes purification process simplify, has very important significance in actual applications.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the present invention
It is not limited to above-mentioned method detailed, does not i.e. mean that the present invention has to rely on above-mentioned method detailed and could implement.
Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, each former to product of the present invention
The equivalence of material is replaced and the interpolation of auxiliary element, concrete way choice etc., all falls within the protection model of the present invention
Within the scope of enclosing and disclosing.
Claims (10)
1. the chitosan nano fiber composite membrane for adsorbing separation heavy metal ion, it is characterised in that
Described composite membrane is formed by the bottom of chitosan nano fiber and nonwoven fabric base.
Composite membrane the most according to claim 1, it is characterised in that containing of described chitosan nano fiber
Amount is 0.5-4g/m2, preferably 1-3.5g/m2, more preferably 2.5g/m2；
Preferably, the deacetylation of described chitosan is 75-95%, preferably 80-90%, more preferably
90%；
Preferably, the molecular weight of described chitosan is 15-30 ten thousand, preferably 18-25 ten thousand, more preferably
200000.
Composite membrane the most according to claim 1 and 2, it is characterised in that be poly-at the bottom of described nonwoven fabric base
Ester fiber, polypropylene fibre, Fypro, vinal, polyacrylonitrile fibre, cotton fiber,
Any one or the mixing of at least two in viscose rayon, flaxen fiber or glass fibre, preferably polyester are fine
Any one or the mixing of at least two in dimension, vinal or viscose rayon, more preferably
Polyester fiber.
4. according to the preparation method of the composite membrane described in any one of claim 1-3, it is characterised in that include
Following steps:
(1) preparation of chitosan nano fiber；
(2) use step (1) preparation method by chitosan nano fiber electrospinning at the bottom of nonwoven fabric base,
Obtain described chitosan nano fiber composite membrane.
Preparation method the most according to claim 4, it is characterised in that step (1) described chitosan
The preparation method of nanofiber is method of electrostatic spinning；
Preferably, described method of electrostatic spinning includes: dissolved in a solvent by described chitosan, stirs to shell poly-
Sugar is completely dissolved, and stands 2h deaeration, obtains chitosan solution；The technique of described electrostatic spinning is: voltage 15-30
KV, receiving range 6-15cm, spinning liquid liquid supply rate 0.5-1.5mL/h；
Preferably, described solvent be trifluoroacetic acid or acetum, preferably mass concentration be the vinegar of 85-90%
Acid solution；
Preferably, the concentration of described chitosan solution is 3-5wt%, preferably 3.5-4wt%, further preferably
For 4wt%；
Preferably, a diameter of 60-200nm of described chitosan nano fiber prepared by step (1).
6. according to the preparation method described in claim 4 or 5, it is characterised in that further comprising the steps of:
(3) chitosan nano fiber composite membrane step (2) prepared uses cross-linking agent to cross-link；
(4) by the described composite membrane combination of the different numbers of plies, obtain composite membrane and filter separating medium；
(5) described composite membrane filtration separating medium is installed in filter separator.
Preparation method the most according to claim 6, it is characterised in that step (3) described cross-linking agent
For any one in epoxychloropropane, formaldehyde, Biformyl or glutaraldehyde or the mixing of at least two, preferably
For formaldehyde or glutaraldehyde, more preferably glutaraldehyde；
Preferably, the mode of step (4) described composite membrane combination is superposing type and/or rolling；Preferably, institute
The number of plies stating composite membrane is 1-20 layer, preferably 2-15 layer, more preferably 10 layers.
8. according to the preparation method described in any one of claim 4-7, it is characterised in that comprise the following steps:
(1) preparation of chitosan nano fiber: described chitosan is dissolved in trifluoroacetic acid or mass concentration is
In the acetum of 85-90%, stirring and be completely dissolved to chitosan, stand 2h deaeration, obtaining mass fraction is
The uniform spinning liquid of 3-5wt%；Electrospinning process is utilized to prepare chitosan nano fiber, described electrostatic
The technique of spinning is: voltage 15-30kV, receiving range 6-15cm, spinning liquid liquid supply rate 0.5-1.5mL/h；
A diameter of 60-200nm of the described chitosan nano fiber prepared；
(2) use step (1) preparation method by chitosan nano fiber electrospinning at the bottom of nonwoven fabric base,
Obtain described chitosan nano fiber/nonwoven fabrics composite film；
(3) chitosan nano fiber composite membrane step (2) prepared uses cross-linking agent to cross-link, institute
Stating cross-linking agent is the mixed of any one or at least two in epoxychloropropane, formaldehyde, Biformyl or glutaraldehyde
Close；
(4) use superposing type and/or rolling to be combined the described composite membrane of 1-20 layer, obtain composite membrane
Filter separating medium；
(5) described composite membrane filtration separating medium is installed in filter separator.
9. according to the application in adsorbing separation heavy metal ion of the composite membrane described in any one of claim 1-3.
Application the most according to claim 9, it is characterised in that described heavy metal ion is Pb2+、
Cd2+、Cu2+、Zn2+、Ni2+Or Cr6+In any one or the mixing of at least two, preferably Cr6+,
The more preferably low concentration Cr in drinking water or industrial wastewater6+。
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