CN105498550A - Nonwoven cloth composite nanofiltration membrane and preparation method and application thereof - Google Patents

Nonwoven cloth composite nanofiltration membrane and preparation method and application thereof Download PDF

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Publication number
CN105498550A
CN105498550A CN201510920598.0A CN201510920598A CN105498550A CN 105498550 A CN105498550 A CN 105498550A CN 201510920598 A CN201510920598 A CN 201510920598A CN 105498550 A CN105498550 A CN 105498550A
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fibre
fiber
membrane
slurry
fibre length
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王习文
张洪锋
颜鑫
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South China University of Technology SCUT
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South China University of Technology SCUT
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    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Microbiology (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)
  • Nonwoven Fabrics (AREA)

Abstract

The invention belongs to the technical field of membrane separating materials, and discloses a nonwoven cloth composite nanofiltration membrane and a preparation method and an application thereof. The composite nanofiltration membrane is prepared by compounding a nonwoven cloth support layer with average hole diameter of 5-20mum and quantity of 5-30g/m2, a nonwoven cloth transition layer with average hole diameter of 100nm-3mum and quantity of 5-20g/m2, and a nonwoven cloth separating layer with average hole diameter of 1-50nm and quantity of 2-15g/m2. The composite nanofiltration membrane has the advantages that by selecting and combining the raw fibers of the three layers, and adopting the one-time overlapping, copying and forming, the separating layer has good separating property; the retention rate of nanocellulose in the separating layer is improved by the transition layer; the support layer has better pressure-resistant property and physical-chemical stability, the higher flux and operational stability can be guaranteed, and the application prospect in the water treatment field and membrane biological reactors is good.

Description

A kind of non-woven fabric compounded NF membrane and preparation method thereof and application
Technical field
The invention belongs to separation membrane technical field, be specifically related to a kind of non-woven fabric compounded NF membrane and preparation method thereof and application.
Background technology
Membrane separation technique is as the optimization technique of 21 century water treatment, with conventional water treatment Technical comparing, have that energy consumption is low, separative efficiency is high, technique is simple, without the need to adding additive, not affecting the advantages such as health, be therefore widely used in fields such as oiliness sewage treatment, fiber industry wastewater treatment, metal electrophoresis lacquering process liquid waste processing, pulping wastewater treatment, membrane bioreactors.
Membrane separating process mainly contains micro-filtration (MF), ultrafiltration (UF), nanofiltration (NF) and counter-infiltration (RO).NF membrane is the pressure-actuated Novel separation film of one between reverse osmosis membrane and milipore filter, it can retain organic molecule and most of monovalent inorganic salt be passed through, the separation of different valence state ion can be realized, the very little same amino acid of relative molecular mass difference and same proteinoid can be separated, and high relative molecular weight can be realized be separated with the organic of low relative molecular weight, due to cut-off region (the cutoff scope 200-1000Da of its acumen, and its aperture is in nanoscale), in petrochemical industry, biochemical and medical, food, papermaking, be used widely in the fields such as textile printing and dyeing and water treatment procedure.The eighties in 20th century, U.S.'s FilmteC companies develops the NF membrane of the models such as NF-40, NF-50, NF-70.At present, Nanofiltration-membrane technique is separation advanced in the world and filtering technique, and due to extensive market, the numerous and confused organizational strength in countries in the world is put in the exploitation of Nanofiltration-membrane technique.The kind of NF membrane constantly increases, and performance improves constantly.Its development trend is exploitation heat-resisting, acid and alkali-resistance, resistance to oxidation, resistance to free chlorine, high water flux, high rejection, resistant to pollution high-performance NF membrane.Membrane material has cellulose acetate, fragrance poly-phthalein amine, sulfonated polyether alum etc.From the engineering of water treatment example of nanofiltration successful operation at home and abroad, its separating property is good, and stable effluent quality is reliable, and energy consumption low, there is good Technical Economy and operating cost.
Although the domestic development of NF membrane is in recent years very fast, successively researched and developed multiple NF membrane, major part is all also in the laboratory research development phase, not yet commercialization.The water flux of film, chemical stability and resistance tocrocking are all poor.Wherein crucial be also the selection of membrane material and preparation technology immature.
Summary of the invention
In order to solve the shortcoming and defect part of above prior art, primary and foremost purpose of the present invention is to provide a kind of non-woven fabric compounded NF membrane.
Another object of the present invention is to the preparation method that above-mentioned non-woven fabric compounded NF membrane is provided.
Another object of the present invention is to provide above-mentioned non-woven fabric compounded NF membrane in water treatment and as the application of membrane material in membrane bioreactor.
The object of the invention is achieved through the following technical solutions:
A kind of non-woven fabric compounded NF membrane, being 5 ~ 20 μm by average pore size, is quantitatively 5 ~ 30g/m 2non-woven fabrics supporting layer, average pore size is 100nm ~ 3 μm, is quantitatively 5 ~ 20g/m 2non-woven fabrics transition zone and average pore size be 1 ~ 50nm, be quantitatively 2 ~ 15g/m 2non-woven fabrics separating layer be prepared from through compound.
The material of preparing of described supporting layer is preferably one or more mixing in vinal, vinylon, polypropylene fibre, polyethylene fibre, ethylene-vinyl alcohol copolymer fiber, composite fibre, polyester fiber, natural plant fibre, viscose rayon, aramid fiber, polyparaphenylene's benzo dioxazole fiber and fibrillation tencel fiber.More preferably by the polyester fiber of 40wt% ~ 60wt%, the vinal of 20wt% ~ 35wt%, the polypropylene fibre of 10wt% ~ 30wt% and the viscose rayon composition of 10wt% ~ 15wt%.The preferred fiber number of described polyester fiber is 0.1 ~ 0.3dtex, and fibre length is the polyester fiber of 3mm; The preferred fiber number of described vinal is 0.3dtex, and fibre length is the vinal of 6mm; The preferred fiber number of described polypropylene fibre is 0.3 ~ 0.7dtex, and fibre length is the polypropylene fibre of 3mm; The preferred fiber number of described viscose rayon is 0.3 ~ 1.1dtex, and fibre length is the viscose rayon of 3mm.
The material of preparing of described transition zone is preferably one or more mixing in vinal, pet fiber (polyester fiber), vinylon, polypropylene fibre, polyethylene fibre, ethylene-vinyl alcohol copolymer fiber, composite fibre, natural plant fibre, viscose rayon, aramid fiber, polyparaphenylene's benzo dioxazole fiber, fibrillating fibre and nano-cellulose fiber.More preferably fibrous by least one be selected from vinal, polypropylene fibre, polyethylene fibre, polyester fiber, aramid fiber and vinylon of at least one fiber in the natural plant fibre of 50wt% ~ 70wt% and fibrillation tencel fiber and 30wt% ~ 50wt%.The preferred beating degree of described natural plant fibre is 40 ~ 50 ° of SR, and length is 2 ~ 4mm; The described preferred beating degree of fibrillation tencel fiber is 30 ~ 80 ° of SR, and length is 0.38 ~ 0.51mm; The preferred fiber number of described polyester fiber is 0.1 ~ 0.3dtex, and fibre length is 3mm; The preferred fiber number of described polyethylene fibre is 0.7 ~ 1.1dtex, and fibre length is 3mm; The preferred fiber number of described aramid fiber is 0.5dtex, fibre length 3mm; The preferred fiber number of described vinal is 0.5dtex, and fibre length is 3mm; The preferred fiber number of described polypropylene fibre is 1.1dtex, and fibre length is 3mm; The preferred fiber number 0.3dtex of described vinylon, fibre length is 3mm.
The material of preparing of described separating layer is preferably one or more mixing in pet fiber, vinal, polypropylene fibre, polyethylene fibre, ethylene-vinyl alcohol copolymer fiber, composite fibre, natural plant fibre, viscose rayon, aramid fiber, polyparaphenylene's benzo dioxazole fiber, fibrillation tencel fiber and nano-cellulose fiber.More preferably by least one fiber in the natural plant fibre of 20wt% ~ 35wt% and fibrillation tencel fiber, the nano-cellulose fiber being selected from least one fiber in vinal, vinylon, composite fibre and ethylene-vinyl alcohol copolymer fiber and 45wt% ~ 70wt% of 10wt% ~ 20wt% forms.The beating degree of described natural plant fibre and fibrillation tencel fiber is preferably 65-90 ° of SR; The fibre length of described natural plant fibre is preferably 0.6 ~ 2mm, and the fibre length of fibrillation tencel fiber is preferably 0.23 ~ 0.51mm, and the fibre length of described nano-cellulose fiber is preferably 1 ~ 5nm.
Preferably, described separating layer accounts for 10% ~ 30% of described NF membrane gross mass, and described transition zone accounts for 20% ~ 50% of described NF membrane gross mass, and described supporting layer accounts for 30% ~ 60% of described NF membrane gross mass.
Preferably, the thickness of described non-woven fabric compounded NF membrane is 15 ~ 200 μm.
Preferably, in order to increase the wetting property of NF membrane, the surface of described separating layer also has one deck glue application layer, and described glue application layer is made up of polyethylene glycol oxide (PEO), surfactant and other conventional sheet surface treating agent.
The preparation method of above-mentioned non-woven fabric compounded NF membrane, comprises following preparation process:
(1) by separating layer raw fibre through with slurry, making beating, be diluted with water to the fibre concentration of 0.1wt%-0.005wt%, obtain separating layer slurry;
(2) by transition zone raw fibre through with slurry, making beating, be diluted with water to the fibre concentration of 0.1wt%-0.005wt%, obtain transition zone slurry;
(3) by supporting layer raw fibre through with slurry, making beating, be diluted with water to the fibre concentration of 0.1wt%-0.005wt%, be supported a layer slurry;
(4) by step (1) ~ (3) gained slurry through stacked shaping of manufacturing paper with pulp, obtain described non-woven fabric compounded NF membrane.
Preferably, described in step (4), the process of stacked shaping of manufacturing paper with pulp is as follows: step (1) ~ (3) gained slurry is independently entered three layers of head box, have in head box independently that runner is for three layers of slurry respectively, each runner has pulp distributing device with taper pipe independent separately and tube bank to carry out cloth slurry and neat and well spaced to respective slurry, each layer slurry is made all to be in good dispersion and the state of steady flow, three runners are separated by division board, last in the end of nozzle accelerating region, three layers of slurry stream combine, and spray to forming net and carry out dehydration forming, again through squeezing, dry, three layers of slurry are combined closely, stacked shaping of manufacturing paper with pulp.
As an example, the present invention provides a kind of equipment that can realize above-mentioned stacked forming process of manufacturing paper with pulp, as shown in Figure 1, a kind of for the stacked three layers of head box oblique net paper machine be shaped of manufacturing paper with pulp, and comprises multilayer head box main body 1, wite roll 2, forming net 3; A, B and C represent separating layer slurry stream respectively, and transition zone slurry stream and supporting layer slurry stream, D represents drying zone.After A, B, C tri-layers of slurry flow through good dispersion and rectification, respectively from the different runners of these three layers of head boxs, three runners are separated by division board, last in the end of nozzle accelerating region, three layers of slurry stream combine, and spray to forming net and carry out dewatered slurry and be injected on forming net through head box, and this just enables low concentration slurry dewater in a large number when surfing the Net, three-ply paper width is closely linked, and so just can reach of the present invention and once be shaped on wire-cloth.Because paper-making process has one to fill up effect, may be there is larger hole in non-woven fabrics, have the slurry of hole part less, and dehydration resistance is less, then slurry prioritizing selection hole place is shaped and makes up the defect of macropore, so just can ensure that NF membrane there will not be more macropore.Paper after even shaping, press section through oblique net paper machine then carries out squeezing the mass dryness fraction to suitable by it, dried by Flying Dutchman or multi-cylinder drying cylinder, through applying glue process, dried by drying cylinder again, with calender, film surface is processed again, be switched to the width of needs finally by cutting machine.This preparation method can obtain the membrane material that aperture is controlled, gap structure is evenly distributed, interfacial bonding strength is good.
Preferably, after stacked shaping of manufacturing paper with pulp described in step (4), top sizing process and the press polish process of separating layer is also comprised.
Above-mentioned non-woven fabric compounded NF membrane is in water treatment and as the application of membrane material in membrane bioreactor.
Relative to prior art, tool of the present invention has the following advantages and beneficial effect:
(1) composite nanometer filtering film of the present invention comprises three-decker, by selecting the raw fibre of three-decker and combining, and by disposable stacked shaping of manufacturing paper with pulp, make separating layer have less aperture, good separating property, effectively can improve removal effect; Transition zone has uniform micro/nano level pore size distribution, improves the retention of separating layer nano-cellulose; Supporting layer has certain intensity, hole density, pore size and pore size distribution, and has good withstand voltage properties, physicochemical stability can ensure higher flux and operation stability;
(2) preparation method of the present invention is simple, and technological operation is convenient, is easy to suitability for industrialized production; Obtained composite nanometer filtering film has good chemical stability and resistance tocrocking, and pure water flux is greater than 70L/ (m 2h), be greater than 92% to sodium sulphate rejection, molecular cut off is 185 ~ 320Da, and glucose rejection is greater than 90%, and sucrose rejection is greater than 92%.
Accompanying drawing explanation
Fig. 1 is the present invention's a kind of three layers of head box oblique net paper machine for stacked shaping of manufacturing paper with pulp as an example; Number description is as follows: 1-multilayer head box main body, 2-wite roll, 3-forming net; A, B and C represent separating layer slurry stream, transition zone slurry stream and supporting layer slurry stream respectively, and D represents drying zone.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) by separating layer raw fibre through with slurry, making beating, be diluted with water to the fiber total concentration of 0.05wt%, obtain separating layer slurry; This step is with slurry with following raw fibre:
1. beating degree 70 ~ 80 ° of SR, fibre length 0.6-2mm hardwood pulp (15wt%);
2. the viscose rayon (20wt%) of fiber number 0.06dtex, fibre length 3mm;
3. beating degree 65 ~ 70 ° of SR, fibre length 0.51mm tencel fiber (20wt%);
4. nano-cellulose (45wt%);
(2) by transition zone raw fibre through with slurry, making beating, be diluted with water to the fiber total concentration of 0.05wt%, obtain transition zone slurry; This step is with slurry with following raw fibre:
1. the hardwood pulp (10wt%) of beating degree 40 ~ 50 ° of SR, fibre length 2-4mm;
2. the polyester fiber (20wt%) of fiber number 0.3dtex, fibre length 3mm;
3. the tencel fiber (40wt%) of beating degree 30 ~ 40 ° of SR, fibre length 0.51mm;
4. the polyethylene fibre (15wt%) of fiber number 1.1dtex, fibre length 3mm;
5. the aramid fiber (15wt%) of fiber number 0.5dtex, fibre length 3mm;
(3) by supporting layer raw fibre through with slurry, making beating, be diluted with water to the fiber total concentration of 0.05wt%, be supported a layer slurry; This step is with slurry with following raw fibre:
1. the vinal (35wt%) of fiber number 0.3dtex, fibre length 6mm;
2. the polyester fiber (40wt%) of fiber number 0.3dtex, fibre length 3mm;
3. the polypropylene fibre (20wt%) of fiber number 0.7dtex, fibre length 3mm;
4. the viscose rayon (15wt%) of fiber number 1.1dtex, fibre length 3mm;
(4) by step (1) ~ (3) gained slurry through three layers of disposable stacked shaping of manufacturing paper with pulp of head box oblique net paper machine, obtain described non-woven fabric compounded NF membrane.
Embodiment 2
(1) by separating layer raw fibre through with slurry, making beating, be diluted with water to the fiber total concentration of 0.05wt%, obtain separating layer slurry; This step is with slurry with following raw fibre:
1. beating degree 70-80 ° of SR, fibre length 0.6-2mm hardwood pulp (10wt%);
2. the vinylon (20wt%) of fiber number 0.06dtex, fibre length 3mm;
3. beating degree 70-80 ° of SR, fibre length 0.44mm tencel fiber (20wt%);
4. nano-cellulose (50wt%);
(2) by transition zone raw fibre through with slurry, making beating, be diluted with water to the fiber total concentration of 0.05wt%, obtain transition zone slurry; This step is with slurry with following raw fibre:
1. beating degree 40-50 ° of SR, fibre length 2-4mm hardwood pulp (10wt%);
2. the polyester fiber (15wt%) of fiber number 0.3dtex, fibre length 3mm;
3. beating degree 40-50 ° of SR, fibre length 0.44mm tencel fiber (50wt%);
4. the polypropylene fibre (10wt%) of fiber number 1.1dtex, fibre length 3mm;
5. the aramid fiber (15wt%) of fiber number 0.5dtex, fibre length 3mm;
(3) by supporting layer raw fibre through with slurry, making beating, be diluted with water to the fiber total concentration of 0.05wt%, be supported a layer slurry; This step is with slurry with following raw fibre:
1. the vinal (30wt%) of fiber number 0.3dtex, fibre length 6mm;
2. the polyester fiber (40wt%) of fiber number 0.3dtex, fibre length 3mm;
3. the polypropylene fibre (30wt%) of fiber number 0.7dtex, fibre length 3mm;
4. the viscose rayon (10wt%) of fiber number 1.1dtex, fibre length 3mm;
(4) by step (1) ~ (3) gained slurry through three layers of disposable stacked shaping of manufacturing paper with pulp of head box oblique net paper machine, obtain described non-woven fabric compounded NF membrane.
Embodiment 3
(1) by separating layer raw fibre through with slurry, making beating, be diluted with water to the fiber total concentration of 0.05wt%, obtain separating layer slurry; This step is with slurry with following raw fibre:
1. beating degree 70-80 ° of SR, fibre length 0.6-2mm hardwood pulp (15wt%);
2. the ethylene-vinyl alcohol copolymer fiber (10wt%) of fiber number 0.06dtex, fibre length 3mm;
3. beating degree 75-80 ° of SR, fibre length 0.38mm tencel fiber (20wt%);
4. nano-cellulose (55wt%);
(2) by transition zone raw fibre through with slurry, making beating, be diluted with water to the fiber total concentration of 0.05wt%, obtain transition zone slurry; This step is with slurry with following raw fibre:
1. beating degree 40-50 ° of SR, fibre length 2-4mm hardwood pulp (10wt%);
2. the polyester fiber (10wt%) of fiber number 0.3dtex, fibre length 3mm;
3. beating degree 50-60 ° of SR, fibre length 0.38mm tencel fiber (55wt%);
4. the polyethylene fibre (10wt%) of fiber number 0.7dtex, fibre length 3mm;
5. the aramid fiber (15wt%) of fiber number 0.5dtex, fibre length 3mm;
(3) by supporting layer raw fibre through with slurry, making beating, be diluted with water to the fiber total concentration of 0.05wt%, be supported a layer slurry; This step is with slurry with following raw fibre:
1. the vinal (30wt%) of fiber number 0.3dtex, fibre length 6mm;
2. the polyester fiber (50wt%) of fiber number 0.3dtex, fibre length 3mm;
3. the polypropylene fibre (10wt%) of fiber number 0.7dtex, fibre length 3mm;
4. the viscose rayon (10wt%) of fiber number 0.7dtex, fibre length 3mm;
(4) by step (1) ~ (3) gained slurry through three layers of disposable stacked shaping of manufacturing paper with pulp of head box oblique net paper machine, obtain described non-woven fabric compounded NF membrane.
Embodiment 4
(1) by separating layer raw fibre through with slurry, making beating, be diluted with water to the fiber total concentration of 0.05wt%, obtain separating layer slurry; This step is with slurry with following raw fibre:
1. beating degree 70-80 ° of SR, fibre length 0.6-2mm hardwood pulp (10wt%);
2. the composite fibre (20wt%) of fiber number 0.06dtex, fibre length 3mm;
3. beating degree 80-85 ° of SR, fibre length 0.3mm tencel fiber (15wt%);
4. nano-cellulose (55wt%);
(2) by transition zone raw fibre through with slurry, making beating, be diluted with water to the fiber total concentration of 0.05wt%, obtain transition zone slurry; This step is with slurry with following raw fibre:
1. beating degree 40-50 ° of SR, fibre length 2-4mm hardwood pulp (10wt%);
2. the polyester fiber (10wt%) of fiber number 0.1dtex, fibre length 3mm;
3. beating degree 60-70 ° of SR, fibre length 0.38mm tencel fiber (55wt%);
4. the vinal (10wt%) of fiber number 0.5dtex, fibre length 3mm;
5. the aramid fiber (15wt%) of fiber number 0.5dtex, fibre length 3mm;
(3) by supporting layer raw fibre through with slurry, making beating, be diluted with water to the fiber total concentration of 0.05wt%, be supported a layer slurry; This step is with slurry with following raw fibre:
1. the vinal (30wt%) of fiber number 0.3dtex, fibre length 6mm;
2. the polyester fiber (50wt%) of fiber number 0.1dtex, fibre length 3mm;
3. the polypropylene fibre (10wt%) of fiber number 0.5dtex, fibre length 3mm;
4. the viscose rayon (10wt%) of fiber number 0.5dtex, fibre length 3mm;
(4) by step (1) ~ (3) gained slurry through three layers of disposable stacked shaping of manufacturing paper with pulp of head box oblique net paper machine, obtain described non-woven fabric compounded NF membrane.
Embodiment 5
(1) by separating layer raw fibre through with slurry, making beating, be diluted with water to the fiber total concentration of 0.05wt%, obtain separating layer slurry; This step is with slurry with following raw fibre:
1. beating degree 70-80 ° of SR, fibre length 0.6-2mm hardwood pulp (10wt%);
2. the vinal (10wt%) of fiber number 0.06dtex, fibre length 3mm;
3. beating degree 85-90 ° of SR, fibre length 0.23mm tencel fiber (10wt%);
4. nano-cellulose (70wt%);
(2) by transition zone raw fibre through with slurry, making beating, be diluted with water to the fiber total concentration of 0.05wt%, obtain transition zone slurry; This step is with slurry with following raw fibre:
1. beating degree 40-50 ° of SR, fibre length 2-4mm hardwood pulp (10wt%);
2. the polyester fiber (10wt%) of fiber number 0.1dtex, fibre length 3mm;
3. beating degree 70-80 ° of SR, fibre length 0.38mm tencel fiber (60wt%);
4. the vinylon (10wt%) of fiber number 0.3dtex, fibre length 3m;
5. the aramid fiber (10wt%) of fiber number 0.5dtex, fibre length 3mm;
(3) by supporting layer raw fibre through with slurry, making beating, be diluted with water to the fiber total concentration of 0.05wt%, be supported a layer slurry; This step is with slurry with following raw fibre:
1. the vinal (20wt%) of fiber number 0.3dtex, fibre length 6mm;
2. the polyester fiber (60wt%) of fiber number 0.1dtex, fibre length 3mm;
3. the polypropylene fibre (10wt%) of fiber number 0.3dtex, fibre length 3mm;
4. the viscose rayon (10wt%) of fiber number 0.3dtex, fibre length 3mm;
(4) by step (1) ~ (3) gained slurry through three layers of disposable stacked shaping of manufacturing paper with pulp of head box oblique net paper machine, obtain described non-woven fabric compounded NF membrane.
The performance of composite nanometer filtering film prepared by embodiment 1-5 is tested by following method.
1. test item and method
(1) pure water flux (F)
The penetrating power of NF membrane represents with pure water flux, refers to the unit interval interior pure water volume by per membrane area under a certain pressure.Calculate by formula 1-1.
F＝V/(A×t)(1-1)
In formula: F-pure water flux (L/ (m 2h))
The pure water volume (L) collected in V-time t
A-membrane area (m 2)
T-running time (h)
Prepare gained NF membrane under 0.5MPa, use pure water precompressed 1h, then measure pure water flux.Condition determination pressure is 0.5MPa, and temperature is 25 DEG C.
(2) rejection (R)
NF membrane directly can illustrate the cutoff performance of film to this kind of solute to the rejection of different solute.Calculate by formula (1-2):
R = ( 1 - c p c f ) × 100 % - - - ( 1 - 2 )
In formula: R-rejection (%)
C pthe concentration (mg/L) of a certain specific solute in-permeate
C fthe concentration (mg/L) of a certain specific solute in-original solution.
A. the rejection of high-valence state inorganic salts
NF membrane is mainly used in the separation of divalence or multivalent ion, for monovalention (as Na +and Cl -) then freely can pass through NF membrane.Due to the charge effect of NF membrane, to the inorganic salts of high-valence state, there is good electrostatic repulsion, high to the salt rejection of high valence ion; On the other hand, due to the sieving actoion of NF membrane, SO 4 2-radius ratio Cl -radius is large, so high to the rejection of sulfate.
NF membrane with deionized water precompressed 1h, then measures its cutoff performance under the pressure of 0.5MPa.In experiment, the mensuration of high-valence state inorganic salts rejection is 7.0 at 0.5MPa, pH, measures the Na of 1000mg/L (ppm) under the condition that temperature is 25 DEG C 2sO 4.
B. molecular cut off
The rejection of micromolecular organic matter (PEG600 and PEG1000) is measured.NF membrane with deionized water precompressed 1h, then measures its cutoff performance under the pressure of 0.5MPa.PEG600 and the PEG1000 solution of preparation 500ppm, at pH=7, under 25 DEG C of conditions, records NF membrane rejection to PEG under 0.5MPa.
C. the rejection of centering neutral material
NF membrane retains uncharged material (as dextrose plus saccharose), is the nanometer level microporous molecular sieving effect according to film.
NF membrane with deionized water precompressed 1h, then measures its cutoff performance under the pressure of 0.5MPa.The preparation glucose solution of 1g/L and sucrose solution, at pH=7, under 25 DEG C of conditions, record NF membrane rejection to glucose solution and sucrose solution under 0.5MPa.
2. measurement result
The every testing result of NF membrane prepared by embodiment 1-5 is in table 1.
The performance test results of composite nanometer filtering film prepared by table 1 embodiment 1-5
3. conclusion
Result shows, and multilayer NF membrane superior performance prepared by embodiment 1-5, is mainly reflected in: composite nanometer filtering film has good chemical stability and resistance tocrocking, and its water flux is large, and average water flux is greater than 70L/ (m 2h), be greater than 92% to sodium sulphate rejection, glucose rejection is greater than 90%, and sucrose rejection is greater than 92%, and molecular cut off scope 185-320Da meets the requirement of water treatment NF membrane completely.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (10)

1. a non-woven fabric compounded NF membrane, is characterized in that: described composite nanometer filtering film is 5 ~ 20 μm by average pore size, is quantitatively 5 ~ 30g/m 2non-woven fabrics supporting layer, average pore size is 100nm ~ 3 μm, is quantitatively 5 ~ 20g/m 2non-woven fabrics transition zone and average pore size be 1 ~ 50nm, be quantitatively 2 ~ 15g/m 2non-woven fabrics separating layer be prepared from through compound.
2. the non-woven fabric compounded NF membrane of one according to claim 1, is characterized in that: the material of preparing of described supporting layer is one or more mixing in vinal, vinylon, polypropylene fibre, polyethylene fibre, ethylene-vinyl alcohol copolymer fiber, composite fibre, polyester fiber, natural plant fibre, viscose rayon, aramid fiber, polyparaphenylene's benzo dioxazole fiber and fibrillation tencel fiber; The material of preparing of described transition zone is one or more mixing in vinal, pet fiber, vinylon, polypropylene fibre, polyethylene fibre, ethylene-vinyl alcohol copolymer fiber, composite fibre, natural plant fibre, viscose rayon, aramid fiber, polyparaphenylene's benzo dioxazole fiber, fibrillating fibre and nano-cellulose fiber; The material of preparing of described separating layer is one or more mixing in pet fiber, vinal, polypropylene fibre, polyethylene fibre, ethylene-vinyl alcohol copolymer fiber, composite fibre, natural plant fibre, viscose rayon, aramid fiber, polyparaphenylene's benzo dioxazole fiber, fibrillation tencel fiber and nano-cellulose fiber.
3. the non-woven fabric compounded NF membrane of one according to claim 2, it is characterized in that: described supporting layer is by the polyester fiber of 40wt% ~ 60wt%, the vinal of 20wt% ~ 35wt%, the polypropylene fibre of 10wt% ~ 30wt% and the viscose rayon composition of 10wt% ~ 15wt%; Described transition zone is fibrous by least one be selected from vinal, polypropylene fibre, polyethylene fibre, polyester fiber, aramid fiber and vinylon of at least one fiber in the natural plant fibre of 50wt% ~ 70wt% and fibrillation tencel fiber and 30wt% ~ 50wt%; Described separating layer is by least one fiber in the natural plant fibre of 20wt% ~ 35wt% and fibrillation tencel fiber, and the nano-cellulose fiber being selected from least one fiber in vinal, vinylon, composite fibre and ethylene-vinyl alcohol copolymer fiber and 45wt% ~ 70wt% of 10wt% ~ 20wt% forms.
4. the non-woven fabric compounded NF membrane of one according to claim 3, is characterized in that: in described supporting layer: polyester fiber refers to that fiber number is 0.1 ~ 0.3dtex, and fibre length is the polyester fiber of 3mm; Vinal refers to that fiber number is 0.3dtex, and fibre length is the vinal of 6mm; Polypropylene fibre refers to that fiber number is 0.3 ~ 0.7dtex, and fibre length is the polypropylene fibre of 3mm; Viscose rayon refers to that fiber number is 0.3 ~ 1.1dtex, and fibre length is the viscose rayon of 3mm; In described transition zone: the beating degree of natural plant fibre is 40 ~ 50 ° of SR, and fibre length is 2 ~ 4mm; The beating degree of fibrillation tencel fiber is 30 ~ 80 ° of SR, and fibre length is 0.38 ~ 0.51mm; The fiber number of polyester fiber is 0.1 ~ 0.3dtex, and fibre length is 3mm; The fiber number of polyethylene fibre is 0.7 ~ 1.1dtex, and fibre length is 3mm; The fiber number of aramid fiber is 0.5dtex, fibre length 3mm; The fiber number of vinal is 0.5dtex, and fibre length is 3mm; The fiber number of polypropylene fibre is 1.1dtex, and fibre length is 3mm; The fiber number 0.3dtex of vinylon, fibre length is 3mm; In described separating layer: the beating degree of natural plant fibre and fibrillation tencel fiber is 65 ~ 90 ° of SR; The fibre length of natural plant fibre is 0.6 ~ 2mm, and the fibre length of fibrillation tencel fiber is 0.23 ~ 0.51mm, and the fibre length of nano-cellulose fiber is 1 ~ 5nm.
5. the non-woven fabric compounded NF membrane of the one according to any one of Claims 1 to 4, it is characterized in that: described separating layer accounts for 10% ~ 30% of described NF membrane gross mass, described transition zone accounts for 20% ~ 50% of described NF membrane gross mass, and described supporting layer accounts for 30% ~ 60% of described NF membrane gross mass.
6. the non-woven fabric compounded NF membrane of the one according to any one of Claims 1 to 4, is characterized in that: the thickness of described non-woven fabric compounded NF membrane is 15 ~ 200 μm.
7. the non-woven fabric compounded NF membrane of the one according to any one of Claims 1 to 4, it is characterized in that: the surface of described separating layer also has one deck glue application layer, described glue application layer is made up of polyethylene glycol oxide, surfactant and other conventional sheet surface treating agent.
8. the preparation method of a kind of non-woven fabric compounded NF membrane described in any one of claim 1 ~ 7, is characterized in that comprising following preparation process:
(1) by separating layer raw fibre through with slurry, making beating, be diluted with water to the fibre concentration of 0.1wt%-0.005wt%, obtain separating layer slurry;
(2) by transition zone raw fibre through with slurry, making beating, be diluted with water to the fibre concentration of 0.1wt%-0.005wt%, obtain transition zone slurry;
(3) by supporting layer raw fibre through with slurry, making beating, be diluted with water to the fibre concentration of 0.1wt%-0.005wt%, be supported a layer slurry;
(4) by step (1) ~ (3) gained slurry through stacked shaping of manufacturing paper with pulp, obtain described non-woven fabric compounded NF membrane.
9. the preparation method of a kind of non-woven fabric compounded NF membrane according to claim 8, it is characterized in that, described in step (4), the process of stacked shaping of manufacturing paper with pulp is as follows: step (1) ~ (3) gained slurry is independently entered three layers of head box, have in head box independently that runner is for three layers of slurry respectively, each runner has pulp distributing device with taper pipe independent separately and tube bank to carry out cloth slurry and neat and well spaced to respective slurry, each layer slurry is made all to be in good dispersion and the state of steady flow, three runners are separated by division board, last in the end of nozzle accelerating region, three layers of slurry stream combine, and spray to forming net and carry out dehydration forming, again through squeezing, dry, three layers of slurry are combined closely, stacked shaping of manufacturing paper with pulp.
10. the non-woven fabric compounded NF membrane described in any one of claim 1 ~ 7 is in water treatment and as the application of membrane material in membrane bioreactor.
CN201510920598.0A 2015-12-10 2015-12-10 Nonwoven cloth composite nanofiltration membrane and preparation method and application thereof Pending CN105498550A (en)

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CN112501951A (en) * 2020-11-23 2021-03-16 江苏展宝新材料有限公司 Preparation method of separation membrane composite support
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CN111939767A (en) * 2020-08-25 2020-11-17 中国海诚工程科技股份有限公司 Flat-plate denitrification film for wastewater treatment and preparation method thereof
WO2022095100A1 (en) * 2020-11-09 2022-05-12 苏州纳昇源新材料科技有限公司 Preparation method for multi-scale nanocellulose film based on flax fibers
CN112501951A (en) * 2020-11-23 2021-03-16 江苏展宝新材料有限公司 Preparation method of separation membrane composite support
CN112588135A (en) * 2020-11-25 2021-04-02 中国海诚工程科技股份有限公司 MBR flat membrane and preparation method thereof
CN113648849A (en) * 2021-09-02 2021-11-16 前沿新材料研究院（深圳）有限公司 Water treatment membrane supporting layer and water treatment membrane
CN115117555A (en) * 2022-04-13 2022-09-27 中国制浆造纸研究院有限公司 Composite diaphragm material for alkaline manganese battery and preparation method thereof
CN117732281A (en) * 2023-12-25 2024-03-22 浙江大学 Cellulose-based degradable separation membrane and preparation method and application thereof

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Application publication date: 20160420