CN116240674A - Preparation method of magnetic nanofiber membrane - Google Patents
Preparation method of magnetic nanofiber membrane Download PDFInfo
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- CN116240674A CN116240674A CN202310165934.XA CN202310165934A CN116240674A CN 116240674 A CN116240674 A CN 116240674A CN 202310165934 A CN202310165934 A CN 202310165934A CN 116240674 A CN116240674 A CN 116240674A
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43838—Ultrafine fibres, e.g. microfibres
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
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- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/541—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres
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- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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Abstract
The preparation method of the magnetic nanofiber membrane is characterized by comprising the following steps of: (1) preparation of resin-supported Fe 2 O 3 A nanocomposite; (2) preparing humic acid sodium salt solution; (3) taking resin to load Fe 2 O 3 Nanocomposite material, humic acidSodium solution and ammonia water, reacting, cooling and cleaning to obtain humic acid modified resin-carried Fe 2 O 3 A nanocomposite; (4) humic acid modified resin-carried Fe 2 O 3 Uniformly stirring the nanocomposite and polyvinyl alcohol to prepare electrostatic spinning precursor liquid; (5) and placing the electrostatic spinning precursor liquid into a liquid storage tank of electrostatic spinning equipment, and spinning by using non-woven fabrics as receiving base materials to prepare the nanofiber membrane. Adding humic acid modified resin-carried Fe in the process of electrostatic spinning of polyvinyl alcohol 2 O 3 The nanocomposite can improve the adsorption capacity to heavy metal and can be repeatedly used, and can be widely applied to the field of liquid filtration.
Description
Technical Field
The invention relates to a preparation method of a fiber membrane, which can remove heavy metals in water.
Background
Along with the further acceleration of the industrialization process, the demands of various enterprises for heavy metals are increased day by day, and meanwhile, a large amount of composite pollutants, such as heavy metal ions Cd, are inevitably discharged to the environment 2+ 、Pb 2+ Etc. The heavy metal ions not only seriously pollute surface water and underground water and lead to the rapid decline of global available water resources, but also increase the heavy metal content in soil and endanger ecological environment and human health.
Currently, methods for heavy metal treatment mainly include precipitation, membrane separation, ion exchange and adsorption. The precipitation method is to convert heavy metal ions in the wastewater solution into precipitate by using a certain mass of precipitant; membrane separation techniques, which generally use the action of an external force to cause a solution to pass through a selective semipermeable membrane to separate the solvent from the solution, mainly include: ultrafiltration, nanofiltration, reverse osmosis, microfiltration, etc.; the ion exchange resin is an active group substance which is reacted with heavy metal and is arranged on the ion exchange resin, and the group can form chelation with the heavy metal ion, so that the purpose of removing the heavy metal ion is achieved. The adsorption method can deeply treat low-concentration heavy metal wastewater, and the treated effluent has high water quality, strong operability, economy and effectiveness, and the currently used adsorption materials are substances such as zeolite, quartz sand, lignin, cellulose and the like.
The magnetic nano material has the advantages of large specific surface area, easy functionalization, stable property and the like. Wherein, magnetic Fe 2 O 3 The nanoparticles are directionally movable in the magnetic field and can be further separated. Thus, regarding magnetic Fe 2 O 3 The removal of contaminants from wastewater by nanoparticles has been studied more. But Fe is 2 O 3 The nano particles have the defects of easy agglomeration and the like, thereby affecting the stability of the composite material, so the nano particles have the advantages of magnetic Fe 2 O 3 Modification studies of nanoparticles are an important method for improving the performance of the nanoparticles.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a magnetic nanofiber membrane capable of adsorbing heavy metals.
The technical scheme adopted for solving the technical problems is as follows: the preparation method of the magnetic nanofiber membrane is characterized by comprising the following steps of:
(1) taking Fe 2 O 3 Adding ethanol and ultrapure water into the nano particles in a first container to obtain Fe 3 O 4 An ethanol suspension; adding solvent and polyethylene oxide into the suspension, uniformly mixing, slowly adding initiator, and reacting to obtain resin-loaded Fe 2 O 3 A nanocomposite;
(2) adding sodium humate in a second container, adding ultrapure water, and stirring to obtain sodium humate solution;
(3) taking resin to load Fe 2 O 3 Adding ultrapure water into a third container, heating in water bath, rapidly adding sodium humate solution and ammonia water (the ammonia water mainly plays a role in catalysis, creating a weak base environment, promoting the reaction between humic acid and resin-carried ferric oxide), reacting under stirring,cooling, and cleaning the material to be neutral by using ultrapure water to obtain the humic acid modified resin-loaded Fe2O3 nanocomposite;
(4) adding N, N-dimethylformamide solvent and humic acid modified resin-carried Fe into a fourth container 2 O 3 Stirring the nanocomposite into a homogeneous solution, adding dodecyldimethylamine oxide, stirring, adding polyvinyl alcohol, stirring to completely dissolve the polyvinyl alcohol, cooling after completely dissolving, adding lithium salt, and stirring uniformly to prepare an electrostatic spinning precursor solution;
(5) and placing the electrostatic spinning precursor liquid into a liquid storage tank of electrostatic spinning equipment, and spinning by using non-woven fabrics as receiving base materials to prepare the nanofiber membrane.
Preferably, the Fe in step (1) 2 O 3 The diameter of the nano particles is 20-50 nm, fe 2 O 3 The weight ratio of the nano particles to the polyethylene oxide is 0.1-0.3:30-40, and the resin carries Fe 2 O 3 In the nanocomposite material, fe 2 O 3 The loading amount of (2) is 10-15 mol%.
Preferably, the solvent in the step (1) is at least one of cyclohexane, oleic acid, methyl acetate and ethyl acetate; the initiator is at least one of potassium persulfate, azodiisobutyronitrile and tert-butyl hydroperoxide.
Preferably, the humic acid modified resin-supported Fe2O3 nanocomposite obtained in the step (3) is a microsphere with a diameter of 0.6-1.0 mm.
Preferably, in the step (4), the mass ratio of the N, N-dimethylformamide solvent to the polyvinyl alcohol is 70:8-70:20, the mass ratio of the N, N-dimethylformamide solvent to the resin-carried Fe2O3 nanocomposite is 70:1-70:9, and the mass ratio of the N, N-dimethylformamide solvent to the lithium salt is 70:1-70:4; the mass ratio of the N, N-dimethylformamide solvent to the dodecyl dimethyl amine oxide is 70:4-70:8.
Preferably, the spinning conditions in step (5) are as follows: the spinning voltage is 70-95 kv, the distance between the electrode thread and the collector is 15-25 cm, the liquid supply speed is 5-200 ml/h, the collector speed is 0.01-0.05 m/min, the spinning temperature is 20-40 ℃, and the humidity is 20-40%.
Preferably, the specific surface area of the nanofiber membrane obtained in the step (5) is 600-760 m2/g, the porosity is 70-80%, and the fiber diameter is 50-150 nm.
Preferably, the lithium salt in the step (5) is at least one of lithium chloride, lithium acetate and lithium formate.
Preferably, the molecular weight of the polyvinyl alcohol in the step (5) is 60000 to 120000, and the viscosity of the electrospinning precursor solution is 200 to 2000mpa·s.
The whole preparation of the nanofiber membrane can be concretely realized by adopting the following technical contents: the method comprises the following steps:
weighing 0.1g-0.3g Fe 2 O 3 Adding the nano material into a round bottom flask, adding 80ml-150ml ethanol and 45ml-60ml ultrapure water to obtain Fe 3 O 4 Ethanol suspension. Adding 20ml-30ml solvent and 30g-40g polyethylene oxide into the suspension, stirring for 20-30 min at room temperature, slowly adding 10ml-15ml initiator after mixing uniformly, reacting for 1h to obtain resin-carried Fe 2 O 3 A nanocomposite.
Weighing 0.5g-1.5g of humic acid sodium salt in a round bottom flask, adding 50ml-60ml of ultrapure water, continuously stirring for 30-40 min, and weighing 40g-50g of resin-loaded Fe 2 O 3 The nanocomposite material was placed in a three-necked flask, and 100ml to 120ml of ultrapure water was added thereto, and the mixture was heated to 80℃in a water bath. Rapidly adding the sodium humate solution dissolved by shaking and 5ml-10ml of ammonia water, stirring for 1.5-2 h, and continuously maintaining the reaction at 80 ℃. Then the heating was stopped and cooled to room temperature, and the material was washed to neutrality with ultrapure water.
Third step, adding N, N-dimethylformamide solvent and humic acid modified resin-carried Fe into a round-bottomed flask 2 O 3 Stirring the nano composite material for 50-60 min at 30-40 ℃ to form a homogeneous solution, adding dodecyldimethylamine oxide, keeping the temperature unchanged, continuously stirring for 20-30 min, adding polyvinyl alcohol, stirring for 10-20 min at 60 ℃ to completely dissolve the polyvinyl alcohol, cooling after completely dissolving, adding lithium salt, and stirring for 25-35min to uniformly prepare the electrostatic spinningPrecursor liquid.
And fourthly, placing the electrostatic spinning precursor liquid into a liquid storage tank of electrostatic spinning equipment, taking non-woven fabrics as receiving base materials, and starting spinning after the power is turned on to prepare the nanofiber membrane.
Preparing and testing performance of the filter element: the spun nanofiber membrane is rolled into a filter core with the length of 2.5 meters by a central tube and a diversion cloth, 26g of standard solution of cadmium ions and lead ions are respectively weighed in a water bucket with the length of 1000 liters to prepare the standard solution with the concentration of 26ug/L, the PH value of the standard solution is regulated by sodium hydroxide, the standard solution containing the heavy metal ions passes through the filter core through a lapped waterway, the adsorbed water sample is taken every other hour, diluted and stored by 0.2 percent dilute nitric acid, and the solubility of residual heavy metal in the sample is measured by an atomic absorption spectrophotometer.
Compared with the prior art, the invention has the advantages that: fe (Fe) 2 O 3 The nano material has the characteristics of superparamagnetism, easy synthesis, no toxicity and the like, can be applied to enrichment and separation of heavy metal ions in seawater, has superparamagnetism and magnetic responsiveness, so that the separation method becomes very simple and convenient, and can rapidly realize Fe only under the action of an external magnetic field 2 O 3 The adsorbent is separated and recycled, so that the subsequent treatment of heavy metal ion adsorption is simplified. Fe of 2 O 3 After being loaded on polyethylene oxide, the specific surface area is increased, and the Fe is relieved 2 O 3 The polymer is easy to agglomerate, and the humic acid is used for loading Fe on resin 2 O 3 After the nano composite material is modified, the surface activity of the material is effectively improved, and meanwhile, the excellent heavy metal adsorption capacity is endowed to the material, so that the adsorption capacity is improved. Fe carried on resin by humic acid 2 O 3 The nano composite material is modified, because humic acid contains a large amount of carboxyl, phenolic hydroxyl and quinone, the functional groups have strong capability of complexing heavy metals, and meanwhile, the functional groups can act with ferric oxide, so that the humic acid can be covalently bonded to resin-carried Fe 2 O 3 The surface of the nano composite material is endowed with resin-carried Fe 2 O 3 The ability of the nanocomposite to adsorb heavy metals.
The polyvinyl alcohol is selected as the polymer for electrostatic spinning mainly because the molecular structure contains hydroxyl and can carry Fe with resin 2 O 3 The hydrogen bond is formed between ether bonds in the polyethylene oxide in the nanocomposite, so that the crystal structure of the polyvinyl alcohol is influenced, the morphology of the fiber is further influenced, and the fiber with smaller diameter and larger specific surface area is obtained. Meanwhile, after hydrogen bond is formed, fe can be improved 2 O 3 Stability in fibrous membranes, thereby providing efficient separation and recovery. The dodecyl dimethyl amine has good chemical stability, can effectively solve the problems of uniform pore diameter and size control, improves the porosity and pore permeability, and can effectively adsorb even under the condition of low heavy metal concentration. In addition, the introduction of the dodecyl dimethyl amine can provide a water channel, can combine a large number of water molecules, improves the hydrophilicity of the surface of the membrane, forms a hydration layer on the surface of the membrane, and can effectively improve the flux.
The electrostatic spinning method has the advantages of wide raw material source range, good controllability of fiber structure, strong expansibility of preparation process and the like, the diameter of the fiber obtained by electrostatic spinning is hundreds of nanometers, and the material piled by the fiber has the characteristics of small pore diameter, high porosity, good fiber continuity, controllable stacking density and the like, and has wide application prospect in the fields of electronic information, environmental management, energy, safety protection, tissue engineering and the like.
The preparation method has the advantages of simple process, mild condition and easy control, the adopted raw materials are nontoxic or low-toxicity raw materials, the raw material consumption is low in the reaction process, the cost is low, toxic byproducts are not generated, and the preparation method belongs to an environment-friendly synthesis method. The fiber has higher content of functional groups, keeps good shape and strength, and has wide application prospect in aspects of functional textiles, water and air purification, chemical substance separation and extraction and the like.
Adding humic acid modified resin-carried Fe in the process of electrostatic spinning of polyvinyl alcohol 2 O 3 The nanocomposite and the dodecyl dimethyl amine oxide can improve the adsorption capacity to heavy metals and can be repeatedly utilized, and can be widely applied to the field of liquid filtration.
Detailed Description
The present invention is described in further detail below with reference to examples.
Example 1
(1) Weigh 0.1g Fe 2 O 3 Adding the nano material into a round-bottomed flask, adding 80ml of ethanol and 45ml of ultrapure water to obtain Fe 3 O 4 -ethanol suspension. Adding 20ml of cyclohexane and 30g of polyethylene oxide into the suspension, continuously stirring at room temperature for 20min, slowly adding 10ml of azodiisobutyronitrile after uniformly mixing, and reacting for 1h to obtain resin-carried Fe 2 O 3 A nanocomposite.
(2) Weighing 0.5g of humic acid sodium salt into a round bottom flask, adding 50ml of ultrapure water, continuously stirring for 30min, and weighing 40g of resin-carried Fe 2 O 3 The nanocomposite was placed in a three-necked flask, and 100ml of ultrapure water was added thereto, followed by heating in a water bath to 80 ℃. Rapidly adding the sodium humate solution dissolved by shaking and 5ml of ammonia water, and continuously maintaining the temperature of 80 ℃ for reaction for 1.5h under stirring. Then the heating was stopped and cooled to room temperature, and the material was washed to neutrality with ultrapure water.
(3) 700g of N, N-dimethylformamide solvent and 50g of humic acid modified resin-supported Fe were charged into a round bottom flask 2 O 3 Stirring the nanocomposite at 30 ℃ for 50min to form a homogeneous solution, adding 50g of dodecyl dimethyl amine oxide, keeping the temperature unchanged, continuously stirring for 20min, adding 120g of polyvinyl alcohol with the molecular weight of 60000, continuously stirring at 60 ℃ to enable the polyvinyl alcohol to be completely dissolved, cooling to 0 ℃, adding 25g of lithium chloride, stirring for 10min to uniformly prepare an electrostatic spinning precursor solution, wherein the viscosity of the spinning solution is 300 mPa.s.
(4) And placing the electrostatic spinning precursor liquid prepared in the steps in a liquid storage device of electrostatic spinning equipment, connecting the device with a spinning needle head, and switching on a power supply to spin. The voltage during electrostatic spinning was set at 70kv, the distance between the electrode screw and the collector was 15cm, the liquid supply speed was 5ml/h, the collector speed was 0.01m/min, the spinning temperature was 20℃and the humidity was 20%, and the spun nanofiber membrane was collected with a nonwoven fabric.
(5) Preparation and performance test of the filter element: the spun nanofiber membrane is rolled into a filter core with the length of 2.5 meters by a central tube and a diversion cloth, 26g of standard solution of cadmium ions and lead ions are respectively weighed in a water bucket with the length of 1000 liters to prepare the standard solution with the concentration of 26ug/L, the PH value of the standard solution is regulated by sodium hydroxide, the standard solution containing the heavy metal ions passes through the filter core through a lapped waterway, the adsorbed water sample is taken every other hour, diluted and stored by 0.2 percent dilute nitric acid, and the solubility of residual heavy metal in the sample is measured by an atomic absorption spectrophotometer.
Example 2
(1) Weigh 0.2g Fe 2 O 3 Adding the nano material into a round-bottomed flask, adding 100ml of ethanol and 50ml of ultrapure water to obtain Fe 3 O 4 -ethanol suspension. Adding 25ml of cyclohexane and 35g of polyethylene oxide into the suspension, continuously stirring at room temperature for 25min, slowly adding 12ml of azodiisobutyronitrile after uniformly mixing, and reacting for 1h to obtain resin-carried Fe 2 O 3 A nanocomposite.
(2) 1.0g of humic acid sodium salt is weighed into a round bottom flask, 55ml of ultrapure water is added for continuous stirring for 35min, and 45g of resin-carried Fe is weighed 2 O 3 The nanocomposite was placed in a three-necked flask, 110ml of ultrapure water was added thereto, and the mixture was heated to 80℃in a water bath. Rapidly adding the sodium humate solution dissolved by shaking and 8ml of ammonia water, and continuously maintaining the temperature of 80 ℃ for reaction for 1.7h under stirring. Then the heating was stopped and cooled to room temperature, and the material was washed to neutrality with ultrapure water.
(3) 700g of N, N-dimethylformamide solvent and 50g of humic acid modified resin-supported Fe were charged into a round bottom flask 2 O 3 Stirring the nanocomposite material at 35 ℃ for 55min to form a homogeneous solution, adding 50g of dodecyl dimethyl amine oxide, keeping the temperature unchanged, continuously stirring for 25min, adding 120g of polyvinyl alcohol with molecular weight of 90000, continuously stirring at 60 ℃ to enable the polyvinyl alcohol to be completely dissolved, cooling to 3 ℃, adding 50g of lithium chloride, stirring for 15min to uniformly prepare an electrostatic spinning precursor solution, wherein the viscosity of the spinning solution is 700 mPa.s.
(4) And placing the electrostatic spinning precursor liquid prepared in the steps in a liquid storage device of electrostatic spinning equipment, connecting the device with a spinning needle head, and switching on a power supply to spin. The voltage during electrostatic spinning was set at 80kv, the distance between the electrode screw thread and the collector was 20cm, the liquid feeding speed was 50ml/h, the collector speed was 0.03m/min, the spinning temperature was 30℃and the humidity was 30%, and the spun nanofiber membrane was collected with a nonwoven fabric.
(5) Preparation and performance test of the filter element: the spun nanofiber membrane is rolled into a filter core with the length of 2.5 meters by a central tube and a diversion cloth, 26g of standard solution of cadmium ions and lead ions are respectively weighed in a water bucket with the length of 1000 liters to prepare the standard solution with the concentration of 26ug/L, the PH value of the standard solution is regulated by sodium hydroxide, the standard solution containing the heavy metal ions passes through the filter core through a lapped waterway, the adsorbed water sample is taken every other hour, diluted and stored by 0.2 percent dilute nitric acid, and the solubility of residual heavy metal in the sample is measured by an atomic absorption spectrophotometer.
Example 3
(1) Weigh 0.3gFe 2 O 3 Adding the nano material into a round-bottomed flask, adding 150ml of ethanol and 60ml of ultrapure water to obtain Fe 3 O 4 -ethanol suspension. Adding 30ml of cyclohexane and 40g of polyethylene oxide into the suspension, continuously stirring for 30min at room temperature, slowly adding 15ml of azodiisobutyronitrile after uniformly mixing, and reacting for 1h to obtain resin-carried Fe 2 O 3 A nanocomposite.
(2) 1.5g of humic acid sodium salt is weighed into a round bottom flask, 60ml of ultrapure water is added and is continuously stirred for 40min, and 50g of resin-carried Fe is weighed 2 O 3 The nanocomposite was placed in a three-necked flask, 120ml of ultrapure water was added thereto, and the mixture was heated to 80℃in a water bath. Rapidly adding the sodium humate solution dissolved by shaking and 10ml of ammonia water, and continuously maintaining the temperature of 80 ℃ for reaction for 2 hours under stirring. Then the heating was stopped and cooled to room temperature, and the material was washed to neutrality with ultrapure water.
(3) 700g of N, N-dimethylformamide solvent and 50g of humic acid modified resin-supported Fe were charged into a round bottom flask 2 O 3 Stirring the nanocomposite at 40 ℃ for 60min to obtain a homogeneous solution, adding 50g of dodecyldimethylamine oxide, keeping the temperature unchanged, continuously stirring for 30min, and adding 120g of molecular weightAnd (3) stirring the mixture at 60 ℃ continuously to dissolve the polyvinyl alcohol completely, cooling to 5 ℃ after dissolving the polyvinyl alcohol completely, adding 50g of lithium chloride, and stirring the mixture for 20min uniformly to prepare the electrostatic spinning precursor solution, wherein the viscosity of the spinning solution is 1500 mPa.s.
(4) And placing the electrostatic spinning precursor liquid prepared in the steps in a liquid storage device of electrostatic spinning equipment, connecting the device with a spinning needle head, and switching on a power supply to spin. The voltage during electrostatic spinning was 95kv, the distance between the electrode screw thread and the collector was 25cm, the liquid feeding speed was 150ml/h, the collector speed was 0.05m/min, the spinning temperature was 40℃and the humidity was 40%, and the spun nanofiber membrane was collected with a nonwoven fabric.
(5) Preparation and performance test of the filter element: the spun nanofiber membrane is rolled into a filter core with the length of 2.5 meters by a central tube and a diversion cloth, 26g of standard solution of cadmium ions and lead ions are respectively weighed in a water bucket with the length of 1000 liters to prepare the standard solution with the concentration of 26ug/L, the PH value of the standard solution is regulated by sodium hydroxide, the standard solution containing the heavy metal ions passes through the filter core through a lapped waterway, the adsorbed water sample is taken every other hour, diluted and stored by 0.2 percent dilute nitric acid, and the solubility of residual heavy metal in the sample is measured by an atomic absorption spectrophotometer.
Comparative example 1 comparative Fe without polyethylene oxide 2 O 3 Modification
(1) 1.5g of humic acid sodium salt is weighed into a round bottom flask, 60ml of ultrapure water is added and is continuously stirred for 40min, and 50g of Fe is weighed 2 O 3 The nanomaterial was placed in a three-necked flask, 120ml of ultra-pure water was added, and the flask was heated to 80℃in a water bath. Rapidly adding the sodium humate solution dissolved by shaking and 10ml of ammonia water, and continuously maintaining the temperature of 80 ℃ for reaction for 2 hours under stirring. Then the heating was stopped and cooled to room temperature, and the material was washed to neutrality with ultrapure water.
(2) 700g of N, N-dimethylformamide solvent and 50g of humic acid-modified Fe were introduced into a round-bottomed flask 2 O 3 Stirring nanometer material at 40deg.C for 60min to obtain homogeneous solution, adding 50g of dodecyldimethylamine oxide, keeping the temperature unchanged, stirring for 30min, adding 120g of 120000 molecular weight polyvinyl alcohol, and stirring at 60deg.CAnd (3) completely dissolving the polyvinyl alcohol, cooling to 5 ℃, adding 50g of lithium chloride, and stirring for 20min uniformly to prepare an electrostatic spinning precursor solution, wherein the viscosity of the spinning solution is 1500 mPa.s.
(3) And placing the electrostatic spinning precursor liquid prepared in the steps in a liquid storage device of electrostatic spinning equipment, connecting the device with a spinning needle head, and switching on a power supply to spin. The voltage during electrostatic spinning was 95kv, the distance between the electrode screw thread and the collector was 25cm, the liquid feeding speed was 150ml/h, the collector speed was 0.05m/min, the spinning temperature was 40℃and the humidity was 40%, and the spun nanofiber membrane was collected with a nonwoven fabric.
(4) Preparation and performance test of the filter element: the spun nanofiber membrane is rolled into a filter core with the length of 2.5 meters by a central tube and a diversion cloth, 26g of standard solution of cadmium ions and lead ions are respectively weighed in a water bucket with the length of 1000 liters to prepare the standard solution with the concentration of 26ug/L, the PH value of the standard solution is regulated by sodium hydroxide, the standard solution containing the heavy metal ions passes through the filter core through a lapped waterway, the adsorbed water sample is taken every other hour, diluted and stored by 0.2 percent dilute nitric acid, and the solubility of residual heavy metal in the sample is measured by an atomic absorption spectrophotometer.
Comparative example 2 resin-supported Fe without humic acid 2 O 3 Nanocomposite modification
(1) Weigh 0.3gFe 2 O 3 Adding the nano material into a round-bottomed flask, adding 150ml of ethanol and 60ml of ultrapure water to obtain Fe 3 O 4 -ethanol suspension. Adding 30ml of cyclohexane and 40g of polyethylene oxide into the suspension, continuously stirring for 30min at room temperature, slowly adding 15ml of azodiisobutyronitrile after uniformly mixing, and reacting for 1h to obtain resin-carried Fe 2 O 3 A nanocomposite.
(2) 700g of N, N-dimethylformamide solvent and 50g of resin-supported Fe were charged into a round-bottomed flask 2 O 3 Stirring the nanocomposite at 40 ℃ for 60min to obtain a homogeneous solution, adding 50g of dodecyldimethylamine oxide, keeping the temperature unchanged, continuously stirring for 30min, adding 120g of polyvinyl alcohol with the molecular weight of 120000, continuously stirring at 60 ℃ to completely dissolve the polyvinyl alcohol,after the solution is completely dissolved and cooled to 5 ℃, 50g of lithium chloride is added, and the solution is stirred for 20min to prepare the electrostatic spinning precursor solution, wherein the viscosity of the spinning solution is 1500 mPa.s.
(3) And placing the electrostatic spinning precursor liquid prepared in the steps in a liquid storage device of electrostatic spinning equipment, connecting the device with a spinning needle head, and switching on a power supply to spin. The voltage during electrostatic spinning was 95kv, the distance between the electrode screw thread and the collector was 25cm, the liquid feeding speed was 150ml/h, the collector speed was 0.05m/min, the spinning temperature was 40℃and the humidity was 40%, and the spun nanofiber membrane was collected with a nonwoven fabric.
(4) Preparation and performance test of the filter element: the spun nanofiber membrane is rolled into a filter core with the length of 2.5 meters by a central tube and a diversion cloth, 26g of standard solution of cadmium ions and lead ions are respectively weighed in a water bucket with the length of 1000 liters to prepare the standard solution with the concentration of 26ug/L, the PH value of the standard solution is regulated by sodium hydroxide, the standard solution containing the heavy metal ions passes through the filter core through a lapped waterway, the adsorbed water sample is taken every other hour, diluted and stored by 0.2 percent dilute nitric acid, and the solubility of residual heavy metal in the sample is measured by an atomic absorption spectrophotometer.
Comparative example 3 no dodecyldimethylamine oxide was added
(1) Weigh 0.3gFe 2 O 3 Adding the nano material into a round-bottomed flask, adding 150ml of ethanol and 60ml of ultrapure water to obtain Fe 3 O 4 -ethanol suspension. Adding 30ml of cyclohexane and 40g of polyethylene oxide into the suspension, continuously stirring for 30min at room temperature, slowly adding 15ml of azodiisobutyronitrile after uniformly mixing, and reacting for 1h to obtain resin-carried Fe 2 O 3 A nanocomposite.
(2) 1.5g of humic acid sodium salt is weighed into a round bottom flask, 60ml of ultrapure water is added and is continuously stirred for 40min, and 50g of resin-carried Fe is weighed 2 O 3 The nanocomposite was placed in a three-necked flask, 120ml of ultrapure water was added thereto, and the mixture was heated to 80℃in a water bath. Rapidly adding the sodium humate solution dissolved by shaking and 10ml of ammonia water, and continuously maintaining the temperature of 80 ℃ for reaction for 2 hours under stirring. Then the heating was stopped and cooled to room temperature, and the material was washed to neutrality with ultrapure water.
(3) 700g of N, N-dimethylformamide solvent and 50g of humic acid modified resin-supported Fe were charged into a round bottom flask 2 O 3 Stirring the nanocomposite material at 40 ℃ for 60min to form a homogeneous solution, adding 120g of polyvinyl alcohol with the molecular weight of 120000, continuously stirring at 60 ℃ to completely dissolve the polyvinyl alcohol, cooling to 5 ℃ after completely dissolving, adding 50g of lithium chloride, and stirring for 20min to uniformly prepare an electrostatic spinning precursor solution, wherein the viscosity of the spinning solution is 1500 mPa.s.
(4) And placing the electrostatic spinning precursor liquid prepared in the steps in a liquid storage device of electrostatic spinning equipment, connecting the device with a spinning needle head, and switching on a power supply to spin. The voltage during electrostatic spinning was 95kv, the distance between the electrode screw thread and the collector was 25cm, the liquid feeding speed was 150ml/h, the collector speed was 0.05m/min, the spinning temperature was 40℃and the humidity was 40%, and the spun nanofiber membrane was collected with a nonwoven fabric
(5) Preparation and performance test of the filter element: the spun nanofiber membrane is rolled into a filter core with the length of 2.5 meters by a central tube and a diversion cloth, 26g of standard solution of cadmium ions and lead ions are respectively weighed in a water bucket with the length of 1000 liters to prepare the standard solution with the concentration of 26ug/L, the PH value of the standard solution is regulated by sodium hydroxide, the standard solution containing the heavy metal ions passes through the filter core through a lapped waterway, the adsorbed water sample is taken every other hour, diluted and stored by 0.2 percent dilute nitric acid, and the solubility of residual heavy metal in the sample is measured by an atomic absorption spectrophotometer.
The results of the heavy metal adsorption experiments performed on the cartridges made of nanofibers of examples 1-3 and comparative examples 1-3 are shown in table 1:
according to the previous description, 26g of standard solution of cadmium ions and lead ions is weighed into a 1000 liter bucket to prepare standard solution with the concentration of 26ug/L, the PH value of the standard solution is regulated by sodium hydroxide, the standard solution containing heavy metal ions passes through a filter core through a lapped waterway, the adsorbed water sample is taken every other hour, the water sample is taken for 10 hours, the water sample is diluted and stored by 0.2% dilute nitric acid, and the solubility of the residual heavy metal in the sample is measured by an atomic absorption spectrophotometer.
TABLE 1
From table 1, it is clear that the nanofiber membrane prepared by the modification method of the present invention has a good adsorption effect on heavy metals.
To further confirm that the addition of dodecyldimethylamine oxide contributes to the improvement of porosity and permeability of the fibrous membrane, relevant tests were performed, the test results being shown in Table 2
The flux test method is as follows: and (3) connecting the pipelines well, allowing water to pass through the filter core, stabilizing the reading of the pressure gauge at 0.1MPa by controlling the switch of the return pipeline, starting water receiving from the water outlet pipeline container after the water outlet is stabilized, stopping water receiving after timing for one minute, and converting the mass of the water into volume.
TABLE 2
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Porosity (%) | 70 | 76 | 80 | 68 | 56 | 24 |
| Specific surface area (m) 2 /g) | 604 | 662 | 758 | 583 | 539 | 298 |
| Flux (L/min) | 4.1 | 4.2 | 4.4 | 3.5 | 3.4 | 1.9 |
From table 2, it can be seen that the addition of dodecyldimethylamine can increase the specific surface area and porosity of the fibrous membrane, thereby increasing the flux of the filter element.
To further verify the modified magnetic Fe 2 The incorporation of O3 improved the recyclability of the fibrous membrane adsorbent material, and related tests were performed, with the test results shown in Table 3.
We add nanofiber membranes that adsorb heavy metal ions to Na 2 Desorbing in EDTA eluent, collecting adsorbent under the action of external magnetic field, washing with deionized water, vacuum drying at 50deg.C, adsorbing for 5 times according to the method described in Table 1, and collecting the result as shown in Table 3
TABLE 3 Table 3
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Cd after 5 times adsorption 2+ Concentration (ug/L) | 2.371 | 2.279 | 2.385 | 16.392 | 23.872 | 14.694 |
| Cd 2+ Adsorption Rate (%) | 90.8 | 91.2 | 90.8 | 36.9 | 8.18 | 43.4 |
| Pb after 5 times adsorption 2+ Concentration (ug/L) | 2.482 | 2.182 | 2.586 | 13.381 | 25.011 | 15.803 |
| Pb 2+ Adsorption Rate (%) | 90.4 | 91.6 | 90.0 | 48.5 | 3.80 | 39.2 |
From the above table, it is clear that the nanofiber membrane of the present invention has excellent recyclability.
Claims (9)
1. The preparation method of the magnetic nanofiber membrane is characterized by comprising the following steps of:
(1) taking Fe 2 O 3 Adding ethanol and ultrapure water into the nano particles in a first container to obtain Fe 3 O 4 An ethanol suspension; adding solvent and polyethylene oxide into the suspension, uniformly mixing, slowly adding initiator, and reacting to obtain resin-loaded Fe 2 O 3 A nanocomposite;
(2) adding sodium humate in a second container, adding ultrapure water, and stirring to obtain sodium humate solution;
(3) taking resin to load Fe 2 O 3 Adding ultrapure water into a third container, heating in a water bath, rapidly adding sodium humate solution and ammonia water, reacting under stirring, cooling, and cleaning the material with ultrapure water to neutrality to obtain humic acid modified resin-carried Fe 2 O 3 A nanocomposite;
(4) adding N, N-dimethyl into a fourth containerResin-supported Fe modified by formamide solvent and humic acid 2 O 3 Stirring the nanocomposite into a homogeneous solution, adding dodecyldimethylamine oxide, stirring, adding polyvinyl alcohol, stirring to completely dissolve the polyvinyl alcohol, cooling after completely dissolving, adding lithium salt, and stirring uniformly to prepare an electrostatic spinning precursor solution;
(5) and placing the electrostatic spinning precursor liquid into a liquid storage tank of electrostatic spinning equipment, and spinning by using non-woven fabrics as receiving base materials to prepare the nanofiber membrane.
2. The production method according to claim 1, characterized in that the Fe in step (1) 2 O 3 The diameter of the nano particles is 20-50 nm, fe 2 O 3 The weight ratio of the nano particles to the polyethylene oxide is 0.1-0.3:30-40, and the resin carries Fe 2 O 3 In the nanocomposite material, fe 2 O 3 The loading amount of (2) is 10-15 mol%.
3. The preparation method according to claim 1, wherein the solvent in the step (1) is at least one of cyclohexane, oleic acid, methyl acetate and ethyl acetate; the initiator is at least one of potassium persulfate, azodiisobutyronitrile and tert-butyl hydroperoxide.
4. The preparation method according to claim 1, wherein the humic acid modified resin-supported Fe2O3 nanocomposite obtained in the step (3) is a microsphere having a diameter of 0.6 to 1.0 mm.
5. The preparation method according to claim 1, wherein in the step (4), the mass ratio of the N, N-dimethylformamide solvent to the polyvinyl alcohol is 70:8-70:20, the mass ratio of the N, N-dimethylformamide solvent to the resin-carried Fe2O3 nanocomposite is 70:1-70:9, and the mass ratio of the N, N-dimethylformamide solvent to the lithium salt is 70:1-70:4; the mass ratio of the N, N-dimethylformamide solvent to the dodecyl dimethyl amine oxide is 70:4-70:8.
6. The process according to claim 1, wherein the spinning conditions in step (5) are as follows: the spinning voltage is 70-95 kv, the distance between the electrode thread and the collector is 15-25 cm, the liquid supply speed is 5-200 ml/h, the collector speed is 0.01-0.05 m/min, the spinning temperature is 20-40 ℃, and the humidity is 20-40%.
7. The method according to claim 1, wherein the nanofiber membrane obtained in the step (5) has a specific surface area of 600 to 760m2/g, a porosity of 70 to 80% and a fiber diameter of 50 to 150nm.
8. The method according to claim 1, wherein the lithium salt in the step (5) is at least one of lithium chloride, lithium acetate and lithium formate.
9. The method according to claim 1, wherein the polyvinyl alcohol in the step (5) has a molecular weight of 60000 to 120000 and a viscosity of 200 to 2000 mPa.s.
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