CN108159902A - A kind of preparation method of chelating type polyacrylonitrile hollow fiber membrane - Google Patents
A kind of preparation method of chelating type polyacrylonitrile hollow fiber membrane Download PDFInfo
- Publication number
- CN108159902A CN108159902A CN201710824401.2A CN201710824401A CN108159902A CN 108159902 A CN108159902 A CN 108159902A CN 201710824401 A CN201710824401 A CN 201710824401A CN 108159902 A CN108159902 A CN 108159902A
- Authority
- CN
- China
- Prior art keywords
- hollow fiber
- fiber membrane
- polyacrylonitrile
- chelating type
- polyacrylonitrile hollow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/78—Graft polymers
-
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/34—Use of radiation
- B01D2323/345—UV-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/40—Fibre reinforced membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The present invention discloses a kind of preparation method of chelating type polyacrylonitrile (PAN) hollow-fibre membrane, preparation method is, polyacrylonitrile resin through NaOH pretreatment, it is mixed with diazo resin solution after carrying out Electrostatic Absorption, it is mixed again with disodium ethylene diamine tetra-acetic acid solution and carries out Electrostatic Absorption, obtained product passes through drying, after uv-exposure, it obtains polyacrylonitrile hollow fiber membrane and repeats repeatedly progress diazo resin Electrostatic Absorption, disodium ethylene diamine tetraacetate Electrostatic Absorption and the processing of follow-up uv-exposure, obtain that there are several layers of diazo resin and the polyacrylonitrile hollow fiber membrane of disodium ethylene diamine tetraacetate modified layer, and chelating type polyacrylonitrile hollow fiber membrane.Had using the method that present invention process prepares the tunica fibrosa simple for process, using water as solvent, save energy consumption, the feature of environmental protection is good, the characteristics of being easily industrialized production, obtained chelating type polyacrylonitrile hollow fiber membrane have good hydrophily, have good adsorption function to the contents of many kinds of heavy metal ion in solution, and use can be repeatedly regenerated, still keep good heavy metal ion adsorbed performance.
Description
Technical field
The present invention relates to polyacrylonitrile (PAN) hollow-fibre membrane fields, and in particular to a kind of to have to various metals ion
The preparation of the chelating type polyacrylonitrile hollow fiber membrane of good adsorption effect.
Background technology
Chemical laboratory, steam power plant is metallurgical, mineral products processing, containing a large amount of in the waste water that the industries such as combustible generate
Heavy metal ion, these heavy metal ion are typically found in acid solution, it is difficult to they are removed, they can be to water, soil
Earth etc. causes very big pollution.
The method for removing heavy metal ions in wastewater at present mainly has absorption method, galvanoplastic, ion-exchange, membrane separation process
With the precipitation method etc., in these methods, absorption method is considered as a kind of effective and environmentally friendly method in water treatment field.
It is in recent years, related due to the excellent properties that electrostatic spinning nano fiber film is shown at heavy metal ion adsorbed aspect
Scientific research personnel carried out the research work of a large amount of preparations and modification, and in textile industry, polyacrylonitrile (PAN) doughnut
Film is not only cheap, but also chemical stabilization, and mechanical performance is excellent, corrosion-resistant, and the resistance to mould and solvent of resistance to characteristic has become the modern times most
One of widely used polymer.
Recently, the heavy metal ion that people are exploring the modification of polyacrylonitrile film to be used in water removal always, patent
CN102140705A discloses a kind of preparation method for the thioamides base chelated nano fiber for adsorbing heavy metal ion, through electrostatic
After spinning obtains nanofiber, through precrosslink, the chelated nano fiber of absorption heavy metal ion is made in thioamides, obtains
Fiber thermal stability and solvent resistance are good, there is good adsorptivity to heavy metal ion, but because only in surface grafting
Thio polyamide, so the adsorbance to heavy metal ion is insufficient, and method of modifying is relatively complicated.Patent CN105568423A is public
Cloth a kind of amidoxime polyacryl-nitrile spinning fluid and nanoscale ion exchange fiber prepared therefrom, by polyacrylonitrile solution
Middle addition oxammonium hydrochloride and catalyst, high-temperature stirring, filtering obtain spinning solution, using electrostatic spinning technique after adding cross-linked inhibitor
Nano fibrous membrane is made, it is post-treated to obtain the nanoscale ion exchange fiber that have suction-operated to heavy metal ion.Patent
105195110A discloses a kind of membranaceous sorbing material of amine-modified fiber and preparation method thereof, using polyacrylonitrile powder as base
Matter prepares fluid matrix by Solid-Phase Grafting Polymerization and aminating reaction, and the membranaceous sorbing material of tencel is made through electrostatic spinning.
The membranaceous sorbing material of gained has high water absorption surface and can effectively adsorb contents of many kinds of heavy metal ion in water, but this method amine
Spinning is carried out after change, method is cumbersome and wastes raw material, and only surface amination group chelated mineral, therefore to the absorption of metal
Amount is not high.
Invention content
The technical problems to be solved by the invention are to provide a kind of chelating type polyacrylonitrile (PAN) hollow-fibre membrane
Preparation method, the preparation method raw material are easy to get, are simple for process, is easily operated, meanwhile, prepared chelating type polyacrylonitrile is hollow
Tunica fibrosa has good suction-operated to various metals ion.
The present invention carries out polyacrylonitrile (PAN) doughnut using diazo resin grafting disodium ethylene diamine tetraacetate (EDTA)
The modification of film, method of modifying are：The pretreated polyacrylonitrile hollow fiber membrane of sodium hydrate aqueous solution and diazo resin are water-soluble
Liquid mixing carries out Electrostatic Absorption, and the polyacrylonitrile hollow fiber membrane for being adsorbed with diazo resin is water-soluble with disodium ethylene diamine tetraacetate again
Liquid mixing carries out Electrostatic Absorption, and obtained product is exposed processing after drying, with ultraviolet light, obtains having one layer of modified layer
Chelating type PAN hollow-fibre membranes；The film repeats above-mentioned two steps Electrostatic Absorption and exposure-processed, obtains with multilayer modified layer
Chelating type polyacrylonitrile hollow fiber membrane.
A kind of preparation method of chelating type polyacrylonitrile hollow fiber membrane provided by the invention is：
1. the preparation of each material solution
(1) sodium hydrate aqueous solution：Sodium hydroxide is mixed with water, obtains sodium hydrate aqueous solution；
(2) diazo resin solution：Diazo resin is mixed with water, obtains diazo resin aqueous solution；
(3) EDTA solution：EDTA is mixed with water, obtains EDTA aqueous solutions.
A concentration of 0.5-2.5mol/L of the sodium hydrate aqueous solution；
A concentration of 0.5-2mg/mL of the diazo resin aqueous solution；
A concentration of 1-4mg/mL of the EDTA aqueous solutions.
2. the pretreatment of polyacrylonitrile hollow fiber membrane：
(1) polyacrylonitrile hollow fiber membrane is cut into segment, rear drying for standby is washed with water；
(2) it is water-soluble that the polyacrylonitrile hollow fiber membrane obtained by (1) is placed in 40-60 DEG C of 0.5-2.5mol/L sodium hydroxides
In liquid, 1-5h is reacted, then takes out, is washed with water, be dried in vacuo；The preferred 1-2mol/L of sodium hydrate aqueous solution concentration, reaction
The excellent time is 2-4h；
(3) it is the polyacrylonitrile hollow fiber membrane obtained by (2) is dry in vacuum drying chamber, it obtains completing the poly- of pretreatment
Acrylonitrile hollow-fibre membrane.
3. the LBL self-assembly of polyacrylonitrile hollow fiber membrane modified layer and the system of chelating type polyacrylonitrile hollow fiber membrane
It is standby：
(1) the pretreated polyacrylonitrile hollow fiber membrane obtained in step 2 is put into the diazonium tree prepared in step 1
First step Electrostatic Absorption, a concentration of 0.5-2mg/mL of diazo resin aqueous solution, preferably 0.8-1.5mg/ are carried out in fat aqueous solution
mL；Adsorption time is 5h--50h, preferably 20-30h.
(2) the PAN hollow-fibre membranes that diazo resin is adsorbed with obtained by (1) are washed with water, are then placed in ethylenediamine tetrem
Second step Electrostatic Absorption is carried out in acid disodium aqueous solution.A concentration of 1-4mg/ of disodium ethylene diamine tetra-acetic acid aqueous solution
ML, preferably 1.2-1.8mg/mL；Adsorption time is 5h-50h, preferably 20-30h；The number of water washing is 2-3 times preferred.
(3) hollow-fibre membrane obtained by (2) is washed with water, then dried, it is dry to complete to be placed on progress purple under ultraviolet lamp
Outer exposure-processed.Time for exposure is 1-6h, preferably 2-4h；The water washing number is 2-3 times preferred.
(4) the chelating type polyacrylonitrile hollow fiber membrane with one layer of modified layer obtained by (3) is repeated as many times progress
(1), (2) and (3) step, carries out Electrostatic Absorption twice and exposure in an identical manner, is further added by multilayer diazo resin and second two
Amine tetraacethyl disodium modified layer has the chelating type polyacrylonitrile hollow fiber membrane of multilayer modified layer.Repeat step (1), (2) and
(3) number preferably 1 time -5 times.
A kind of preparation method of chelating type polyacrylonitrile hollow fiber membrane provided by the invention, the operation in step 3 is except purple
Outside outer exposing operation, other operations carry out under light protected environment.
A kind of preparation method of chelating type polyacrylonitrile hollow fiber membrane provided by the invention, first step Electrostatic Absorption and
Two step Electrostatic Absorptions preferably carry out at room temperature.
A kind of preparation method of chelating type polyacrylonitrile hollow fiber membrane provided by the invention, the water used in each step operation
It is preferred that distilled water or deionized water.
A kind of preparation method of chelating type polyacrylonitrile hollow fiber membrane provided by the invention, the molecular weight of diazo resin are
500-6000, preferably 1000-4000.
The present invention by polyacrylonitrile hollow fiber membrane carry out grafting diazo resin and disodium ethylene diamine tetraacetate side
Method is prepared for a kind of chelating type polyacrylonitrile hollow fiber to contents of many kinds of heavy metal ion in water with extraordinary suction-operated
Film, and it is simple for process, process saves energy consumption using water as solvent, and the feature of environmental protection is good, it is easy to accomplish industrialized production.
It is hollow being adsorbed onto polyacrylonitrile using Electrostatic Absorption since used diazo resin contains a large amount of diazoes
After on tunica fibrosa, these diazoes are provided with the access site of a large amount of chelation group, the ethylenediamine tetraacetic containing a large amount of carboxyls
Acetic acid disodium (EDTA) is linked into weight of the absorption on polyacrylonitrile hollow fiber membrane by carboxyl and diazo Electrostatic Absorption
It on nitrogen resin, is then exposed by purple light, between diazo resin and polyacrylonitrile hollow fiber membrane, between diazo resin and EDTA
Photo-crosslinking occurs simultaneously, generates chemical combination key, diazo resin and EDTA is successfully just introduced into polyacrylonitrile hollow fiber
On film, EDTA in itself has heavy metal ion outstanding sequestering power, while the amine groups that largely swell present in diazo resin,
It also has heavy metal ion certain sequestering power, and therefore, surface is accessed simultaneously in the polyacrylonitrile of diazo resin and EDTA
Empty fiber membrane has heavy metal ion good adsorption capacity, meanwhile, we by the method for LBL self-assembly (each modified layer from
The schematic diagram of assembling is as shown in Figure 1, the polyacrylonitrile hollow fiber membrane that surface is accessed to one layer of diazo resin and EDTA repeats
Absorption diazo resin and EDTA, then the operation of purple light exposure are carried out, the tunica fibrosa is made to form multilayer diazo resin and EDTA modifications
Layer provides further amounts of chelation group on the surface of tunica fibrosa, further enhances its sequestering power, greatly improve the fiber
Film is to the adsorption capacity of heavy metal ion.The obtained tunica fibrosa of the preparation method is due to a large amount of hydrophilic groups in wherein modified layer simultaneously
The introducing of group, significantly increases its hydrophily, so as to more improve the ability that the film adsorbs heavy metal in water environment.
Meanwhile the chelating type polyacrylonitrile hollow fiber membrane prepared by the present invention is after use, by simple desorption
Process can be reused, and still maintain good adsorption effect.
Figure of description
Fig. 1 is the LBL self-assembly schematic diagram of the multilayer modified layer of polyacrylonitrile hollow fiber membrane.
Fig. 2 is the scanning electron microscope diagram and atomic force microscopy diagram of polyacrylonitrile hollow fiber membrane, wherein (a) (b)
(c) it is the polyacrylonitrile hollow fiber membrane of no modified layer；(d) (e) (f) is with three layers of diazo resin and EDTA modified layers
Chelating type polyacrylonitrile hollow fiber membrane.
Fig. 3 be polyacrylonitrile hollow fiber membrane before modified after infrared spectrum.Wherein (a) is the polypropylene of no modified layer
Nitrile hollow-fibre membrane, (b) are the chelating type polyacrylonitrile hollow fiber membrane with diazo resin and EDTA modified layers.
Fig. 4 is the water contact angle of the chelating type polyacrylonitrile hollow fiber membrane with the different modified layer numbers of plies.
Polluted by copper amounts of the Fig. 5 for (a) difference DR (diazo resin)-EDTA number of plies modified fibre films, (b) difference DR-EDTA
The water flux for the polyacrylonitrile hollow fiber membrane that the number of plies is modified, (c) 3 layers of DR-EDTA modified polyacrylonitriles hollow-fibre membrane are different
Polluted by copper amount under the conditions of pH, the polluted by copper under (d) 3 layers of DR-EDTA modified polyacrylonitrile hollow-fibre membrane condition of different temperatures
Amount.
Fig. 6 is chelating type polyacrylonitrile hollow fiber membrane absorbing copper ions, mercury ion, cadmium ion and lead ion and its mixing
Color change and energy spectrum diagram after liquid.
Fig. 7 is that the chelating type polyacrylonitrile hollow fiber membrane that 3 layers of DR-EDTA are modified repeats copper ion after desorption, absorption
Adsorbance.
Specific embodiment
Embodiment 1
The preparation of individual layer diazo resin and the chelating type polyacrylonitrile hollow fiber membrane of EDTA modified layers
(1) preparation of each material solution：
a：Sodium hydrate aqueous solution：Sodium hydroxide is mixed with distilled water under room temperature, and stirring is configured to a concentration of 1mol/L hydrogen
Sodium hydroxide solution.
b：Diazo resin solution：Diazo resin is mixed with distilled water under room temperature, and stirring is configured to a concentration of 1mg/mL diazonium
Resin solution, the molecular weight of diazo resin is 1248-3120.
c：Disodium ethylene diamine tetra-acetic acid solution：Disodium ethylene diamine tetraacetate is mixed with distilled water under room temperature, is prepared into
A concentration of 1.5mg/mL disodium ethylene diamine tetra-acetic acid aqueous solutions.
(2) pretreatment of polyacrylonitrile hollow fiber membrane：
a：Polyacrylonitrile hollow fiber membrane is cut into the segment of 3cm-5cm, is washed with distilled water clean rear drying for standby.
b:Polyacrylonitrile hollow fiber membrane obtained by (a) is placed in sodium hydroxide solution and is reacted 4 hours for 40 DEG C.It has reacted
It is washed with water into rear taking-up to neutrality.
c：Polyacrylonitrile hollow fiber membrane obtained by (b) is 24 hours dry in vacuum drying chamber.
(3) preparation of chelating type polyacrylonitrile hollow fiber membrane：
a:Aforementioned pretreated polyacrylonitrile hollow fiber membrane addition is filled to room temperature in the beaker of diazo resin solution
Lower carry out Electrostatic Absorption, the time is for 24 hours.
b:The polyacrylonitrile hollow fiber membrane that diazo resin is adsorbed with obtained by a is washed with distilled water 2-3 times.
c：Polyacrylonitrile hollow fiber membrane addition obtained by (b) is filled to room temperature in the beaker of disodium ethylene diamine tetra-acetic acid solution
Lower carry out Electrostatic Absorption, the time is for 24 hours.
d:Polyacrylonitrile hollow fiber membrane obtained by c is washed with distilled water 1-2 times.
e：Polyacrylonitrile hollow fiber membrane obtained by d is placed on air drying, dry be placed under ultraviolet lamp is exposed
Processing, 3 hours time for exposure obtain the chelating type polyacrylonitrile hollow fiber with individual layer diazo resin and EDTA modified layers
Film, above-mentioned experimentation are operated in addition to ultraviolet lamp exposure process under the conditions of being protected from light.
Embodiment 2
The preparation of chelating type polyacrylonitrile hollow fiber membrane with two layers of diazo resin and EDTA modified layers
Experimentation obtains tunica fibrosa and repeats (3) a-e operations one with embodiment 1, but in (3) are completed after step e
Time, obtain the chelating type polyacrylonitrile hollow fiber membrane with two layers of diazo resin and EDTA modified layers.
Embodiment 3
The preparation of chelating type polyacrylonitrile hollow fiber membrane with three layers of diazo resin and EDTA modified layers
What is obtained in embodiment 2 has the chelating type polyacrylonitrile hollow fiber membrane of two layers of modified layer, according in embodiment 1
(3) a-e operations are handled in, obtain the chelating type polyacrylonitrile hollow fiber with three layers of diazo resin and EDTA modified layers
Film.
Embodiment 4
The preparation of chelating type polyacrylonitrile hollow fiber membrane with four layers of diazo resin and EDTA modified layers
(1) preparation of each material solution：Preparation method is obtained with embodiment 1
The sodium hydroxide solution of a concentration of 2mol/L,
The diazo resin solution of a concentration of 1.8mg/mL.
A concentration of 1.8mg/mL disodium ethylene diamine tetra-acetic acid aqueous solutions.
(2) pretreatment of polyacrylonitrile hollow fiber membrane：
a：Polyacrylonitrile hollow fiber membrane is cut into the segment of 3cm-5cm, is washed with distilled water clean rear drying for standby.
b:Polyacrylonitrile hollow fiber membrane obtained by (a) is placed in sodium hydroxide solution and is reacted 2 hours for 60 DEG C.It has reacted
It is washed with water into rear taking-up to neutrality.
c：Polyacrylonitrile hollow fiber membrane obtained by (b) is dried.
(3) preparation of chelating type polyacrylonitrile hollow fiber membrane：
a:Aforementioned pretreated polyacrylonitrile hollow fiber membrane addition is filled to room temperature in the beaker of diazo resin solution
Lower carry out Electrostatic Absorption, time 15h.
b:The polyacrylonitrile hollow fiber membrane that diazo resin is adsorbed with obtained by a is washed with deionized 2-3 times.
c：Polyacrylonitrile hollow fiber membrane addition obtained by (b) is filled to room temperature in the beaker of disodium ethylene diamine tetra-acetic acid solution
Lower carry out Electrostatic Absorption, time 15h.
d:Polyacrylonitrile hollow fiber membrane obtained by c is washed with deionized 1-2 times.
e：Polyacrylonitrile hollow fiber membrane obtained by d is placed on air drying, dry be placed under ultraviolet lamp is exposed
Processing, 4 hours time for exposure obtain the chelating type polyacrylonitrile hollow fiber with individual layer diazo resin and EDTA modified layers
Film；Operation before uv-exposure carries out under the conditions of being protected from light.The film repeats a-e steps three times, obtains having four layers of modification
The chelating type polyacrylonitrile hollow fiber membrane of layer.
Embodiment 5
The preparation of chelating type polyacrylonitrile hollow fiber membrane with five layers of diazo resin and EDTA modified layers
What is obtained in embodiment 4 has the chelating type polyacrylonitrile hollow fiber membrane of four layers of modified layer, according in embodiment 4
(3) a-e operations are handled in, obtain the chelating type polyacrylonitrile hollow fiber with five layers of diazo resin and EDTA modified layers
Film.
Embodiment 6
Obtained chelating type polyacrylonitrile hollow fiber membrane in embodiment 1-5 and non-modified polyacrylonitrile are carried out
Analysis and performance comparison test
(1) scanning electron microscope (SEM) photograph to each polyacrylonitrile hollow fiber membrane and atomic force Electronic Speculum map analysis, are as a result shown in Fig. 2.Fig. 2
(a) it is the polyacrylonitrile hollow fiber membrane not being modified, the mean size of surface holes is about 1.44um；Fig. 2 (b)
(c) it is its atomic force microscope, it can be seen that pure PAN hollow-fibre membranes are smooth neat, surface roughness 15.9nm, figure
(d) the PAN films being modified for three layers of DR-EDTA, the mean size of surface holes is about 0.92um；Fig. 2 (e) (f) is its atom
Force microscope, it can be seen that the PAN film surfaces that three layers of DR-EDTA are modified show coarse peak, and surface roughness is
57.6um, this shows to introduce DR-EDTA layers in PAN film surfaces, changes roughness.Rough surface can increase between film and water
Contact area, this can increase film to the absorption of copper and the infiltration of water indirectly.
(2) it carries out infrared spectrum (IR) to the polyacrylonitrile hollow fiber membrane after before modified to analyze, as a result sees Fig. 3.Fig. 3
(a) be no modified layer tunica fibrosa, Fig. 3 (b) is three layers of modified chelating type polyacrylonitrile hollow fiber membrane.It is found that Fig. 3
(a) and (b) is in 2245cm-1There is absorption peak in place, this is the characteristic peak of itrile group.In Fig. 3 (b), it is attributed to the vibration of C=O
1646cm-1The peak at place and the 3031cm of stretching vibration for being attributed to unsaturated C-H-1The peak at place confirms the presence of phenyl ring.
3388cm-1The characteristic peak of secondary amino group further prove that diazo resin is successfully grafted on polyacrylonitrile hollow fiber membrane.
About 3400cm-1Observe the vibration of O-H in place.Other than the presence of C=O, the grafting of EDTA is had also demonstrated.Hence it is demonstrated that diazonium
Resin and EDTA are successfully connected on polyacrylonitrile hollow fiber membrane.
(3) water contact angle of polyacrylonitrile hollow fiber membrane after before modified is analyzed, as a result sees Fig. 4, in figure, curve
On water contact angle figure from left to right be followed successively by the tunica fibrosa with 0,1,2,3,4,5 layer of diazo resin and EDTA modified layers,
This it appears that the variation tendency of water contact angle, when not having modified layer, the water contact angle of film is 87.8 DEG C, and applies the weight that is of five storeys
The water contact angle of nitrogen resin and the polyacrylonitrile hollow fiber membrane of EDTA modified layers falls below 63.45 DEG C, the descension theory at hydrophilic angle
Bright process increases diazo resin and the tunica fibrosa of EDTA modified layers, has better hydrophily, it should be due in modified layer
The effect that the introducing of a large amount of hydrophilic radicals is played.
(4) rear tunica fibrosa before modified to analyze the absorption test of copper ion, the quality of the film used is 0.006g,
Film is immersed in certain density copper ion solution, 1mL solution is taken out at regular intervals and measures concentration, the principle utilized is copper
Ion can form a kind of complex compound with sodium diethyldithiocarbamate, and this complex compound can be by chloroform extraction simultaneously
And can be come out by ultraviolet detection, concentration and the variation of copper ion are detected with this method, then by the way that absorption is calculated
Copper ion amount, as a result see Fig. 5 a, wherein, pure fiber PAN, PAN- (DR-EDTA) in each figure1-PAN-(DR-EDTA)5
No modified layer is represented respectively, the polyacrylonitrile hollow fiber membrane for there are 1-5 layers of DR-EDTA modified layers.It can be seen that from Fig. 5 a
PAN fiber film is to the adsorption capacity of copper ion, as can be seen that having without modified PAN hollow-fibre membranes to copper a small amount of from Fig. 5 a
Sequestering power has the ability of absorbing copper, and with DR and EDTA layers of increase, the adsorbance of copper increases to from 21.9mg/g
50.3mg/g, incrementss reach 230%, and PAN- (DR-EDTA)3Adsorbance to copper is 37.5mg/g, and incrementss are
171%, the increase of polluted by copper amount is attributed to DR-EDTA layers of introducing, contains a large amount of chelation group in DR-EDTA layers, so
It will be seen that often increasing by one layer DR-EDTA layers from figure, the adsorption capacity of copper ion can all be increased.Polypropylene
The result that the water flux of nitrile hollow-fibre membrane measures represents in figure 5b, it can be seen that under pressure 19.79kp, no modified layer
PAN fiber film, PAN- (DR_EDTA)1-5Water flux be respectively 733.30,1049.80,1085.94,1068.85,679.30,
350.30g·m-1·h-1,PAN-(DR-EDTA)1The increase of water flux is attributed to polyacrylonitrile hollow fiber membrane surface hydrophilicity
The introducing of group, because DR and EDTA are hydrophilic radicals.And PAN- (DR-EDTA)1-3Bucket amount tends towards stability mainly by two
Aspect reason：1, the introducing of hydrophilic radical can increase the water flux of film, and 2.DR-EDTA chains are introduced into polyacrylonitrile
The hole on empty fiber membrane surface has certain plugging action, and with reference to the factor of these two aspects, water flux tends towards stability substantially.PAN-
(DR-EDTA)3-5Water flux declines, the reason is that with the introducing of DR-EDTA, polymer chain is to the plugging action in the hole of film surface
The promotion considerably beyond hydrophilic radical for water flux.In order to probe into Modified Membrane under various circumstances to the adsorption energy of copper
Power, we test the influence of pH and temperature for absorption, from Fig. 5 c it will be seen that modified tunica fibrosa is to copper ion
Adsorbance increases (4.0-6.5) with the increase of pH and (6.5-7.0) is tended towards stability with the increase of pH, the results showed that, modified PAN
There can be better absorption to copper in neutral environment, can prove that acidic environment can make ion-ligand reaction towards desorption
Direction carry out, this is attributed in acid condition, on amino on N atoms and proton with reference to and lose coordination, make the chela of film
Conjunction ability reduces.As can be seen that as the temperature increases, the adsorbance of copper increases from Fig. 5 d, after this is attributed to temperature increase,
The free volume of polymer chain increases, and more copper ions can be entered in polymer chain, so as to cause Modified Membrane to copper more
More absorptions, and when temperature reaches 70 DEG C -80 DEG C, the structure of film changes, and has not been suitable for adsorbing copper ion.,
(5) to adsorption analysis of the modified obtained chelating type polyacrylonitrile hollow fiber membrane to various heavy metal ion,
The film of several groups of phase homogenous quantities is immersed in copper ion respectively, chromium ion, mercury ion, the mixed solution of lead ion and more than ion
In, it takes the film out and is washed with distilled water totally after absorbing 12 hours, will be dry after the survivor ion wash clean on surface, utilize power spectrum
The absorption to various ions is measured as a result, absorbing result sees Fig. 6.From figure it will be seen that respectively to copper, chromium, mercury, lead weight
Metal ion is individually after absorption, can detect a large amount of corresponding heavy metal example absorption on film respectively, and to copper, chromium, mercury,
After the absorption of lead heavy metal ion mixed solution, the presence of various heavy metal ion can be also detected on film.It is found that modified is poly-
Acrylonitrile hollow-fibre membrane has good suction-operated to heavy metal ion such as copper, chromium, mercury, lead.
(6) it in order to study stability of the chelating type polyacrylonitrile hollow fiber membrane to heavy metal ion adsorbed performance, measures
The repetition absorption of copper ion and desorption experiment 720h.Fig. 7 displays repeat the polluted by copper capacity after desorbing.The result shows that PAN-
DR(EDTA)3Film remains to keep stronger adsorption capacity after 720h Adsorption and desorptions, the first time adsorbance with 37.47mg/g
Compared to remaining to reach 37.12mg/g.Stablize well it can be proved that chelating type polyacrylonitrile hollow fiber membrane has copper ion
The film may be reused in absorbability.
Claims (9)
1. a kind of preparation method of chelating type polyacrylonitrile hollow fiber membrane, the pretreated polyacrylonitrile of sodium hydrate aqueous solution
Hollow-fibre membrane is mixed with diazo resin aqueous solution carries out first step Electrostatic Absorption, and the polyacrylonitrile for being adsorbed with diazo resin is hollow
Tunica fibrosa mixes again with disodium ethylene diamine tetra-acetic acid aqueous solution carries out second step Electrostatic Absorption, and obtained product is through washing, drying
Afterwards, processing is exposed with ultraviolet light, obtains the chelating type polyacrylonitrile hollow fiber membrane with one layer of modified layer；The tunica fibrosa
It repeats to carry out the first step successively and the Electrostatic Absorption and product of second step washes, are dry, ultraviolet photoetching processing obtains having more
The chelating type polyacrylonitrile hollow fiber membrane of layer modified layer.
2. the preparation method of the chelating type polyacrylonitrile hollow fiber membrane of claim 1, includes the following steps：
(1) pretreatment of polyacrylonitrile hollow fiber membrane：Polyacrylonitrile hollow fiber membrane is cut into segment, drying is washed with water,
It is subsequently placed in 40-60 DEG C of 0.5-2.5mol/L sodium hydrate aqueous solutions, reacts 1-5h, then take out, be washed with water, do
It is dry；
(2) Electrostatic Absorption and uv-exposure of polyacrylonitrile hollow fiber membrane：The polyacrylonitrile hollow fiber membrane that (1) obtains is put
First step Electrostatic Absorption, reaction time 5-50h, Ran Houyong are carried out in the diazo resin aqueous solution of a concentration of 0.5-2mg/mL
Water washing polyacrylonitrile hollow fiber membrane, then place it in a concentration of 1-4mg/mL disodium ethylene diamine tetra-acetic acid solutions and carry out
Two step Electrostatic Absorptions, reaction carry out 5-50 hours, polyacrylonitrile hollow fiber membrane and drying are then washed with water, after the completion of dry
It is exposed with ultraviolet lamp, obtains the polypropylene hollow fiber membrane with one layer of modified layer；
(3) LBL self-assembly of polyacrylonitrile hollow fiber membrane modified layer：The polyacrylonitrile hollow fiber membrane that (2) are obtained repeats
Step (2), obtains the modified polyacrylonitrile hollow-fibre membrane with multilayer diazo resin and EDTA coatings and completion chelating type gathers
The preparation of acrylonitrile hollow-fibre membrane；
It respectively operates in the step (2) and is carried out under the conditions of being protected from light before uv-exposure；
Water in each step is distilled water or deionized water.
3. the preparation method of chelating type polyacrylonitrile hollow fiber membrane according to claim 2, the repetition step in the step (3)
Suddenly (2) operate, and the number repeated is 1 time -- and 5 times.
It is used in the step (2) 4. the preparation method of chelating type polyacrylonitrile hollow fiber membrane according to claim 2
A concentration of 1-2mol/L of sodium hydrate aqueous solution, reaction time are 2-4 hours.
5. the preparation method of chelating type polyacrylonitrile hollow fiber membrane according to claim 2, diazonium in the step (2)
The concentration of resin aqueous solution is 0.8-1.5mg/mL, a concentration of 1.2-1.8mg/ of disodium ethylene diamine tetra-acetic acid aqueous solution
ML is for the first time 20-30 hours with the time used in second of Electrostatic Absorption.
6. the preparation method of chelating type acrylonitrile hollow-fibre membrane according to claim 2, the first step is quiet in the step (2)
The operation temperature of Electro Sorb and second step Electrostatic Absorption is room temperature.
7. the preparation method of chelating type acrylonitrile hollow-fibre membrane according to claim 2, the step (2) is middle to complete absorption
The time of tunica fibrosa ultraviolet lamp exposure afterwards is 1-6h.
8. the preparation method of chelating type acrylonitrile hollow-fibre membrane according to claim 7, the step (2) is middle to complete absorption
Tunica fibrosa afterwards is 2-4h with the time that ultraviolet lamp exposes.
9. the weight in waste water is adsorbed of the chelating type polyacrylonitrile film prepared by the preparation method according to claim 1-8 out
The application of metal ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710824401.2A CN108159902B (en) | 2017-09-13 | 2017-09-13 | Preparation method of chelate polyacrylonitrile hollow fiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710824401.2A CN108159902B (en) | 2017-09-13 | 2017-09-13 | Preparation method of chelate polyacrylonitrile hollow fiber membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108159902A true CN108159902A (en) | 2018-06-15 |
| CN108159902B CN108159902B (en) | 2020-11-27 |
Family
ID=62526725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710824401.2A Active CN108159902B (en) | 2017-09-13 | 2017-09-13 | Preparation method of chelate polyacrylonitrile hollow fiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108159902B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114904403A (en) * | 2022-06-28 | 2022-08-16 | 江苏久膜高科技股份有限公司 | Preparation method of chelating membrane for purifying wet electronic chemicals |
| CN115975238A (en) * | 2023-02-10 | 2023-04-18 | 中南大学湘雅医院 | Ethylene diamine tetraacetic acid modified membrane type artificial organ material and preparation method thereof |
| CN116371451A (en) * | 2023-04-14 | 2023-07-04 | 西安交通大学 | Cerium doped nickel-based catalyst suitable for methane dry reforming and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103357277A (en) * | 2013-07-24 | 2013-10-23 | 浙江师范大学 | Ultrafiltration membrane with heavy metal ion adsorption function, and preparation method thereof |
| CN103463999A (en) * | 2013-09-06 | 2013-12-25 | 烟台绿水赋膜材料有限公司 | Preparation method of novel ultrathin salt-cutting separation membrane |
| CN104190264A (en) * | 2014-09-24 | 2014-12-10 | 青岛大学 | Preparation method for hollow fiber ultrafiltration membrane with chelation function |
| US8925736B2 (en) * | 2011-09-12 | 2015-01-06 | University Of Houston | Nanocomposite polymer-carbon based nanomaterial filters for the simultaneous removal of bacteria and heavy metals |
| CN104562666A (en) * | 2014-12-18 | 2015-04-29 | 昆明理工大学 | Surface modification method of polypropylene non-woven fabric |
| CN104549178A (en) * | 2014-12-18 | 2015-04-29 | 昆明理工大学 | Adsorbing material for azide method coupling gelatin and preparation method of adsorbing material |
| CN106902655A (en) * | 2017-03-20 | 2017-06-30 | 浙江工业大学 | A kind of preparation method and application of mercapto-functionalized polymer separation film |
-
2017
- 2017-09-13 CN CN201710824401.2A patent/CN108159902B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8925736B2 (en) * | 2011-09-12 | 2015-01-06 | University Of Houston | Nanocomposite polymer-carbon based nanomaterial filters for the simultaneous removal of bacteria and heavy metals |
| CN103357277A (en) * | 2013-07-24 | 2013-10-23 | 浙江师范大学 | Ultrafiltration membrane with heavy metal ion adsorption function, and preparation method thereof |
| CN103463999A (en) * | 2013-09-06 | 2013-12-25 | 烟台绿水赋膜材料有限公司 | Preparation method of novel ultrathin salt-cutting separation membrane |
| CN104190264A (en) * | 2014-09-24 | 2014-12-10 | 青岛大学 | Preparation method for hollow fiber ultrafiltration membrane with chelation function |
| CN104562666A (en) * | 2014-12-18 | 2015-04-29 | 昆明理工大学 | Surface modification method of polypropylene non-woven fabric |
| CN104549178A (en) * | 2014-12-18 | 2015-04-29 | 昆明理工大学 | Adsorbing material for azide method coupling gelatin and preparation method of adsorbing material |
| CN106902655A (en) * | 2017-03-20 | 2017-06-30 | 浙江工业大学 | A kind of preparation method and application of mercapto-functionalized polymer separation film |
Non-Patent Citations (2)
| Title |
|---|
| 李甫等: "改性聚丙烯腈纤维与金属离子的配位反应及其应用进展", 《纺织学报》 * |
| 袁玉兵等: "吸附混合重金属离子的聚电解质层复合纤维膜", 《印染》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114904403A (en) * | 2022-06-28 | 2022-08-16 | 江苏久膜高科技股份有限公司 | Preparation method of chelating membrane for purifying wet electronic chemicals |
| CN114904403B (en) * | 2022-06-28 | 2023-08-04 | 江苏久膜高科技股份有限公司 | Preparation method of chelating membrane for wet electronic chemical purification |
| CN115975238A (en) * | 2023-02-10 | 2023-04-18 | 中南大学湘雅医院 | Ethylene diamine tetraacetic acid modified membrane type artificial organ material and preparation method thereof |
| CN116371451A (en) * | 2023-04-14 | 2023-07-04 | 西安交通大学 | Cerium doped nickel-based catalyst suitable for methane dry reforming and preparation method thereof |
| CN116371451B (en) * | 2023-04-14 | 2024-05-17 | 西安交通大学 | Cerium doped nickel-based catalyst suitable for methane dry reforming and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108159902B (en) | 2020-11-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Feng et al. | Electrospun AOPAN/RC blend nanofiber membrane for efficient removal of heavy metal ions from water | |
| Usman et al. | Simultaneous adsorption of heavy metals and organic dyes by β-Cyclodextrin-Chitosan based cross-linked adsorbent | |
| Maatar et al. | Poly (methacylic acid-co-maleic acid) grafted nanofibrillated cellulose as a reusable novel heavy metal ions adsorbent | |
| Hanif et al. | Polypyrrole multilayer-laminated cellulose for large-scale repeatable mercury ion removal | |
| Zhao et al. | α-ketoglutaric acid modified chitosan/polyacrylamide semi-interpenetrating polymer network hydrogel for removal of heavy metal ions | |
| CN108339410B (en) | Polyion liquid modified three-dimensional structure net film and preparation method and application thereof | |
| Wang et al. | Fabrication of graphene oxide/polydopamine adsorptive membrane by stepwise in-situ growth for removal of rhodamine B from water | |
| Zhang et al. | High-performance TFNC membrane with adsorption assisted for removal of Pb (II) and other contaminants | |
| CN108159902A (en) | A kind of preparation method of chelating type polyacrylonitrile hollow fiber membrane | |
| Niu et al. | Fast removal of copper ions from aqueous solution using an eco–friendly fibrous adsorbent | |
| Xing et al. | MOFs self-assembled molecularly imprinted membranes with photoinduced regeneration ability for long-lasting selective separation | |
| CN110115984B (en) | Magnetic cyclodextrin-based cross-linked polymer adsorption material and preparation method thereof | |
| CN110115982B (en) | Magnetic cyclodextrin-based chelating and decolorizing adsorption material and preparation method thereof | |
| Maru et al. | Dye contaminated wastewater treatment through metal–organic framework (MOF) based materials | |
| CN110918067B (en) | Grafted cellulose adsorbent and preparation method and application thereof | |
| CN115155322B (en) | Polyamide reverse osmosis membrane online repairing agent and preparation and repairing methods thereof | |
| CN105797596B (en) | A kind of preparation method of filter membrane for Water warfare | |
| CN103161064B (en) | A kind of preparation method of electrostatic spinning modified membrane sorbing material and application thereof | |
| Chen et al. | Functionalization of biodegradable PLA nonwoven fabrics as super-wetting membranes for simultaneous efficient dye and oil/water separation | |
| Yao et al. | Phosphoric acid functionalized superhydrophilic and underwater superoleophobic UiO-66/polyester fabric composite membrane for efficient oil/water separation and Gd (III) recovery | |
| CN112619622A (en) | Nano composite fiber membrane capable of efficiently removing ionic dye and heavy metal ions in water, and preparation method and application thereof | |
| Wen et al. | Adsorption of congo red from solution by iron doped PVA-chitosan composite film | |
| Wang et al. | Recyclable adsorbent aerogels by in-situ growth of ZIF-8 on aramid nanofibers/poly (vinyl alcohol) for multiple water pollutants | |
| Zhu et al. | Polymer brush-grafted cotton fiber for the efficient removal of aromatic halogenated disinfection by-products in drinking water | |
| Gao et al. | Amidoxime functionalized PVDF-based chelating membranes enable synchronous elimination of heavy metals and organic contaminants from wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |