CN104209018B - A kind of attapulgite/polyvinylidene fluoride nanometer composite hyperfiltration membrane and preparation method thereof - Google Patents
A kind of attapulgite/polyvinylidene fluoride nanometer composite hyperfiltration membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of attapulgite/polyvinylidene fluoride nanometer composite hyperfiltration membrane and preparation method thereof, comprise the following steps: selection triethyl phosphate is solvent, a certain amount of nano-attapulgite stone is added wherein, after vigorous mechanical agitation and supersound process are uniform, add Kynoar powder body stirring and dissolving, add Polyethylene Glycol and stir to obtain casting solution；With water for coagulating bath, immersion precipitation phase inversion process is adopted to prepare attapulgite/polyvinylidene fluoride nanometer composite hyperfiltration membrane.Nanofibrous structures that the attapulgite of the present invention/polyvinylidene fluoride nanometer composite hyperfiltration membrane utilizes attapulgite unique by nano-attapulgite stone introduces polyvinylidene fluoride (PVDF) ultrafiltration membrane and the tridimensional network formed with Kynoar thereof are effectively improved structure and the intensity of polyvinylidene fluoride (PVDF) ultrafiltration membrane；Utilize attapulgite height water-wet behavior to improve the permeability of polyvinylidene fluoride (PVDF) ultrafiltration membrane, hydrophilic and contamination resistance simultaneously.
Description
Technical field
The present invention relates to a kind of attapulgite/polyvinylidene fluoride nanometer composite hyperfiltration membrane and preparation method thereof, belong to separation membrane technical field.
Background technology
Kynoar (PVDF) has the excellent properties such as high-strength corrosion-resisting, chemical resistance, heat-resisting quantity, oxidative resistance, and because PVDF pliability is good, oneself is widely used in preparation hollow fiber ultrafiltration membrane material.But Kynoar has relatively low surface energy and stronger hydrophobicity, causes its water penetration comparison of resistance high, limits its application in aqueous phase separation system；Hydrophobicity also leads to film and is subject to pollution simultaneously, deteriorates its separating property, and directly influences the economy of membrane separating process.Therefore, polyvinylidene fluoride film is carried out hydrophilically modified, improve its permeance property and suppress pollution capacity, being the simple and effective approach improving Kynoar film properties.
Blending and modifying is a kind of the most frequently used also most practical polymeric membrane method of modifying.The film blending and modifying agent of early stage is mainly the water-soluble polymer such as Polyethylene Glycol and polyvinylpyrrolidone or LiCl, CaCl2Deng inorganic salt, owing to these modifying agent are soluble in water, not only easily run off in being inverted into membrane process, and in use also easily progressively run off from membrane material, thus having a strong impact on its hydrophilic modifying effect, so this type of modifying agent is primarily used to improve the structure of film and improve the porosity of film, it is difficult to obtain good antifouling property.In recent years, by blended to inorganic nano-particle and conventional polymer membrane material, the method preparing hydrophilic separation film causes the attention of people, owing to inorganic nano-particle is hydrophilic but water insoluble, it is possible to avoids it to run off from membrane material, obtains lasting modified effect.Inorganic nano-particle blending and modifying is easy to operate with it, technique is simply also widely used, and improves the hydrophilic of film by adding inorganic nano-particle, reduces fouling membrane；Additionally, due to introduce inorganic particle in organic network, improve network structure, enhance the mechanical performance of polymeric membrane, improve heat stability so that it is have the toughness of polymeric membrane and the heat-resisting quantity of inoranic membrane concurrently.
It is presently used for the inorganic nano-particle such as Al of blending and modifying2O3、TiO2、ZrO2And SiO2Etc. being graininess, these nano level inorganic particles can fall off in film preparation and use procedure, and affects performance and the modified effect of film.By contrast, the monodimension nanometer materials such as CNT have superpower mechanical property, high length-width ratio and high-ratio surface, and it is dispersed in the monodimension nanometer material in polymeric membrane, its stability in membrane material can be effectively improved by the spiral winding of macromolecular chain.But, the artificial synthesizing one-dimensional nano material preparation cost such as CNT is high, purity and yielding poorly down, it is difficult to dispersion, which greatly limits its scale in film blending and modifying application.
Summary of the invention
It is an object of the invention to provide a kind of high flux attapulgite/polyvinylidene fluoride nanometer composite hyperfiltration membrane, the nanofibrous structures utilizing attapulgite uniqueness and the tridimensional network formed with Kynoar thereof are effectively improved structure and the intensity of polyvinylidene fluoride (PVDF) ultrafiltration membrane, utilize attapulgite height water-wet behavior to improve the permeability of polyvinylidene fluoride (PVDF) ultrafiltration membrane, hydrophilic, stability and contamination resistance simultaneously.
According to an aspect of the present invention, a kind of attapulgite/polyvinylidene fluoride nanometer composite hyperfiltration membrane, by weight, its raw material of preparing includes following component: polyvinylidene fluoride resin 15～20 parts, organic solvent 80～85 parts, nano-attapulgite stone, additive；The weight of described nano-attapulgite stone is 0.5～15% (preferably 6.7～10%) of polyvinylidene fluoride resin weight, and the weight of described additive is the 2～6% of polyvinylidene fluoride resin and organic solvent gross mass.
Further, described organic solvent is selected from METHYLPYRROLIDONE, oxolane, dimethyl sulfoxide, tetramethylurea, amide solvent, esters solvent or lactone solvent.
Further, described amide solvent is selected from dimethyl acetylamide, dimethylformamide etc.；Described esters solvent is selected from trimethyl phosphate or triethyl phosphate etc.；Described lactone solvent is selected from gamma-butyrolacton etc.；It most preferably is triethyl phosphate.
Further, described additive is selected from Polyethylene Glycol, polyvinyl pyrrolidone, polyvinyl alcohol, polyacrylic acid, Polyethylene Glycol, lithium chloride, sodium chloride, calcium chloride, lithium nitrate, formaldehyde, Methanamide；Preferred Polyethylene Glycol.
Further, the fibre length of nano-attapulgite stone is 500～2000nm, and diameter is 30～70nm, and attapulgite content is not less than 95%.
Further, nano-attapulgite stone is that cationic surfactant modifiied.
According to another aspect of the present invention, the preparation method of attapulgite/polyvinylidene fluoride nanometer composite hyperfiltration membrane, comprise the steps: to add in organic solvent by nano-attapulgite stone, make mixed system homogenization, casting solution is obtained after adding polyvinylidene fluoride resin and organic additive stirring and dissolving, standing and defoaming, adopts immersion precipitation phase inversion process to prepare ultrafilter membrane.
Further, nano-attapulgite stone is that cationic surfactant modifiied.
Further, phase inversion adopts water as coagulating bath.
Further, phase inversion adopts spin processes.
Further, the temperature in the process of homogenization controls at 75～85 DEG C.
Further, the time of stirring and dissolving is 24～36 hours.
Further, the time of standing and defoaming is 12 ~ 24 hours；The temperature of standing and defoaming is 75～85 DEG C.
Further, the technological parameter in spin processes is: the dry journey of air is 0～30cm；Casting solution flow velocity is 2～10mL/min；Core liquid is deionized water, and its flow velocity is 2～6mL/min；The water temperature of coagulating bath is at 20～30 DEG C.
Beneficial effect
1. this nano combined hollow fiber ultrafiltration membrane utilizes the unique nanofibrous structures of attapulgite and the tridimensional network that formed with Kynoar thereof to be effectively improved structure and the intensity of polyvinylidene fluoride (PVDF) ultrafiltration membrane, utilizes attapulgite height water-wet behavior to be effectively increased the permeability of polyvinylidene fluoride (PVDF) ultrafiltration membrane, hydrophilic and contamination resistance simultaneously.
2. compared with particulate inorganic nano-particle, attapulgite is that monodimension nanometer material has the mechanical property of excellence, high length-width ratio, high-ratio surface and nano level structure pore, and it is dispersed in the monodimension nanometer material in polymeric membrane, its stability in membrane material can be effectively improved by the spiral winding of macromolecular chain.
3., compared with unmodified nano-attapulgite stone, effectively dissociated nano-attapulgite stone crystalline substance bundle by cationic surfactant modification, improve nano-attapulgite stone dispersibility and and Kynoar between the compatibility and the stability of composite membrane.
4. compared with the nano material of synthetic, natural nano attapulgite clay is huge at China's reserves, cheap, and it is extremely low to develop process energy consumption, it does not have the negative effect of environment aspect, its cost performance is substantially better than synthetic nano-fiber material.
Detailed description of the invention
Below by detailed description of the invention, the present invention is described in further detail.It will be apparent, however, to one skilled in the art, that the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Unreceipted concrete technology or condition person in embodiment, technology or condition described by the document in this area or carry out according to product description.Agents useful for same or the unreceipted production firm person of instrument, be can pass through city available from conventional products.
Approximate language used herein can be used for modifying the statement of any quantity in entire disclosure and claims, and it can be changed being not resulted in allowance when its relevant basic function changes.Therefore, such as term " about " value modified is not limited to specified exact value.In at least some cases, approximate language can be corresponding with the precision of the instrument for measuring this value.Unless indicated otherwise in context or statement, otherwise range limit can be combined and/or exchange, and this scope is confirmed as and includes all subranges contained herein.Except indicating in operation embodiment or elsewhere, the numeral of the amount of all expression compositions that uses in specification and claims, reaction condition etc. or express and shall be construed as the modification being subject to word " about " in all cases.
The numerical value as range limit not only including clearly listing should be interpreted as using the value of range format expression in a flexible way, but also include all single numerical value or the subinterval that are encompassed within the scope of this, be expressly recited out just as each numerical value and subinterval.Such as, the concentration range of " about 0.1% to about 5% " should be understood to not only to include the concentration of about 0.1% to about 5% clearly listed, also include single concentration in institute's how (as, 1%, 2%, 3% and 4%) and subinterval (such as, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%).
Nano-attapulgite stone (nanoattapulgite) is the alumina magnesia silicate of a kind of layer of chain structure, and its profile is fibrous or bar-shaped, has the crystal diameter of nanoscale, diameter 30～70nm, length about 0.5～5 μm, belongs to typical monodimension nanometer material.Natural nano attapulgite has one-dimensional nano-scale structure on the external appearance characteristic such as form, size, consistent with the one-dimentional structure nano material of synthetic, this means that they have same or analogous purposes, but compared with the nano material of synthetic, nano-attapulgite stone wide material sources.Attapulgite clay (is called for short attapulgite clay, it is mainly composed of nano-attapulgite stone) huge at China's reserves, only Huai'an, Jiangsu Province Xuyi County has verified attapulgite clay ore resources reserves is 1.03 hundred million tons, account for the whole nation and verify the 73% of attapulgite clay reserves, accounting for the whole world and verified the 44% of attapulgite clay reserves, prospective reserves reaches 11.7 hundred million tons.The production cost of nano-attapulgite stone is low, it is prone to relatively produce in enormous quantities, exploitation process energy consumption is extremely low, and nano-attapulgite stone has environment compatibility and the compatibility of excellence, its cost performance is substantially better than synthetic nano-fiber material, can solve artificial nano unit material little, the high in cost of production problem of batch preferably.
The present invention is by introducing polyvinylidene fluoride (PVDF) ultrafiltration membrane by nano-attapulgite stone, the nanofibrous structures utilizing attapulgite uniqueness and the tridimensional network formed with Kynoar thereof are effectively improved structure and the intensity of polyvinylidene fluoride (PVDF) ultrafiltration membrane, utilize attapulgite height water-wet behavior to improve the permeability of polyvinylidene fluoride (PVDF) ultrafiltration membrane, hydrophilic and contamination resistance simultaneously, this membrane preparation method is simple, membrane aperture is controlled, it is adaptable in the practical applications such as sewage disposal, Industrial Wastewater Treatment, Treated sewage reusing, rural potable water of today.The fibre length of the nano-attapulgite stone adopted in following example is 500～2000nm, and diameter is 30～70nm, and attapulgite content is not less than 95%.
The raw material of this ultrafilter membrane includes Kynoar, has additionally included nano-attapulgite stone, be doped in casting solution and can prepare composite hyperfiltration membrane, casting solution also includes the organic solvent dissolving polyvinylidene fluoride resin.
Herein, organic solvent refers to the material dissolving polyvinylidene fluoride resin, it is possible to enumerate: such as, METHYLPYRROLIDONE, oxolane, dimethyl sulfoxide, tetramethylurea；The amide such as dimethyl acetylamide, dimethylformamide；Ester or the lactones such as trimethyl phosphate, triethyl phosphate, gamma-butyrolacton；And their mixed solvent.
It addition, the component of casting solution can also contain the organic additive supporting the aperture of film, porosity, hydrophilic, elastic modelling quantity etc. for regulating the micro-porous of gained.As the additive for adjustment aperture and porosity, alcohols can be enumerated, water soluble polymer or their salt such as Polyethylene Glycol, polyvinyl pyrrolidone, polyvinyl alcohol, polyacrylic acid, also have the inorganic salts such as lithium chloride, sodium chloride, calcium chloride, lithium nitrate, formaldehyde, Methanamide etc., but be not limited to that this.Following example adopt PEG400 as expanding agent.
The preparation method of this ultrafilter membrane can adopt the method for common inversion of phases obtained, is occurred by casting solution after inversion of phases, it is possible to obtain the ultrafilter membrane with microcellular structure in solidification liquid.
In said method, solidification liquid is as non-solvent, it is possible to enumerate: such as, water；The aliphatic hydrocarbons such as hexane, pentane, trichloro ethylene；The aromatic hydrocarbon such as benzene, toluene etc.；And their mixed solvent etc..When by Kynoar be used as polymer raw material, as the non-solvent of coagulating bath, it is usually preferred to use water, as long as but the material of insoluble Kynoar, it does not have limit especially.The micro-porous obtained supports that the film form of film changes according to the composition of macromolecular solution, and the film formative of composite semipermeable membrane also changes therewith.It addition, the temperature of coagulating bath is preferably 10 DEG C～90 DEG C.More preferably 20～30 DEG C.If the temperature of coagulating bath is higher than this scope, then the vibration in coagulating bath face becomes fierce due to warm-up movement, film formed after the flatness on film surface be easily reduced.Otherwise, if temperature is too low, then setting rate is slack-off, generation problem in masking.
It follows that for the casting solution removing obtained ultrafilter membrane, it is preferable that described film is carried out hot water cleaning.Hot water temperature now is preferably 50～100 DEG C, more preferably 60～95 DEG C.If the temperature of hot water is higher than this scope, then micro-porous supports that the degree of shrinkage of film becomes big, and water penetration reduces.Otherwise, if the temperature of hot water is low, then cleaning effect is little.
An improved procedure according to the present invention, nano-attapulgite stone is through cationic surfactant modification, effectively dissociated nano-attapulgite stone crystalline substance bundle by cationic surfactant modification, improve nano-attapulgite stone dispersibility and and Kynoar between the compatibility and the stability of composite membrane, and the modified of attapulgite is swapped by the cation on its attapulgite to carry out by cationic surfactant, do not affect the hydroxyl on attapulgite surface, after these hydroxyls are retained on attapulgite, more can guarantee that it has good hydrophilic modifying effect, improve the stability of the compatibility between nano-attapulgite stone and Kynoar and composite membrane.
In the present invention, adopting molecular cut off that ultrafilter membrane performance is characterized, molecular cut off is the molecular weight of the clearance of film solute when can reach 90%.Being determined as follows of molecular cut off.First, filter the every kind of water-soluble polymer (glucosan etc.) containing the multiple different molecular weight weak solution as respective solute with film, and try to achieve the clearance to every kind of water-soluble polymer.It follows that using the molecular weight of water-soluble polymer as transverse axis, map using clearance as the longitudinal axis, draw curve of approximation, and using with the molecular weight in the cross point that clearance is 90% as molecular cut off.
In the present invention, fracture strength is adopted to characterize the mechanical performance of ultrafilter membrane.Method: cut the sample of 5cm length from film, this sample is arranged on initial jaw separation in the mode that the length direction that makes sample is draw direction and is set as on the autoplotter of 2cm, ambient temperature be 25 DEG C, till draw speed is stretched to sample breakage when being 20cm/ minute.Measure fracture strength during sample breakage.
Film pure water flux is measured on self-control ultrafilter membrane evaluating apparatus, and operation pressure is 0.1MPa, and flow velocity is 1m/s, and the operation time is 30min；Under room temperature and 0.1MPa pressure, replace deionized water, on film properties evaluating apparatus, ultrafilter membrane is easily separated performance test by bovine serum albumin (BSA) phosphate buffered solution that mass concentration is 50mg/L, to measure the contamination resistance of film.After running 120 minutes, measure the attenuation of flux, attenuation=(1-filters flux/initial flux when terminating) × 100%.
Drying after membrane sample soaks 48h in ethanol, measure the deionized water contact angle on film surface with contact angle instrument, every kind of film 5 samples of test are averaged.
Embodiment 1
1 gram of nano-attapulgite stone is joined among 80 grams of triethyl phosphates, after vigorous mechanical agitation and supersound process are uniform, add 20 grams of Kynoar powder body stirring and dissolving 24 hours at 80 DEG C, add 5 grams of Polyethylene Glycol and stir 12 hours to obtain casting solution, standing and defoaming 24 hours at 80 DEG C, adopting immersion precipitation phase inversion process, condition is: the dry journey of air is 0cm；Casting solution flow velocity is 2mL/min；Core liquid is deionized water, and its flow velocity is 2mL/min；Coagulating bath is deionized water, and water temperature, at 20～30 DEG C, prepares attapulgite/polyvinylidene fluoride nanometer composite hollow fibre ultrafilter membrane, and film thickness about 200 μm, external diameter is about 1.0mm.After measured, the pure water flux at 0.1MPa and 20 DEG C is 160L/ (m2H)；Being demarcate thing with glucosan, its molecular cut off is 150000Da；Film average pore size is about 23nm, and water droplet contact angle is 60.3 °；Fracture strength is about 3.2MPa, filters the flux decline about 75% of BSA solution.
Reference examples 1
It is distinctive in that with embodiment 1: in casting solution, do not add nano-attapulgite stone, prepare the PVDF ultrafiltration membrane of routine.20 grams of Kynoar powder body stirring and dissolving 24 hours at 80 DEG C are added among 80 grams of triethyl phosphates, add 5 grams of Polyethylene Glycol and stir 12 hours to obtain casting solution, standing and defoaming 24 hours at 80 DEG C, adopt immersion precipitation phase inversion process, and condition is: the dry journey of air is 0cm；Casting solution flow velocity is 2mL/min；Core liquid is deionized water, and its flow velocity is 2mL/min；Coagulating bath is deionized water, and water temperature, at 20～30 DEG C, prepares polyvinylidene fluoride hollow fiber ultrafiltration membrane, and film thickness about 200 μm, external diameter is about 1.0mm.After measured, the pure water flux at 0.1MPa and 20 DEG C is 106L/ (m2H)；Being demarcate thing with glucosan, its molecular cut off is 200000Da；Water droplet contact angle is 94.1 °；Fracture strength is about 2.8MPa, filters the flux decline about 89% of BSA solution.Be can be seen that by embodiment 1 and reference examples 1, after adding nano-attapulgite stone in casting solution, its three dimensional structure and hydrophilic can be utilized to make the surface of ultrafilter membrane produce hydrophilic, water flux is bigger, and its molecular cut off can be significantly decreased, improve separation accuracy, it can in addition contain improve its drawing mechanical performance.
Embodiment 2
Respectively 0.1,0.5,1,1.5,2 grams of nano-attapulgite stones are joined 85 grams of triethyl phosphates wherein, after vigorous mechanical agitation and supersound process are uniform, add 15 grams of Kynoar powder body stirring and dissolving 24 hours at 80 DEG C, add 5 grams of Polyethylene Glycol and stir 12 hours to obtain casting solution, standing and defoaming 24 hours at 80 DEG C, adopting immersion precipitation phase inversion process, condition is: the dry journey of air is 0cm；Casting solution flow velocity is 2mL/min；Core liquid is deionized water, and its flow velocity is 2mL/min；Coagulating bath is deionized water, and water temperature, at 20 ~ 30 DEG C, prepares attapulgite/polyvinylidene fluoride nanometer composite hollow fibre ultrafilter membrane.When different nano-attapulgite stone additions, film properties data are as shown in the table:
As can be seen from the table, the addition controlling nano-attapulgite stone can obtain the composite hyperfiltration membrane that flux is big preferably, and in the scope of the addition of 0.5～1.5g, flux is more excellent；And there is less molecular cut off, there is good separating property.
Embodiment 3
1 gram of nano-attapulgite stone is joined in 80 grams of organic solvents and (is respectively adopted METHYLPYRROLIDONE, gamma-butyrolacton, triethyl phosphate, dimethylformamide), after vigorous mechanical agitation and supersound process are uniform, add 20 grams of Kynoar powder body stirring and dissolving 24 hours at 80 DEG C, add 4 grams of Polyethylene Glycol and stir 12 hours to obtain casting solution, standing and defoaming 24 hours at 80 DEG C, adopting immersion precipitation phase inversion process, condition is: the dry journey of air is 30cm；Casting solution flow velocity is 2mL/min；Core liquid is deionized water, and its flow velocity is 6mL/min；Coagulating bath is deionized water, and water temperature, at 20～30 DEG C, prepares attapulgite/polyvinylidene fluoride nanometer composite hollow fibre ultrafilter membrane.Film properties parameter is as follows:
Embodiment 4
It is distinctive in that with embodiment 2: nano-attapulgite stone is before use through cationic surfactant modification, and method of modifying is: being added to the deionized water of 500ml by the nano-attapulgite stone of 5g, stirring prepares suspension；The temperature of suspension is regulated to 80 DEG C, adds the cationic surfactant of nano-attapulgite stone weight 3%, maintain temperature, stir 3h, after reaction bonded, sucking filtration, successively respectively washs 3 times with deionized water and dehydrated alcohol, dry, pulverize, to obtain final product.
1 gram of above-mentioned modified nano-attapulgite stone is joined 85 grams of triethyl phosphates wherein, after vigorous mechanical agitation and supersound process are uniform, add 15 grams of Kynoar powder body stirring and dissolving 24 hours at 80 DEG C, add 5 grams of Polyethylene Glycol and stir 12 hours to obtain casting solution, standing and defoaming 24 hours at 80 DEG C, adopting immersion precipitation phase inversion process, condition is: the dry journey of air is 30cm；Casting solution flow velocity is 2mL/min；Core liquid is deionized water, and its flow velocity is 6mL/min；Coagulating bath is deionized water, and water temperature, at 20～30 DEG C, prepares high flux attapulgite/polyvinylidene fluoride nanometer composite hollow fibre ultrafilter membrane.Film properties parameter is as follows:
As can be seen from the table, after nano-attapulgite stone is modified, ultrafilter membrane flux decline in filter process is less than unmodified, and this can improve the compatibility between nano-attapulgite stone and polymer after being likely due to modifiy.
Reference examples 2
It is different in that it is by obtaining modified for attapulgite Silane coupling reagent KH-570 with embodiment 3, method of modifying is: be sequentially added into 100ml toluene, 1ml water and 3.0g nano-attapulgite stone (at 105 DEG C predrying 2h) in the reactor, add 3ml silane coupler, ultrasonic 40min at 40～45 DEG C subsequently while stirring；Then under agitation constant temperature 45～50 DEG C reaction 4h, product removes unnecessary silane coupler with toluene, dehydrated alcohol and deionized water wash after being separated by filtration successively, drying at 105 DEG C, obtain silane coupler modified nano-attapulgite stone, ground 200 mesh sieves are standby.1 gram of above-mentioned modified nano-attapulgite stone is joined 85 grams of triethyl phosphates wherein, after vigorous mechanical agitation and supersound process are uniform, add 15 grams of Kynoar powder body stirring and dissolving 24 hours at 80 DEG C, add 5 grams of Polyethylene Glycol and stir 12 hours to obtain casting solution, standing and defoaming 24 hours at 80 DEG C, adopting immersion precipitation phase inversion process, condition is: the dry journey of air is 30cm；Casting solution flow velocity is 2mL/min；Core liquid is deionized water, and its flow velocity is 6mL/min；Coagulating bath is deionized water, and water temperature, at 20～30 DEG C, prepares high flux attapulgite/polyvinylidene fluoride nanometer composite hollow fibre ultrafilter membrane.
After measured, the pure water flux at 0.1MPa and 20 DEG C is 230L/ (m2H)；Being demarcate thing with glucosan, its molecular cut off is 210000Da；Film average pore size is about 30nm, and water droplet contact angle is 55.7 °；Fracture strength is about 3.2MPa, filters the flux decline about 70% of BSA solution.Compared with silane coupler modified nano-attapulgite stone, the modified of attapulgite is swapped by the cation on its attapulgite to carry out by cationic surfactant, do not affect the hydroxyl on attapulgite surface, and silane coupler modified nano-attapulgite stone is to be undertaken by the hydroxyl reaction of coupling agent Yu attapulgite surface, cause that the final flux of ultrafilter membrane for preparing, antifouling property all be not so good as employing cationic surfactant and modifiy the film obtained.
Claims (4)
1. attapulgite/polyvinylidene fluoride nanometer composite hyperfiltration membrane, it is characterised in that by weight, its raw material of preparing includes following component: polyvinylidene fluoride resin 15～20 parts, organic solvent 85～80 parts, nano-attapulgite stone, additive；The weight of described nano-attapulgite stone is the 0.5～15% of polyvinylidene fluoride resin weight, and the weight of described additive is the 2～6% of polyvinylidene fluoride resin and organic solvent gross mass；Described organic solvent is triethyl phosphate；The preparation method of described ultrafilter membrane comprises the steps: to add in organic solvent by nano-attapulgite stone, make mixed system homogenization, obtain casting solution, standing and defoaming after adding polyvinylidene fluoride resin and additive stirring and dissolving, adopt immersion precipitation phase inversion process to prepare ultrafilter membrane；Phase inversion adopts water as coagulating bath；Phase inversion adopts spin processes；Temperature in the process of homogenization controls at 75～85 DEG C；The time of stirring and dissolving is 24～36 hours；The time of standing and defoaming is 12～24 hours；The temperature of standing and defoaming is 75～85 DEG C；Technological parameter in spin processes is: the dry journey of air is 0～30cm；Casting solution flow velocity is 2～10mL/min；Core liquid is deionized water, and its flow velocity is 2～6mL/min；The water temperature of coagulating bath is at 20～30 DEG C.
2. attapulgite according to claim 1/polyvinylidene fluoride nanometer composite hyperfiltration membrane, it is characterised in that: described additive is selected from polyvinyl pyrrolidone, polyvinyl alcohol, polyacrylic acid, Polyethylene Glycol, lithium chloride, sodium chloride, calcium chloride, lithium nitrate, formaldehyde, Methanamide.
3. attapulgite according to claim 1/polyvinylidene fluoride nanometer composite hyperfiltration membrane, it is characterised in that: the fibre length of nano-attapulgite stone is 500～2000nm, and diameter is 30～70nm, and attapulgite content is not less than 95%.
4. attapulgite according to claim 1/polyvinylidene fluoride nanometer composite hyperfiltration membrane, it is characterised in that: described nano-attapulgite stone is that cationic surfactant modifiied.
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| CN108993171B (en) * | 2017-04-13 | 2021-06-11 | 淮阴师范学院 | Application of attapulgite in improving filtering flux of polyvinylidene fluoride ultrafiltration membrane |
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