CN103223299B - Macromolecular negative-charge ultrafiltration membrane and preparation method thereof - Google Patents
Macromolecular negative-charge ultrafiltration membrane and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a macromolecular negative-charge ultrafiltration membrane and a preparation method thereof, and relates to the technical field of membrane separation. The preparation method comprises the following steps of: preparing a nanowire dispersion solution; preparing a negative-charge macromolecular material dilute solution; filtering 2-20mg/mL of nanowire dispersion solution to a macroporous support layer to form a nanowire template layer; filtering 0.5-5mg/mL of 0.05-10mg/mL negative-charge macromolecular dilute solution through the nanowire template layer; enabling negative-charge macromolecules to be self-assembled onto the outer surface of the nanowire template layer to form a self-assembly layer; and dissolving/removing a nanowire template to form a negative-charge mesoporous separation layer, thereby finally obtaining the macromolecular negative-charge ultrafiltration membrane. According to the prepared macromolecular negative-charge ultrafiltration membrane, the pore size is smaller than 10nm and the thickness of the separation layer is adjustable within a range of 50-500nm; and the prepared membrane has the characteristics of high permeation flux, high separation efficiency, good pollution resistance, and the like.
Description
Technical field
The present invention relates to technical field of membrane separation, be specifically related to a kind of Macromolecular negative-charge ultrafiltration membrane and preparation method thereof.
Background technology
Membrane technology, as a kind of green, energy-conservation new industry technology, is the important technology solving resource-type lack of water and water quality type water shortage problem, has become the mainstream technology of water treatment.Ultrafiltration is the main force of embrane method sewage disposal, and simultaneously it is also widely used in the field such as food industry and life science, and along with the whole world giving more sustained attention healthy and living environment, its importance is more and more outstanding.The core of ultra-filtration process be flux high, retain excellent in efficiency, pollute little, that pore diameter range is 1 ~ 100nm high performance ultra filtration film.But the usual pore-size distribution of commodity milipore filter is wide, separating layer thickness is large, the deficiency such as cause that the rejection of film is low, the large and flux of trapped substance loss is little in film, the film that aperture is less than 10nm is particularly serious.As can be seen here, the research and development of high performance ultra filtration film have great practical value, can be the industry developments such as water treatment, food industry and life science and provide new power and technical support.
Polymeric membrane is the chief component of commodity milipore filter, is usually prepared by inversion of phases process or coating method, correspondingly obtains integrated anisotropic membrane or composite membrane.Integration anisotropic membrane obtains through same material one-shot forming, is made up of, there is the deficiency that pore-size distribution is wide, filtration resistance is large separating layer (cortex), transition zone and supporting layer.Composite membrane obtains through inversion of phases process by apply casting film liquid layer on supporting layer after again, be made up of separating layer and supporting layer, pore-size distribution is wide, filtration resistance is little, but in coating process easily there is hole and ooze phenomenon and cause effective separating layer thickness to increase in casting solution, can not give full play to the high-throughout advantage of composite membrane.At present, maximum challenge is to prepare that flux is high, aperture is less than 10nm and the high performance polymer milipore filter of narrowly distributing.According to Carman-Kozeny filtration theory, the flux of milipore filter and the thick layer inverse ratio of effective separating layer, namely separating layer is thinner, then permeation flux is larger.Therefore, ultrathin be high-throughput isolation film direct, prepare one of approach efficiently.
Charged milipore filter has become the large class that polymeric membrane receives much concern.Different from neutral milipore filter, these charged membrane surfaces externally and internallies also exist the milipore filter of fixed charge, except physics screening, also there is Donnan effect, there is special absorption and repel separating property; Can reduce fouling membrane by means of charged repulsive interaction, the gel layer that membrane interface place is formed becomes loose, can ensure the long-time stability of film.In recent years, the research of macromolecule charged membrane aspect concentrates on synthesis and the performance study thereof of charged macromolecular material, normally first make it connect suitable anionic group (such as carboxyl, sulfonic group) or cation group (such as quaternary ammonium group) to polymer base material graft modification, then prepare the charged milipore filter of macromolecule through inversion of phases or coating process.As previously mentioned, phase inversion and coating process prepare ultra-thin parting absciss layer, flux is large, aperture is less than 10nm ultrafiltration is still a challenge.Although the charged composite membrane of film-type macromolecule not only has permeable good, antipollution and the selective penetrated property advantage of charged membrane, and there is ultra-high throughput, feature that resistance is little, also there is no simple, general film-forming method at present.Recently, the people such as Park (M.H.Park, C.Subramani, S.Rana, V.M.Rotello, Adv.Mater.2012,24,5862 – 5866) to be prepared in glass fibre microfiltration membranes by nano particle and dendritic macromole self assembly there is ultra-thin charged separating layer, form the charged composite membrane of film-type with chemo-selective.This film can allow Small molecular quickly through, and the diffusion of the charged molecule of selective prevention, has been successfully applied to dialysis isolated protein.
As from the foregoing, the charged polymer ultrafiltration membrane of ultrathin not only has permeable good, antipollution and the selective penetrated property advantage of charged membrane, also has ultra-high throughput, feature that resistance is little.But, but also there is no the preparation method of the ultra-thin charged polymer ultrafiltration membrane that technique is simple, operability is good at present.
Therefore, how be less than within the scope of 10nm retaining aperture, the preparation method of development technology is simple, operability the is good ultra-thin polymer ultrafiltration membrane of high flux, particularly charged polymer ultrafiltration membrane, has the important science meaning and good industrial application value.
Summary of the invention
The object of the invention is to for the above-mentioned defect existing for prior art, provide a kind of Macromolecular negative-charge ultrafiltration membrane and preparation method thereof, this method is applicable to the macromolecule of electronegative group on most of strand.Obtained Macromolecular negative-charge ultrafiltration membrane aperture is less than 10nm, and separating layer thickness is adjustable within the scope of 50 ~ 500nm, has the features such as permeation flux is large, separative efficiency is high, resistance tocrocking is good.
The present invention includes following steps:
1) nano wire dispersion soln is prepared;
2) bear electricity macromolecular material weak solution is prepared;
3) 2 ~ 20mg/mL nano wire dispersion soln is filtered on macropore supporting layer, form nano wire template layer;
4) refiltering 0.5 ~ 5mg/mL concentration is that 0.05 ~ 10mg/mL bear electricity Dilute Polymer Solutions is by nano wire template layer, bear electricity macromolecule will be self-assembled to nano wire template layer outer surface by electrostatic interaction and form Iy self-assembled layer, nano wire template is dissolved/is removed and forms the mesoporous separating layer of bear electricity, finally obtains Macromolecular negative-charge ultrafiltration membrane.
In step 1), described nano wire can adopt surface band positive electricity and easily by the nano wire dissolved, described nano wire can be selected from the one in Fe nanowire, cobalt nanowire, copper nano-wire, nano cuprous oxide wire, zinc oxide nanowire, nano silver wire, Kocide SD nano wire, cadmium hydroxide nanowires etc.
In step 2) in, described bear electricity macromolecular material can adopt the bear electricity macromolecular material of electronegative group, and the concentration of described bear electricity macromolecular material weak solution can be 0.05 ~ 10mg/mL; The optional one in polyacrylic acid, polymethylacrylic acid, polystyrolsulfon acid, polyvinyl sulfonic acid, polyvinyl, sulfonated polyether sulfone, sulfonated polyether ketone etc. of described bear electricity macromolecular material.
In step 3), the thickness of described nano wire template layer can be 50 ~ 500nm; Described macropore supporting layer can adopt porous membrane, the optional one in poly tetrafluoroethylene, polycarbonate membrane, cellulose acetate element film, pellumina etc. of described macropore supporting layer; Described porous membrane can adopt the one in Flat Membrane, hollow-fibre membrane, tubular membrane etc.
In step 4), the thickness of described Iy self-assembled layer can be 0 ~ 5nm, and the time of self assembly can be 10 ~ 60min; Described Macromolecular negative-charge ultrafiltration membrane is made up of macropore supporting layer and mesoporous separating layer, and interlayer pore structure is suddenlyd change, and the thickness of mesoporous separating layer can be 50 ~ 500nm, and retain aperture and be less than 10nm, pure water flux is greater than 1000Lm
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The Macromolecular negative-charge ultrafiltration membrane that the present invention obtains can be applicable to multiple fields such as the separation of products of the industries such as wastewater treatment, food, medicine, concentrated, purifying.
The Macromolecular negative-charge ultrafiltration membrane that the present invention develops has that separative efficiency is high, separating layer thickness is adjustable, antipollution, retain that aperture is less than 10nm, pure water flux is greater than 1000Lm
-2h
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-1etc. feature, its preparation method technique is simple, and operability is good, the macromolecule that is applicable to electronegative group on strand.
The present invention is applicable to the bear electricity macromolecule of electronegative group, obtains the controlled Macromolecular negative-charge ultrafiltration membrane of performance by changing the conditions such as bear electricity high molecular kind, solution concentration, built-up time.Preparation method is simple to operate, and the film of preparation has that high flux, resistance are little, the feature such as antipollution, selective penetrated property, and flux, much larger than current commercialization NF membrane, is a kind of ultrafiltration membrane preparation method with applications well prospect.
Accompanying drawing explanation
Fig. 1 is the structural representation prepared nano wire template layer, Iy self-assembled layer in the embodiment of the present invention and dissolve nano wire.
Fig. 2 is that in the embodiment of the present invention, made sulfonation degree is the TEM photo on the sulfonated polyether sulfone Iy self-assembled layer surface of 0.83.In fig. 2, scale is 50nm.
Fig. 3 is that in the embodiment of the present invention, made sulfonation degree is the SEM photo on the sulfonated polyether sulfone Iy self-assembled layer surface of 0.83.In figure 3, scale is 100nm.
Fig. 4 is that in the embodiment of the present invention, made nano wire template layer self assembly sulfonation degree is the SEM photo of section after the sulfonated polyether sulfone of 0.83.In the diagram, scale is 100nm.
Fig. 5 to be sulfonation degree made in the embodiment of the present invention be 0.83 sulfonated polyether sulfone bear electro ultrafiltration film surface SEM photo.In Figure 5, scale is 500nm.
Fig. 6 to be sulfonation degree made in the embodiment of the present invention be 0.83 sulfonated polyether sulfone bear electro ultrafiltration film section SEM photo.In figure 6, scale is 100nm.
Fig. 7 be in the embodiment of the present invention 5nm golden nanometer particle sulfonation degree be 0.83 sulfonated polyether sulfone bear electro ultrafiltration membrane filtration before and after ultraviolet-ray visible absorbing curve.In the figure 7, abscissa is wavelength (nm), and ordinate is absorption value; Curve a is concentrate, and curve b is material liquid, curve c permeate.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated, but it does not limit the scope of the invention.
Explanation one is retained aperture for being less than 5nm, pure water flux higher than 2000Lm by following examples
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-1sulfonated polyether sulfone bear electro ultrafiltration film and preparation method thereof.
By 4mM copper nitrate solution and the mixing of 1.2mM ethanolamine solutions equal-volume, leave standstill 5 ~ 10 days and obtain Kocide SD nano wire monodisperse liquor afterwards.This nanowire surface is with a large amount of positive charge, and diameter is about 2.5nm, and average length is 4 μm.Meanwhile, to take the concentrated sulfuric acid as sulfonating agent carry out sulfonation modifying to polyether sulfone obtains and prepares sulfonated polyether sulfone, obtains the sulfonated polyether sulfone of sulfonation degree in 0.2 ~ 0.9 scope by controlling sulfonation time.The sulfonated polyether sulfone obtained is dissolved in 1-METHYLPYRROLIDONE, is mixed with the sulfonated polyether sulfone weak solution of 0.05mg/mL.
Sulfonated polyether sulfone bear electro ultrafiltration film dissolves preparation through the preparation of nano wire template layer, electrostatic self-assembled and nano wire successively, as shown in Figure 1.Use the glass-film filter that diameter is 25mm, in polytetrafluoroethylene (PTFE) microfiltration membranes, form nano wire template layer by vacuum filtration 10ml Kocide SD nanowire solution; And then filter the sulfonated polyether sulfone weak solution of 2ml0.05mg/mL by nano wire template layer, the self assembly time is 30min, and bear electricity sulfonated polyether sulfone strand will be self-assembled to template layer surfaces externally and internally by electrostatic interaction and form certain thickness Iy self-assembled layer; Finally filter the mesoporous separating layer of hydrochloric acid weak solution dissolved hydrogen cupric oxide nano line template formation sulfonated polyether sulfone that 5ml pH is 3.Sulfonation degree be 0.83 sulfonated polyether sulfone Kocide SD nanowire surface formed thickness be the Iy self-assembled layer of 1 ~ 5nm, by TEM confirm (Fig. 2).It is SEM photo after the self assembly of sulfonated polyether sulfone on nano wire template layer of 0.83 that Fig. 3 shows sulfonation degree, so nano wire is all sulfonated polyether sulfone Iy self-assembled layer parcel.Meanwhile, observe through SEM, the thickness after the self assembly of nano wire template layer is about 100nm(Fig. 4).
High-performance sulfonated polyether sulfone bear electro ultrafiltration film is made up of polytetrafluoroethylene (PTFE) microfiltration membranes and the mesoporous separating layer of sulfonated polyether sulfone, and the former is supporting layer, the latter is cortex.Fig. 5 and 6 display sulfonation degree is surface and the section SEM photo of the sulfonated polyether sulfone bear electro ultrafiltration film of 0.83, and this film surfacing, skin thickness are about 80nm, and pore structure sudden change between supporting layer and cortex.
Under 80kPa pressure reduction, use glass-film filter to determine pure water flux and the cutoff performance of sulfonated polyether sulfone bear electro ultrafiltration film, cutoff performance characterizes with the 5nm solution of gold nanoparticles of 20mg/mL and cytochrome c solution.Table 1 lists the separating property of the sulfonated polyether sulfone bear electro ultrafiltration film of different sulfonation degree.
The different sulfonation degree of table 1 is on the impact of SPEK-C charged membrane performance
As shown in Table 1, along with sulfonation degree increases, pure water flux reduces, and increases the rejection of 5nm golden nanometer particle and cromoci.Fig. 7 to be sulfonation degree be 0.83 sulfonated polyether sulfone 5nm golden nanometer particle is filtered before and after ultraviolet-ray visible absorbing curve, this film up to 93.6%, and film adsorbs little to the rejection of 5nm gold.
Claims (10)
1. the preparation method of Macromolecular negative-charge ultrafiltration membrane, is characterized in that comprising the following steps:
1) nano wire dispersion soln is prepared;
2) bear electricity macromolecular material weak solution is prepared;
3) 2 ~ 20mg/mL nano wire dispersion soln is filtered on macropore supporting layer, form nano wire template layer;
4) refiltering 0.5 ~ 5mL concentration is that 0.05 ~ 10mg/mL bear electricity Dilute Polymer Solutions is by nano wire template layer, bear electricity macromolecule will be self-assembled to nano wire template layer outer surface by electrostatic interaction and form Iy self-assembled layer, nano wire template is dissolved/is removed and forms the mesoporous separating layer of bear electricity, finally obtains Macromolecular negative-charge ultrafiltration membrane.
2. the preparation method of Macromolecular negative-charge ultrafiltration membrane as claimed in claim 1, is characterized in that in step 1) in, described nano wire adopts surface band positive electricity and easily by the nano wire dissolved.
3. the preparation method of Macromolecular negative-charge ultrafiltration membrane as claimed in claim 1, it is characterized in that in step 1) in, the one in described nano wire chosen from Fe nano wire, cobalt nanowire, copper nano-wire, nano cuprous oxide wire, zinc oxide nanowire, nano silver wire, Kocide SD nano wire, cadmium hydroxide nanowires.
4. the preparation method of Macromolecular negative-charge ultrafiltration membrane as claimed in claim 1, is characterized in that in step 2) in, described bear electricity macromolecular material adopts the bear electricity macromolecular material of electronegative group.
5. the preparation method of Macromolecular negative-charge ultrafiltration membrane as claimed in claim 1, it is characterized in that in step 2) in, described bear electricity macromolecular material is selected from the one in polyacrylic acid, polymethylacrylic acid, polystyrolsulfon acid, polyvinyl sulfonic acid, polyvinyl, sulfonated polyether sulfone, sulfonated polyether ketone.
6. the preparation method of Macromolecular negative-charge ultrafiltration membrane as claimed in claim 1, is characterized in that in step 2) in, the concentration of described bear electricity macromolecular material weak solution is 0.05 ~ 10mg/mL.
7. the preparation method of Macromolecular negative-charge ultrafiltration membrane as claimed in claim 1, is characterized in that in step 3) in, the thickness of described nano wire template layer is 50 ~ 500nm.
8. the preparation method of Macromolecular negative-charge ultrafiltration membrane as claimed in claim 1, it is characterized in that in step 3) in, described macropore supporting layer adopts porous membrane, and described macropore supporting layer is selected from the one in poly tetrafluoroethylene, polycarbonate membrane, cellulose acetate element film, pellumina; Described porous membrane adopts the one in Flat Membrane, hollow-fibre membrane, tubular membrane.
9. the preparation method of Macromolecular negative-charge ultrafiltration membrane as claimed in claim 1, is characterized in that in step 4) in, the thickness of described Iy self-assembled layer is 1 ~ 5nm, and the time of self assembly is 10 ~ 60min.
10. the preparation method of Macromolecular negative-charge ultrafiltration membrane as claimed in claim 1, it is characterized in that in step 4) in, described Macromolecular negative-charge ultrafiltration membrane is made up of macropore supporting layer and mesoporous separating layer, interlayer pore structure is suddenlyd change, the thickness of mesoporous separating layer is 50 ~ 500nm, retain aperture and be less than 10nm, pure water flux is greater than 1000Lm
-2h
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