CN116239853A - Preparation method of composite nano microsphere and application of composite nano microsphere in preparation of nanofiber membrane - Google Patents
Preparation method of composite nano microsphere and application of composite nano microsphere in preparation of nanofiber membrane Download PDFInfo
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- CN116239853A CN116239853A CN202310174232.8A CN202310174232A CN116239853A CN 116239853 A CN116239853 A CN 116239853A CN 202310174232 A CN202310174232 A CN 202310174232A CN 116239853 A CN116239853 A CN 116239853A
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- Prior art keywords
- solution
- bentonite
- chitosan
- composite nano
- stirring
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- 239000004005 microsphere Substances 0.000 title claims abstract description 43
- 239000012528 membrane Substances 0.000 title claims abstract description 42
- 239000002121 nanofiber Substances 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 99
- 239000000440 bentonite Substances 0.000 claims abstract description 87
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 87
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 87
- 229920001661 Chitosan Polymers 0.000 claims abstract description 79
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000011259 mixed solution Substances 0.000 claims abstract description 51
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 44
- 229920002635 polyurethane Polymers 0.000 claims abstract description 29
- 239000004814 polyurethane Substances 0.000 claims abstract description 29
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims abstract description 26
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 20
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 18
- 239000012498 ultrapure water Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000001509 sodium citrate Substances 0.000 claims abstract description 15
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- 238000004132 cross linking Methods 0.000 claims abstract description 10
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 94
- 238000003756 stirring Methods 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 64
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 54
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 32
- 238000009987 spinning Methods 0.000 claims description 32
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 238000001291 vacuum drying Methods 0.000 claims description 19
- 239000012456 homogeneous solution Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
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- 238000007664 blowing Methods 0.000 claims description 9
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- 239000011541 reaction mixture Substances 0.000 claims description 8
- 230000008961 swelling Effects 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001523 electrospinning Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 43
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- 239000012086 standard solution Substances 0.000 description 36
- 150000002500 ions Chemical class 0.000 description 19
- 239000011734 sodium Substances 0.000 description 17
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- 238000010521 absorption reaction Methods 0.000 description 9
- 239000003570 air Substances 0.000 description 9
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 9
- -1 lead ions Chemical class 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 9
- 239000004744 fabric Substances 0.000 description 8
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- 238000004090 dissolution Methods 0.000 description 7
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- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 6
- 230000002572 peristaltic effect Effects 0.000 description 6
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- 230000000052 comparative effect Effects 0.000 description 5
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
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- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 239000013535 sea water Substances 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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Abstract
The preparation method of the composite nano microsphere is characterized by comprising the following steps: (1) preparing modified chitosan; (2) preparing acidified bentonite; (3) by means of acidified bentonite, modified chitosan, sodium polyacrylate and ZrO 2 The nano particles obtain uniform bentonite chitosan Zr mixed solution; (4) slowly dripping bentonite chitosan Zr mixed solution into a mixed solution of sodium citrate and sodium hydroxide, and standing; then adding a mixed solution of ultrapure water and ethylene glycol diglycidyl ether, and after crosslinking, alternately washing with ultrapure water and ethanol to obtain the composite nano-microsphere. The invention also discloses application of the composite nano microsphere in a nanofiber membrane. Chitosan sodium polyacrylate acidized bentonite ZrO is added in the process of electrostatic spinning of polyurethane 2 The composite nano microsphere can improve the heavy metal adsorption capacity and can be reused.
Description
Technical Field
The invention relates to a preparation method of a nano microsphere, which can be applied to a nanofiber membrane for adsorbing heavy metals.
Background
With further acceleration of industrialization progress, various types of productsThe demand of enterprises for heavy metals is increasing, and meanwhile, a large amount of complex 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 ZrO 2 The nanoparticles are directionally movable in the magnetic field and can be further separated. Thus, regarding magnetic ZrO 2 The removal of contaminants from wastewater by nanoparticles has been studied more. But ZrO 2 The nano particles have the defects of easy agglomeration and the like, thereby affecting the stability of the composite material, so the composite material has the effect on magnetic ZrO 2 Modification studies of nanoparticles are an important method for improving the performance of the nanoparticles.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a preparation method of composite nano-microspheres capable of adsorbing heavy metals aiming at the state of the art.
The second technical problem to be solved by the inventionThe problem is to provide a ZrO 2 Use of nanocomposite particles in nanofiber membranes.
The technical scheme adopted by the invention for solving the first technical problem is as follows: the preparation method of the composite nano microsphere is characterized by comprising the following steps:
(1) swelling chitosan in acetic acid solution to form transparent paste, adding the transparent paste into sodium hydroxide solution under stirring to precipitate, filtering, washing, taking a first solvent in a first container, adding ethylenediamine tetraacetic acid, heating to dissolve, adding the swelled chitosan, slowly dropwise adding concentrated sulfuric acid, and reacting to obtain modified chitosan;
(2) putting bentonite into a first container, adding an acid solution under the condition of continuous stirring, reacting, filtering a reaction mixture, washing to be neutral, vacuum drying an obtained product, taking out, grinding and sieving to obtain acidified bentonite;
(3) mixing acidified bentonite in acetic acid solution, stirring to obtain bentonite suspension, and adding modified chitosan into the bentonite suspension to uniformly mix the modified chitosan with the bentonite suspension; adding sodium polyacrylate into a second container filled with distilled water under the condition of continuous stirring to form a uniform solution; adding bentonite and chitosan mixed solution into sodium polyacrylate solution, stirring, adding ZrO into the solution 2 The nano particles are continuously stirred to obtain uniform bentonite chitosan Zr mixed solution;
(4) slowly dripping bentonite chitosan Zr mixed solution into a mixed solution of sodium citrate and sodium hydroxide, and standing; then adding a mixed solution of ultrapure water and ethylene glycol diglycidyl ether, and after crosslinking, alternately washing with ultrapure water and ethanol to obtain the composite nano-microsphere.
Preferably, the weight ratio of the chitosan to the ethylenediamine tetraacetic acid in the step (1) is 2-3:1-1.5; the modified chitosan, the acidified bentonite, the sodium polyacrylate and the ZrO 2 The weight ratio of the additive is 5-7:20-30:10-15:1-2.
Preferably, the diameter of the ZrO2 nano-particles is 30-50 nm; zrO in the composite nano microsphere 2 Load amount5 to 10mol percent, and the diameter of the composite nanometer microsphere is 1.0 to 2.0mm.
Preferably, the first solvent in the step (1) is at least one of dimethyl sulfoxide, dimethylformamide or tetrahydrofuran; the acid solution in the step (2) is one of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and the percentage concentration of the acid solution is 0.5-1.0%.
Preferably, in the step (3), the concentration of sodium hydroxide in the mixed solution of sodium citrate and sodium hydroxide is 0.45-1.0 mol/L, the concentration of sodium citrate is 0.25-0.40 mol/L, and the volume ratio of the sodium hydroxide solution to the sodium citrate solution is 1:1.
The invention solves the second technical problem by adopting the technical proposal that: the application of the composite nano microsphere in preparing the nanofiber membrane is characterized by comprising the following steps:
(1) adding a second solvent and composite nano microspheres into a third container, stirring to form a homogeneous solution, adding polyurethane, continuously stirring to completely dissolve the polyurethane, cooling after completely dissolving, adding lithium chloride, and stirring uniformly to prepare an electrostatic spinning precursor solution; the lithium chloride is added into the spinning solution, so that the conductivity of the solution can be increased, and the surface charge of jet flow can be increased under the high-pressure environment of spinning, so that the spinning of fibers is easy, and the spinning efficiency is improved;
(2) 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 obtain the nanofiber membrane.
(3) Adding a mixed solution of ethanol and hydrochloric acid into a water bath container, blowing hot air into the water bath container to remove template holes, and vacuum drying the nanofiber membrane until the quality is unchanged.
Preferably, the second solvent is one or a combination of N, N-dimethylformamide or N, N-dimethylacetamide or butanone; the molecular weight of the polyurethane is 80000-100000, and the viscosity of the electrostatic spinning precursor solution is 700-1500 mPa.s.
Preferably, the mass ratio of the second solvent to the polyurethane is 70:8-70:20; the weight ratio of the second solvent to the composite nano-microsphere is 70:1-70:9; the mass ratio of the second solvent to the lithium chloride is 70:1-70:4.
Preferably, the electrospinning conditions in step (2) 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 is 500-660 m2/g, the porosity is 60-70%, and the fiber diameter is 70-120 nm.
The preparation of the composite nano microsphere and the fibrous membrane can be carried out by adopting the following technical contents:
1) 2-3g of chitosan is weighed and swelled in 20-30ml of 3% acetic acid solution for 1.5h to be transparent pasty, stirred for 20-30min, added into 80-100ml of 0.25mol/L sodium hydroxide solution for precipitation, filtered by a vacuum pump, and washed with deionized water and ethanol for 2 times in sequence. Weighing 40-50ml of solvent, placing into a three-neck flask, adding 1-1.5g of ethylenediamine tetraacetic acid, heating to 60 ℃ for dissolution, then adding the swelled chitosan, slowly dropwise adding 0.25-0.35ml of concentrated sulfuric acid, and reacting for 12h at 40 ℃.
(2) Weighing 10-15g of bentonite, adding 100-120ml of acid solution into a round bottom flask under the condition of continuously stirring for 30-40min, reacting for 3 hours at normal temperature and 25 ℃, filtering the reaction mixture, washing 3 times with deionized water to neutrality, drying the obtained product in a vacuum drying oven at 60 ℃ for 12 hours, taking out, grinding and sieving to obtain the acidified bentonite.
(3) Mixing 20-30g of acidified bentonite in 40-50ml of 3% acetic acid solution, stirring for 1.5-2h to obtain bentonite suspension, and adding 5-7g of modified chitosan into the bentonite suspension to uniformly mix the modified chitosan and the bentonite suspension. 10-15g of sodium polyacrylate was added to a round bottom flask containing 50-60ml of distilled water with constant stirring for 50-60min to form a homogeneous solution. Adding bentonite and chitosan mixed solution into sodium polyacrylate solution, stirring for 20-30min, and adding 1-2g ZrO 2 And continuously stirring for 10-20min to obtain uniform bentonite/chitosan/Zr mixtureMixing the liquid. And slowly dripping 50-60ml of the mixed solution into 70-80ml of the mixed solution of sodium citrate and sodium hydroxide by using a peristaltic pump, and standing for 4 hours. Then adding 100-120ml of ultrapure water and 1-2ml of glycol diglycidyl ether, crosslinking at 25 ℃ for 4 hours, and washing with ultrapure water and ethanol alternately for 5 times to obtain chitosan-sodium polyacrylate-acidified bentonite-ZrO 2 A nanometer microsphere.
(4) Adding solvent and chitosan-sodium polyacrylate-acidified bentonite-ZrO into round bottom flask 2 Stirring the nano microsphere for 30-50min at 30-40 ℃ to form a homogeneous solution, adding polyurethane, continuously stirring for 25-35min at 60 ℃ to completely dissolve the polyurethane, cooling after completely dissolving, adding lithium chloride, and stirring for 40-50min to uniformly prepare the electrostatic spinning precursor solution.
(5) 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 power is turned on to prepare the nanofiber membrane.
(6) Adding ethanol and hydrochloric acid mixed solution with the mass ratio of 1-3:1 into a water bath container, introducing hot air into the container to blow out the template to cause holes, and finally vacuum drying the nanofiber until the mass is unchanged.
(7) 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% 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: chitosan sodium polyacrylate acidized bentonite ZrO is added in the process of electrostatic spinning of polyurethane 2 The composite nano microsphere can improve the heavy metal adsorption capacity, can be reused, and can be widely applied to the field of liquid filtration.
The choice of polyurethane as the polymer for electrospinning is mainly due to the electrospinning solution of polyurethaneThe liquid concentration range is large, the initial voltage is low, the electrostatic spinning spinnability is good, and the mechanical property of the nanofiber membrane of polyurethane is excellent. ZrO (ZrO) 2 The nano material has the characteristics of superparamagnetism, easy synthesis, no toxicity and the like, can be applied to enrichment of heavy metal ions in seawater, and can rapidly realize ZrO under the action of an externally applied magnetic field 2 The adsorbent is separated and recycled, so that the subsequent treatment of heavy metal ion adsorption is simplified, and particularly, the separation method is very simple and convenient due to superparamagnetism and magnetic responsiveness.
The chitosan molecule surface has amino and hydroxyl, can be chelated with heavy metal ions, has certain heavy metal adsorption capacity, but has small heavy metal adsorption capacity, and the chitosan is partially soluble in a solution with low pH of the disc and cannot exist stably. After the chitosan is grafted and modified by ethylenediamine tetraacetic acid and crosslinked with sodium polyacrylate and acidified bentonite, the stability of the chitosan can be improved, meanwhile, the bentonite has a good adsorption effect on heavy metal ions because of hydroxyl on the surface of the bentonite, the adsorption capacity of the chitosan can be obviously improved after the bentonite is crosslinked with the chitosan, meanwhile, the problem that the bentonite is difficult to recover as an adsorbent in an aqueous medium is effectively solved, in addition, the bentonite can loose a dense lamellar stacking structure of the bentonite after the bentonite is acidified, montmorillonite sheets are stripped, particles are dispersed, the interlayer spacing is increased, and thus active sites for adsorbing heavy metals are increased. The main function of the sodium polyacrylate is to serve as a bridge for connecting chitosan and acidified bentonite, so that the two substances can be overlapped, and the sodium polyacrylate structure contains a large number of carboxyl groups, so that the adsorption effect of the microsphere on heavy metals can be improved. ZrO (ZrO) 2 After being loaded on the chitosan-sodium polyacrylate-acidified bentonite, the chitosan-sodium polyacrylate-acidified bentonite can be endowed with recoverability, the adsorbent is easier to separate from the solution after the adsorption is completed, the recycling rate of the adsorbent can be improved, and simultaneously the chitosan-sodium polyacrylate-acidified bentonite also solves the problem of ZrO 2 The problem of easy agglomeration and low surface activity in the polymer.
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 fiber membrane has the advantages of simple whole preparation process, mild and easily controlled conditions, and the adopted raw materials are nontoxic or low-toxicity raw materials, so that the raw materials are consumed less in the reaction process, the cost is lower, toxic byproducts are not generated, and the fiber membrane 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.
Detailed Description
The present invention is described in further detail below with reference to examples.
Example 1
(1) 2g of chitosan is weighed and swelled in 20ml of 3% acetic acid solution for 1.5 hours to make the chitosan become transparent paste, and after stirring for 20 minutes, the chitosan is added into 80ml of 0.25mol/L sodium hydroxide solution to precipitate, and the solution is filtered by a vacuum pump and washed with deionized water and ethanol for 2 times in sequence. 40ml of dimethyl sulfoxide is measured, put into a three-neck flask, 1g of ethylenediamine tetraacetic acid is put into the flask to be heated to 60 ℃ for dissolution, then 0.25ml of concentrated sulfuric acid is slowly added into the mixture after swelling, and the mixture is reacted for 12 hours at 40 ℃.
(2) 10g of bentonite is weighed into a round bottom flask, 100ml of hydrochloric acid solution with the concentration of 0.5% is added under the condition of continuously stirring for 30min, the reaction mixture is filtered under suction after 3 hours at the normal temperature of 25 ℃, deionized water is used for washing 3 times to neutrality, the obtained product is dried for 12 hours in a vacuum drying oven with the temperature of 60 ℃, and the acidified bentonite is obtained after being taken out, ground and screened.
(3) 20g of acidified bentonite is mixed in 40ml of 3% acetic acid solution, stirred for 1.5h to obtain bentonite suspension, and 5g of modified chitosan is added into the bentonite suspension to be uniformly mixed. 10g of sodium polyacrylate was added to the mixture with stirring for 50minIn a round bottom flask with 50ml distilled water, a homogeneous solution was formed. The bentonite and chitosan mixed solution was added to the sodium polyacrylate solution and stirred for 20 minutes, and then 1g of ZrO was added to the solution 2 And stirring for 10min to obtain uniform bentonite/chitosan/Zr mixed solution. 50ml of the mixed solution was slowly dropped into 70ml of a mixed solution of 0.25mol/L sodium citrate and 0.45mol/L sodium hydroxide using a peristaltic pump, and left to stand for 4 hours. Then adding 100ml of ultrapure water and 1ml of glycol diglycidyl ether, crosslinking at 25 ℃ for 4 hours, and washing with ultrapure water and ethanol alternately for 5 times to obtain chitosan-sodium polyacrylate-acidified bentonite-ZrO 2 A nanometer microsphere.
(4) 700g of N, N-dimethylformamide and 50g of chitosan-sodium polyacrylate-acidified bentonite-ZrO were introduced into a round-bottomed flask 2 Stirring the nano microsphere for 30min at 30 ℃ to form a homogeneous solution, adding 120g of polyurethane with molecular weight of 80000, continuously stirring for 25min at 60 ℃ to completely dissolve the polyurethane, cooling to 0 ℃ after completely dissolving, adding 50g of lithium chloride, and stirring for 40min to uniformly prepare the electrostatic spinning precursor solution, wherein the viscosity of the spinning solution is 800 mPa.s.
(5) 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.
(6) Adding a mixed solution of 20g of ethanol and 20g of hydrochloric acid into a water bath container, blowing hot air with the temperature of 200 ℃ into the container to remove template pore-forming, and finally vacuum drying the nanofiber until the quality is unchanged.
(7) 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% dilute nitric acid, and the solubility of residual heavy metal in the sample is measured by an atomic absorption spectrophotometer.
Example 2
(1) 2.5g of chitosan is weighed and swelled in 25ml of 3% acetic acid solution for 1.5h to make the chitosan become transparent pasty, and after stirring for 25min, the chitosan is added into 90ml of 0.25mol/L sodium hydroxide solution for precipitation, and is subjected to suction filtration by a vacuum pump, and is washed with deionized water and ethanol for 2 times in sequence. 45ml of dimethyl sulfoxide is measured, put into a three-neck flask, 1.2g of ethylenediamine tetraacetic acid is put into the flask to be heated to 60 ℃ for dissolution, then 0.30ml of concentrated sulfuric acid is slowly added into the swollen chitosan, and the mixture is reacted for 12 hours at 40 ℃.
(2) Weighing 12g of bentonite into a round-bottom flask, adding 110ml of 0.7% hydrochloric acid solution under the condition of continuously stirring for 35min, reacting for 3 hours at the normal temperature of 25 ℃, filtering the reaction mixture, washing 3 times with deionized water to neutrality, drying the obtained product in a vacuum drying oven at the temperature of 60 ℃ for 12 hours, taking out, grinding and sieving to obtain the acidified bentonite.
(3) 25g of acidified bentonite is mixed in 45ml of 3% acetic acid solution, stirred for 1.7h to obtain bentonite suspension, and 6g of modified chitosan is added into the bentonite suspension to be uniformly mixed. 12g of sodium polyacrylate was added to a round bottom flask with 55ml of distilled water with constant stirring for 55min to form a homogeneous solution. The bentonite and chitosan mixed solution was added to the sodium polyacrylate solution and stirred for 25 minutes, and then 1.5g of ZrO was added to the solution 2 And stirring for 15min to obtain uniform bentonite/chitosan/Zr mixed solution. 55ml of the mixed solution was slowly dropped into 75ml of a mixed solution of 0.35mol/L sodium citrate and 0.75mol/L sodium hydroxide using a peristaltic pump, and left stand for 4 hours. Then adding 110ml of ultrapure water and 1.5ml of glycol diglycidyl ether, crosslinking at 25 ℃ for 4 hours, and washing with ultrapure water and ethanol alternately for 5 times to obtain chitosan-sodium polyacrylate-acidified bentonite-ZrO 2 A nanometer microsphere.
(4) 700g of N, N-dimethylformamide and 50g of chitosan-sodium polyacrylate-acidized swelling were introduced into a round-bottomed flaskearth-ZrO 2 Stirring the nano microsphere for 40min at 35 ℃ to form a homogeneous solution, adding 120g of polyurethane with molecular weight of 90000, continuously stirring for 30min at 60 ℃ to completely dissolve the polyurethane, cooling to 3 ℃ after completely dissolving, adding 50g of lithium chloride, and stirring for 45min to uniformly prepare the electrostatic spinning precursor solution, wherein the viscosity of the spinning solution is 1000 mPa.s.
(5) 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.
(6) Adding 40g of ethanol and 20g of hydrochloric acid mixed solution into a water bath container, blowing hot air with the temperature of 200 ℃ into the container to remove template pore-forming, and finally vacuum drying the nanofiber until the quality is unchanged.
(7) 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% dilute nitric acid, and the solubility of residual heavy metal in the sample is measured by an atomic absorption spectrophotometer.
Example 3
(1) 3g of chitosan is weighed and swelled in 30ml of 3% acetic acid solution for 1.5 hours to make the chitosan become transparent paste, and after stirring for 30 minutes, the chitosan is added into 100ml of 0.25mol/L sodium hydroxide solution for precipitation, and the solution is filtered by a vacuum pump and washed with deionized water and ethanol for 2 times in sequence. 50ml of dimethyl sulfoxide is measured, put into a three-neck flask, 1.5g of ethylenediamine tetraacetic acid is put into the flask to be heated to 60 ℃ for dissolution, then 0.35ml of concentrated sulfuric acid is slowly added into the mixture after swelling, and the mixture is reacted for 12 hours at 40 ℃.
(2) 15g of bentonite is weighed into a round bottom flask, 120ml of hydrochloric acid solution with the concentration of 1.0% is added under the condition of continuously stirring for 40min, the reaction mixture is filtered under suction after 3 hours at the normal temperature of 25 ℃, deionized water is used for washing 3 times to neutrality, the obtained product is dried for 12 hours in a vacuum drying oven with the temperature of 60 ℃, and the acidified bentonite is obtained after being taken out, ground and screened.
(3) 30g of acidified bentonite is mixed in 50ml of 3% acetic acid solution, stirred for 2 hours to obtain bentonite suspension, and 7g of modified chitosan is added into the bentonite suspension to be uniformly mixed. 15g of sodium polyacrylate was added to a round bottom flask with 60ml of distilled water under constant stirring for 60min to form a homogeneous solution. The bentonite and chitosan mixed solution was added to the sodium polyacrylate solution and stirred for 30 minutes, and then 2g of ZrO was added to the solution 2 And continuing stirring for 20min to obtain uniform bentonite/chitosan/Zr mixed solution. 60ml of the mixed solution was slowly dropped into 80ml of a mixed solution of 0.40mol/L sodium citrate and 1.0mol/L sodium hydroxide using a peristaltic pump, and left to stand for 4 hours. Then adding 120ml of ultrapure water and 2ml of glycol diglycidyl ether, crosslinking for 4 hours at 25 ℃, and washing with ultrapure water and ethanol alternately for 5 times to obtain chitosan-sodium polyacrylate-acidified bentonite-ZrO 2 A nanometer microsphere.
(4) 700g of N, N-dimethylformamide and 50g of chitosan-sodium polyacrylate-acidified bentonite-ZrO were introduced into a round-bottomed flask 2 Stirring the nano microsphere for 50min at 40 ℃ to form a homogeneous solution, adding 120g of polyurethane with the molecular weight of 100000, continuously stirring for 35min at 60 ℃ to completely dissolve the polyurethane, cooling to 5 ℃ after completely dissolving, adding 50g of lithium chloride, and stirring for 50min to uniformly prepare the electrostatic spinning precursor solution, wherein the viscosity of the spinning solution is 1300 mPa.s.
(5) 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.
(6) Adding 60g of ethanol and 20g of hydrochloric acid mixed solution into a water bath container, blowing hot air with the temperature of 200 ℃ into the container to remove template pore-forming, and finally vacuum drying the nanofiber until the quality is unchanged.
(7) 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% dilute nitric acid, and the solubility of residual heavy metal in the sample is measured by an atomic absorption spectrophotometer.
Comparative example 1 grafting modification of Chitosan with Ethylenediamine tetraacetic acid
(1) 15g of bentonite is weighed into a round bottom flask, 120ml of hydrochloric acid solution with the concentration of 1.0% is added under the condition of continuously stirring for 40min, the reaction mixture is filtered under suction after 3 hours at the normal temperature of 25 ℃, deionized water is used for washing 3 times to neutrality, the obtained product is dried for 12 hours in a vacuum drying oven with the temperature of 60 ℃, and the acidified bentonite is obtained after being taken out, ground and screened.
(2) 30g of acidified bentonite is mixed in 50ml of 3% acetic acid solution, stirred for 2 hours to obtain bentonite suspension, and 7g of chitosan is added into the bentonite suspension to be uniformly mixed. 15g of sodium polyacrylate was added to a round bottom flask with 60ml of distilled water under constant stirring for 60min to form a homogeneous solution. The bentonite and chitosan mixed solution was added to the sodium polyacrylate solution and stirred for 30 minutes, and then 2g of ZrO was added to the solution 2 And continuing stirring for 20min to obtain uniform bentonite/chitosan/Zr mixed solution. 60ml of the mixed solution was slowly dropped into 80ml of a mixed solution of 0.40mol/L sodium citrate and 1.0mol/L sodium hydroxide using a peristaltic pump, and left to stand for 4 hours. Then adding 120ml of ultrapure water and 2ml of glycol diglycidyl ether, crosslinking for 4 hours at 25 ℃, and washing with ultrapure water and ethanol alternately for 5 times to obtain chitosan-sodium polyacrylate-acidified bentonite-ZrO 2 A nanometer microsphere.
(3) 700g of N, N-dimethylformamide and 50g of chitosan-sodium polyacrylate-acidified bentonite-ZrO were introduced into a round-bottomed flask 2 Stirring the nano microsphere for 50min at 40 ℃ to form a homogeneous solution, adding 120g of polyurethane with the molecular weight of 100000, continuously stirring for 35min at 60 ℃ to completely dissolve the polyurethane, cooling to 5 ℃ after completely dissolving, adding 50g of lithium chloride, and stirring for 50min to uniformly prepare the electrostatic spinning precursor solution, wherein the viscosity of the spinning solution is 1300 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) Adding 60g of ethanol and 20g of hydrochloric acid mixed solution into a water bath container, blowing hot air with the temperature of 200 ℃ into the container to remove template pore-forming, and finally vacuum drying the nanofiber until the quality is unchanged.
(6) 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% dilute nitric acid, and the solubility of residual heavy metal in the sample is measured by an atomic absorption spectrophotometer.
Comparative example 2 no acidification treatment of bentonite
(1) 3g of chitosan is weighed and swelled in 30ml of 3% acetic acid solution for 1.5 hours to make the chitosan become transparent paste, and after stirring for 30 minutes, the chitosan is added into 100ml of 0.25mol/L sodium hydroxide solution for precipitation, and the solution is filtered by a vacuum pump and washed with deionized water and ethanol for 2 times in sequence. 50ml of dimethyl sulfoxide is measured, put into a three-neck flask, 1.5g of ethylenediamine tetraacetic acid is put into the flask to be heated to 60 ℃ for dissolution, then 0.35ml of concentrated sulfuric acid is slowly added into the mixture after swelling, and the mixture is reacted for 12 hours at 40 ℃.
(2) 30g of bentonite is mixed in 50ml of 3% acetic acid solution, the mixture is stirred for 2 hours to obtain bentonite suspension, and 7g of modified chitosan is added into the bentonite suspension to be uniformly mixed. 15g of sodium polyacrylate was added to a round bottom flask with 60ml of distilled water under constant stirring for 60min to form a homogeneous solution. The bentonite and chitosan mixed solution was added to the sodium polyacrylate solution and stirred for 30 minutes, and then 2g of ZrO was added to the solution 2 And continuing stirring for 20min to obtain uniform bentonite/chitosan/Zr mixed solution. 60ml of the mixed solution was slowly dropped into 80ml of a mixed solution of 0.40mol/L sodium citrate and 1.0mol/L sodium hydroxide using a peristaltic pump, and left to stand for 4 hours. Then adding 120ml of ultrapure water and 2ml of glycol diglycidyl ether, crosslinking for 4 hours at 25 ℃, and washing with ultrapure water and ethanol alternately for 5 times to obtain chitosan-sodium polyacrylate-acidified bentonite-ZrO 2 A nanometer microsphere.
(3) 700g of N, N-dimethylformamide and 50g of chitosan-sodium polyacrylate-acidified bentonite-ZrO were introduced into a round-bottomed flask 2 Stirring the nano microsphere for 50min at 40 ℃ to form a homogeneous solution, adding 120g of polyurethane with the molecular weight of 100000, continuously stirring for 35min at 60 ℃ to completely dissolve the polyurethane, cooling to 5 ℃ after completely dissolving, adding 50g of lithium chloride, and stirring for 50min to uniformly prepare the electrostatic spinning precursor solution, wherein the viscosity of the spinning solution is 1300 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) Adding 60g of ethanol and 20g of hydrochloric acid mixed solution into a water bath container, blowing hot air with the temperature of 200 ℃ into the container to remove template pore-forming, and finally vacuum drying the nanofiber until the quality is unchanged.
(6) 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% dilute nitric acid, and the solubility of residual heavy metal in the sample is measured by an atomic absorption spectrophotometer.
Comparative example 3 no crosslinking of chitosan
(1) 3g of chitosan is weighed and swelled in 30ml of 3% acetic acid solution for 1.5 hours to make the chitosan become transparent paste, and after stirring for 30 minutes, the chitosan is added into 100ml of 0.25mol/L sodium hydroxide solution for precipitation, and the solution is filtered by a vacuum pump and washed with deionized water and ethanol for 2 times in sequence. 50ml of dimethyl sulfoxide is measured, put into a three-neck flask, 1.5g of ethylenediamine tetraacetic acid is put into the flask to be heated to 60 ℃ for dissolution, then 0.35ml of concentrated sulfuric acid is slowly added into the mixture after swelling, and the mixture is reacted for 12 hours at 40 ℃. Subsequently, 2g of ZrO was added to the solution 2 And stirring for 20min to obtain uniform chitosan/Zr mixed solution.
(2) 700g of N, N-dimethylformamide and 50g of chitosan/ZrO were introduced into a round-bottomed flask 2 Stirring the nano microsphere for 50min at 40 ℃ to form a homogeneous solution, adding 120g of polyurethane with the molecular weight of 100000, continuously stirring for 35min at 60 ℃ to completely dissolve the polyurethane, cooling to 5 ℃ after completely dissolving, adding 50g of lithium chloride, and stirring for 50min to uniformly prepare the electrostatic spinning precursor solution, wherein the viscosity of the spinning solution is 1300 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) Adding 60g of ethanol and 20g of hydrochloric acid mixed solution into a water bath container, blowing hot air with the temperature of 200 ℃ into the container to remove template pore-forming, and finally vacuum drying the nanofiber until the quality is unchanged.
(5) 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% dilute nitric acid, and the solubility of residual heavy metal in the sample is measured by an atomic absorption spectrophotometer.
Comparative example 4 without adding ZrO 2
(1) 3g of chitosan is weighed and swelled in 30ml of 3% acetic acid solution for 1.5 hours to make the chitosan become transparent paste, and after stirring for 30 minutes, the chitosan is added into 100ml of 0.25mol/L sodium hydroxide solution for precipitation, and the solution is filtered by a vacuum pump and washed with deionized water and ethanol for 2 times in sequence. 50ml of dimethyl sulfoxide is measured, put into a three-neck flask, 1.5g of ethylenediamine tetraacetic acid is put into the flask to be heated to 60 ℃ for dissolution, then 0.35ml of concentrated sulfuric acid is slowly added into the mixture after swelling, and the mixture is reacted for 12 hours at 40 ℃.
(2) 15g of bentonite is weighed into a round bottom flask, 120ml of hydrochloric acid solution with the concentration of 1.0% is added under the condition of continuously stirring for 40min, the reaction mixture is filtered under suction after 3 hours at the normal temperature of 25 ℃, deionized water is used for washing 3 times to neutrality, the obtained product is dried for 12 hours in a vacuum drying oven with the temperature of 60 ℃, and the acidified bentonite is obtained after being taken out, ground and screened.
(3) 30g of acidified bentonite is mixed in 50ml of 3% acetic acid solution, stirred for 2 hours to obtain bentonite suspension, and 7g of modified chitosan is added into the bentonite suspension to be uniformly mixed. 15g of sodium polyacrylate was added to a round bottom flask with 60ml of distilled water under constant stirring for 60min to form a homogeneous solution. And adding the bentonite and chitosan mixed solution into the sodium polyacrylate solution, and continuously stirring for 30min.
(4) 700g of N, N-dimethylformamide and 50g of chitosan-sodium polyacrylate-acidified bentonite are added into a round bottom flask, the mixture is stirred at 40 ℃ for 50min to form a homogeneous solution, 120g of polyurethane with the molecular weight of 100000 is added, the mixture is continuously stirred at 60 ℃ for 35min to completely dissolve the polyurethane, 50g of lithium chloride is added after the polyurethane is completely dissolved and cooled to 5 ℃, and the mixture is stirred for 50min to uniformly prepare an electrostatic spinning precursor solution, wherein the viscosity of the spinning solution is 1300 mPa.s.
(5) 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.
(6) Adding 60g of ethanol and 20g of hydrochloric acid mixed solution into a water bath container, blowing hot air with the temperature of 200 ℃ into the container to remove template pore-forming, and finally vacuum drying the nanofiber until the quality is unchanged.
(7) 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% 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 1-4 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 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 method of the present invention is advantageous for improving the 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
From table 2, it can be seen that the method of the present invention 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 ZrO 2 The introduction of (3) improves the recyclability of the fibrous membrane adsorption material, and related tests are performed, and the test results are 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 the results are shown in Table 3.
TABLE 3 Table 3
From the above table, it is clear that the nanofiber membrane of the present invention has excellent recyclability.
Claims (10)
1. The preparation method of the composite nano microsphere is characterized by comprising the following steps:
(1) swelling chitosan in acetic acid solution to form transparent paste, adding the transparent paste into sodium hydroxide solution under stirring to precipitate, filtering, washing, taking a first solvent in a first container, adding ethylenediamine tetraacetic acid, heating to dissolve, adding the swelled chitosan, slowly dropwise adding concentrated sulfuric acid, and reacting to obtain modified chitosan;
(2) putting bentonite into a first container, adding an acid solution under the condition of continuous stirring, reacting, filtering a reaction mixture, washing to be neutral, vacuum drying an obtained product, taking out, grinding and sieving to obtain acidified bentonite;
(3) mixing acidified bentonite in acetic acid solution, stirring to obtain bentonite suspension, and adding modified chitosan into the bentonite suspension to uniformly mix the modified chitosan with the bentonite suspension; adding sodium polyacrylate into a second container filled with distilled water under the condition of continuous stirring to form a uniform solution; adding bentonite and chitosan mixed solution into sodium polyacrylate solution, stirring, adding ZrO into the solution 2 The nano particles are continuously stirred to obtain uniform bentonite chitosan Zr mixed solution;
(4) slowly dripping bentonite chitosan Zr mixed solution into a mixed solution of sodium citrate and sodium hydroxide, and standing; then adding a mixed solution of ultrapure water and ethylene glycol diglycidyl ether, and after crosslinking, alternately washing with ultrapure water and ethanol to obtain the composite nano-microsphere.
2. The method for preparing composite nano-microspheres according to claim 1, wherein the weight ratio of chitosan to ethylenediamine tetraacetic acid in the step (1) is 2-3:1-1.5; the modified chitosan, the acidified bentonite, the sodium polyacrylate and the ZrO 2 The weight ratio of the additive is 5-7:20-30:10-15:1-2.
3. The method for preparing composite nano-microspheres according to claim 2, wherein the diameter of the ZrO2 nano-particles is 30 to 50nm; zrO in the composite nano microsphere 2 The loading is 5-10 mol%, and the diameter of the composite nano microsphere is 1.0-2.0 mm.
4. The method for preparing composite nano-microspheres according to claim 1, wherein the first solvent in the step (1) is at least one of dimethyl sulfoxide, dimethylformamide or tetrahydrofuran; the acid solution in the step (2) is one of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and the percentage concentration of the acid solution is 0.5-1.0%.
5. The method for preparing composite nano-microspheres according to claim 1, wherein the concentration of sodium hydroxide in the mixed solution of sodium citrate and sodium hydroxide in the step (3) is 0.45-1.0 mol/L, the concentration of sodium citrate is 0.25-0.40 mol/L, and the volume ratio of sodium hydroxide solution to sodium citrate solution is 1:1.
6. Use of the composite nanoparticle according to any one of claims 1 to 5 for the preparation of a nanofiber membrane, characterized by comprising the steps of:
(1) adding a second solvent and composite nano microspheres into a third container, stirring to form a homogeneous solution, adding polyurethane, continuously stirring to completely dissolve the polyurethane, cooling after completely dissolving, adding lithium chloride, and stirring uniformly to prepare an electrostatic spinning precursor solution;
(2) 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 obtain the nanofiber membrane.
(3) Adding a mixed solution of ethanol and hydrochloric acid into a water bath container, blowing hot air into the water bath container to remove template holes, and vacuum drying the nanofiber membrane until the quality is unchanged.
7. The use according to claim 6, wherein the second solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, and butanone; the molecular weight of the polyurethane is 80000-100000, and the viscosity of the electrostatic spinning precursor solution is 700-1500 mPa.s.
8. The use according to claim 7, characterized in that the mass ratio of the second solvent to the polyurethane is 70:8 to 70:20; the weight ratio of the second solvent to the composite nano-microsphere is 70:1-70:9; the mass ratio of the second solvent to the lithium chloride is 70:1-70:4.
9. The use according to claim 6, characterized in that the electrospinning conditions of step (2) 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%.
10. The method according to claim 6, wherein the specific surface area of the nanofiber membrane is 500-660 m2/g, the porosity is 60-70%, and the fiber diameter is 70-120 nm.
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