A kind of heavy metal ion adsorbed type PS hollow fiber ultrafiltration membrane and preparation method thereof
Technical field
The present invention relates to technical field of membrane, particularly relate to a kind of heavy metal ion adsorbed type PS hollow fiber ultrafiltration membrane and
Its preparation method.
Background technology
Along with metallurgical industry and the development of chemical industry, produce during electroplate liquid and metal smelt etc. contains
The contaminated wastewater of the heavy metal ion such as lead, copper, chromium, mercury is on the rise, the health of relation people.At present, heavy metal pollution is
Become serious environmental problem, the problem even rising to society and ecological needed badly the solution of harmonious development.In recent decades,
Membrane technology quickly grows, and has been widely used in the fields such as sewage disposal, desalinization, health care and energy-conserving and environment-protective, and film produces
Industry oneself become independent new high-tech industry.Compared with traditional isolation technics, the separative efficiency height of membrane technology, separation process are relatively
Simply, energy consumption is low and environmental protection, is more suitable for the needs of modern industry.The research of film, development and utilization and energy-conserving and environment-protective, water source
Develop and the process of sewage is closely connected, at energy scarcity, ecological environmental pollution seriously, especially water with serious pollution the present
My god, film and membrane technology are increasingly by favor and the concern of countries in the world researcher.
Chemical stability that polysulfones PS has had, resistance to water, heat resistance, dimensional stability and preferably film forming and machine
Tool intensity, has obtained widely should at aspects such as micro-filtration, counter-infiltration, ultrafiltration, electrodialysis, gas separation, bioengineering and medical treatment
With.The fields such as the hollow fiber ultrafiltration membrane made with polysulfones PS is widely used to concentrate, separates, purifies, refines, recovery.Greatly
Quantity research shows, relative to reverse osmosis membrane and other kinds of film, hollow fiber ultrafiltration membrane has prominent advantage and feature, main
Showing as without supporter, it is big that membrane module can make the loading density in arbitrary size and shape, and membrane module, unit volume
Membrane area is big, flux big, can effectively remove the impurity such as water-borne glue body, suspended particulates, bacterium, iron rust, silt.This makes equipment
Miniaturization, simplifies the structure, and therefore extensively should multi-field obtaining such as biotechnology, gas separation, large-scale industry and medicine
With.But, in the prior art, the function of ultrafiltration membrane technique be based primarily upon physical mechanical screening, and cannot go removing heavy metals from
Son, is applied to water when processing, to be often aided with other multiple water-purifying process, such as absorption, ion exchange, electrodialysis etc., the most right
Equipment investment, occupation of land space aspect are required to higher, and implementation result is undesirable.An a kind of huge sum of money as disclosed in CN102527261A
Belonging to ion type PVDF hollow-fibre membrane, wherein contain attapulgite modified, PVDF and attapulgite modified mass ratio are 1
: 0.01~1: 0.1, this technical scheme is disadvantageous in that, the selectable range of raw material is little, and heavy metal ion is especially
Copper, lead, nickel, chromium ion adsorption capacity the strongest.
Visible, current domestic lack that a kind of hollow fiber ultrafiltration membrane heavy metal ionic adsorption power ability is strong and preparation method
Simple technical scheme.
Summary of the invention
It is an object of the invention to provide a kind of heavy metal ion adsorbed type PS hollow fiber ultrafiltration membrane and preparation method thereof,
Solve PS hollow fiber ultrafiltration membrane heavy metal ion adsorption capacity of the prior art not strong, complex process when water processes
And the problem that effect is undesirable.
The invention provides following technical scheme:
A kind of heavy metal ion adsorbed type PS hollow fiber ultrafiltration membrane, is with dry-wet spinning method after preparation spinning solution
Preparation hollow fiber ultrafiltration membrane, described spinning solution mass percent formula is:
Polysulfones PS10-25%;
Additive 1-20%;
Solvent 60-80%;
Pore-foaming agent 1-20%;
Described additive is ion-exchange type resin, shitosan, sepiolite, mesoporous silicon oxide, molecular sieve, concave convex rod
Stone, bentonite any one or etc. any two of quality;
Described solvent is 1-METHYLPYRROLIDONE (NMP), N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide
(DMAC), dimethyl sulfoxide (DMSO) (DMSO) any one or etc. any two of quality;
Described pore-foaming agent is arbitrary in PEG1000, PEG2000, PEG6000, PEG10000, PVP K15, PVPK30
Kind.
The preparation method of a kind of heavy metal ion adsorbed type PS hollow fiber ultrafiltration membrane, comprises the following steps:
(1) preparation of spinning solution: polysulfones PS, additive, solvent and pore-foaming agent are poured in container by percent mass proportioning,
Then heat 3h at 50-80 DEG C, be sufficiently stirred for spinning solution homodisperse with ultrasonically treated acquisition;
(2) spinning:
Being poured into by spinning solution in dry-wet machine reactor, temperature controls at 20-40 DEG C, vacuum defoamation 60min;
Opening outlet valve, be passed through nitrogen and be forced into 0.2MPa in still, then open spinning pump, rotating speed controls at 15-
40r/min, core liquid pump rotating speed controls at 10-20r/min;
Starting spinning, the doughnut of spinning head extrusion is wound on wind-up roll after the coagulating bath of 20 DEG C, rolling speed
Degree controls at 10-30r/min;
(4) spinning post processing:
After spinning terminates, from spiral filament forming machine, take off hollow fiber ultrafiltration membrane, be subsequently placed in reverse osmosis water immersion 2 days, it
After in the glycerine water solution that mass concentration is 50% soak 2 days, last drying at room temperature obtains heavy metal ion adsorbed type PS hollow
Fiber ultrafiltration membrane.
Described core liquid be the aqueous solution, the NMP aqueous solution, the DMF aqueous solution, the DMAC aqueous solution, glycerine water solution any one.
Described coagulation bath be the aqueous solution, the NMP aqueous solution, the DMF aqueous solution, the DMAC aqueous solution, glycerine water solution arbitrary
Kind.
The present invention heavy metal ion adsorbed type hollow-fibre membrane is for separating the application of the heavy metal ion removed in sewage.
Applicant finds through long term test research, and the separating property of polysulfones PS hollow fiber ultrafiltration membrane is good, ion-exchange type
The absorption property of resin, shitosan, sepiolite, mesoporous silicon oxide, molecular sieve, attapulgite and Bentonite
The strongest.But, by ion-exchange type resin, shitosan, sepiolite, mesoporous silicon oxide, molecular sieve, attapulgite and swollen
The difficulty that profit soil applies to ion type polysulfones PS hollow fiber ultrafiltration membrane system is higher, and its correlative study there is not yet report
Road.The present invention utilizes the heavy metal ion adsorbed performance that ion-exchange type resin, shitosan or inorganic mineral are superior, closes with science
The proportioning of reason joins in the spinning solution of PS hollow fiber ultrafiltration membrane, adds specific spinning process and spinning post-processing approach,
The huge sum of moneys such as copper that the heavy metal ion adsorbed type PS hollow fiber ultrafiltration membrane prepared can effectively be removed in sewage, lead, chromium
Belong to ion.
Beneficial effects of the present invention: compared with prior art, the heavy metal ion adsorbed doughnut that the present invention obtains surpasses
Filter membrane product is better than heavy metal ion adsorbed type hollow-fibre membrane of the prior art, not only has self-supporting, sets up membrane area
With the feature such as flux is big, good pressure-resistant performance, the absorption property of heavy metal ion is stronger;Its preparation technology is simple, process stabilizing,
Effect is obvious, it is easy to industrialization, and the adsorption effect of heavy metal ion is obvious.Use Hollow Fiber Ultrafiltration prepared by the present invention
Film, its pure water flux is up to 200L/m2H bar, to the rejection of PEG100000 more than 80%.Inventive film product pair
Copper, lead, nickel, the adsorption rate of chromium ion are respectively 25%, 22%, 25% and 20%.
Accompanying drawing explanation
Fig. 1 is the heavy metal ion adsorbed type PS hollow fiber ultrafiltration membrane cross section picture that the embodiment of the present invention 1 prepares;
Fig. 2 is the heavy metal ion adsorbed type PS hollow fiber ultrafiltration membrane surface picture that the embodiment of the present invention 1 prepares.
Specific embodiment mode
In order to deepen the understanding of the present invention, below by embodiment and accompanying drawing, the present invention is specifically described.Having must
Want it is pointed out here that be that the present embodiment is served only for being described further invention, it is impossible to be interpreted as the limit to scope
System, if the present invention is made some nonessential improvement and tune according to the invention described above content by the person skilled in the art in this field
Whole, still fall within scope.
Embodiment 1
Design spinning solution mass percent formula is:
Polysulfones PS 10%;
Ion exchange resin (average grain diameter 10um) 15%;
1-METHYLPYRROLIDONE 70%;
PEG1000 5%。
Preparation of spinning solution process is: is added by ion exchange resin 15% and fills in the solvent of NMP 70%, stirs point
After Saning, add PEG10005%, be heated to 50 DEG C and be incubated 3h so that it is dissolve, be finally gradually added polysulfones PS 10%, fully stir
Mix and stir the homodisperse spinning solution of ultrasonically treated acquisition.
Hollow Fiber Ultrafiltration preparation process is: poured into by spinning solution in dry-wet machine reactor, and temperature controls at 20 DEG C, very
Empty deaeration 60min.Then opening outlet valve, be passed through nitrogen and be forced into 0.2MPa in still, then open spinning pump, rotating speed controls
At 15r/min, core liquid NMP aqueous solution rotating speed controls at 10r/min, starts spinning;The doughnut of spinning head extrusion is through 20
DEG C the DMF aqueous solution after be wound on wind-up roll, rolling speed controls at 10r/min.After spinning terminates, take off from spiral filament forming machine
Hollow-fibre membrane, is subsequently placed in reverse osmosis water immersion 2 days, soaks 2 days afterwards in the glycerine water solution that mass ratio is 50%,
Last drying at room temperature obtains heavy metal ion adsorbed type PS hollow fiber ultrafiltration membrane.
Fig. 1 is the heavy metal ion adsorbed type PS hollow fiber ultrafiltration membrane cross section picture that the embodiment of the present invention 1 prepares;
Fig. 2 is the heavy metal ion adsorbed type PS hollow fiber ultrafiltration membrane surface picture that the embodiment of the present invention 1 prepares.
Embodiment 2
Design spinning solution mass percent formula is:
Polysulfones PS 25%;
Shitosan (average grain diameter 10um) 1%;
DMF 60%;
PEG2000 14%。
Preparation of spinning solution process is: added by 1% shitosan in the solvent filling 60%DMF, stirs after dispersion, adds
14%PEG2000, is heated to 60 DEG C and is incubated 3h so that it is dissolves, is finally gradually added 25% polysulfones PS, is sufficiently stirred for and ultrasonic place
Reason obtains homodisperse spinning solution.
Hollow Fiber Ultrafiltration preparation process is: poured into by spinning solution in dry-wet machine reactor, and temperature controls at 25 DEG C, very
Empty deaeration 60min.Then opening outlet valve, be passed through nitrogen and be forced into 0.2MPa in still, then open spinning pump, rotating speed controls
At 35r/min, core liquid DMF aqueous solution rotating speed controls at 15r/min, starts spinning;The doughnut of spinning head extrusion is through 20
DEG C the DMAC aqueous solution after be wound on wind-up roll, rolling speed controls at 12r/min.After spinning terminates, take from spiral filament forming machine
Lower hollow-fibre membrane, is subsequently placed in reverse osmosis water immersion 2 days, soaks 2 afterwards in the glycerine water solution that mass ratio is 50%
My god, last drying at room temperature obtains heavy metal ion adsorbed type PS hollow fiber ultrafiltration membrane.
Embodiment 3
Design spinning solution mass percent formula is:
Polysulfones PS 15%;
Sepiolite (average grain diameter 10um) 20%;
DMAC 60%;
PEG10000 5%。
Preparation of spinning solution process is: added by 20% sepiolite in the container filling 60%DMAC, stirs after dispersion, adds
Enter 15%PEG2000, be heated to 80 DEG C and be incubated 3h so that it is dissolve, be finally gradually added 15% polysulfones PS, be sufficiently stirred for ultrasonic
Process and obtain homodisperse spinning solution.
Hollow Fiber Ultrafiltration preparation process is: poured into by spinning solution in dry-wet machine reactor, and temperature controls at 35 DEG C, very
Empty deaeration 60min.Then opening outlet valve, be passed through nitrogen and be forced into 0.2MPa in still, then open spinning pump, rotating speed controls
At 30r/min, core liquid DMAC aqueous solution rotating speed controls at 20r/min, starts spinning;The doughnut of spinning head extrusion is through 20
DEG C the NMP aqueous solution after be wound on wind-up roll, rolling speed controls at 15r/min.After spinning terminates, take off from spiral filament forming machine
Hollow-fibre membrane, is subsequently placed in reverse osmosis water immersion 2 days, soaks 2 days afterwards in the glycerine water solution that mass ratio is 50%,
Last drying at room temperature obtains heavy metal ion adsorbed type PS hollow fiber ultrafiltration membrane.
Embodiment 4
Design spinning solution mass percent formula is:
Polysulfones PS 12%;
Attapulgite (average grain diameter 10um) 3%;
(DMAC:DMF=32.5:32.5) 65%;
PVPK15 20%。
Preparation of spinning solution process is: is added by 3% sepiolite and fills 65% mixed solvent (DMAC and DMF mass ratio is 1:1)
Container in, stir dispersion after, add 20%PVPK15, be heated to 70 DEG C and be incubated 3h so that it is dissolve, the most progressively add
Enter 12% polysulfones PS, be sufficiently stirred for spinning solution homodisperse with ultrasonically treated acquisition.
Hollow Fiber Ultrafiltration preparation process is: poured into by spinning solution in dry-wet machine reactor, and temperature controls at 25 DEG C, very
Empty deaeration 60min.Then opening outlet valve, be passed through nitrogen and be forced into 0.2MPa in still, then open spinning pump, rotating speed controls
At 25r/min, aqueous solution rotating speed controls at 18r/min, starts spinning;The doughnut of spinning head extrusion is through the glycerine of 20 DEG C
Being wound on after the aqueous solution on wind-up roll, rolling speed controls at 20r/min.After spinning terminates, from spiral filament forming machine, take off hollow fine
Dimension film, is subsequently placed in reverse osmosis water immersion 2 days, soaks 2 days afterwards, rear chamber in the glycerine water solution that mass ratio is 50%
Temperature is dried to obtain heavy metal ion adsorbed type PS hollow fiber ultrafiltration membrane.
Embodiment 5
Design spinning solution mass percent formula is:
Polysulfones PS 10%;
Additive package (shitosan and sepiolite) 9%
(shitosan is 1:1 with the mass ratio of sepiolite, average grain diameter 10um);
DMAC 80%;
PVPK30 1%。
Preparation of spinning solution process is: being added by 9% additive package in the container filling 80%DMAC, stir dispersion
After, add 1%PVPK30, be heated to 80 DEG C and be incubated 3h so that it is dissolve, be finally gradually added 10% polysulfones PS, be sufficiently stirred for and
The homodisperse spinning solution of ultrasonically treated acquisition.
Hollow Fiber Ultrafiltration preparation process is: poured into by spinning solution in dry-wet machine reactor, and temperature controls at 40 DEG C, very
Empty deaeration 60min.Then opening outlet valve, be passed through nitrogen and be forced into 0.2MPa in still, then open spinning pump, rotating speed controls
At 40r/min, glycerine water solution rotating speed controls at 16r/min, starts spinning;The doughnut of spinning head extrusion is through 20 DEG C
Being wound on after the aqueous solution on wind-up roll, rolling speed controls at 18r/min.After spinning terminates, from spiral filament forming machine, take off hollow fine
Dimension film, is subsequently placed in reverse osmosis water immersion 2 days, soaks 2 days afterwards, rear chamber in the glycerine water solution that mass ratio is 50%
Temperature is dried to obtain heavy metal ion adsorbed type PS hollow fiber ultrafiltration membrane.
Use heavy metal ion adsorbed type PS hollow fiber ultrafiltration membrane prepared by the embodiment of the present invention 1 be respectively used to copper, nickel,
The adsorption experiment of the heavy metal ion sewage such as lead, chromium, found that its copper, lead, nickel, the adsorption rate of chromium ion are respectively 25%,
22%, 25% and 20%, it is better than heavy metal ion adsorbed type hollow-fibre membrane of the prior art.