CN102000608B - Method for preparing polymer heterogeneous Fenton-like catalyst-polyvinylidene fluoride (PVDF) catalytic membrane - Google Patents
Method for preparing polymer heterogeneous Fenton-like catalyst-polyvinylidene fluoride (PVDF) catalytic membrane Download PDFInfo
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Abstract
The invention relates to a method for preparing a polymer heterogeneous Fenton-like catalyst-polyvinylidene fluoride (PVDF) catalytic membrane, in particular to a preparation method of a Fenton-like catalytic membrane. By using the preparation method, the problems that iron ions are difficult to recover, and H2O2 has low utilization rate and small application range are solved. The method comprises the following steps: firstly, mixing PVDF powder, a solvent and an additive, stirring, and keeping stand, and carrying out knifing on a clean glass sheet; secondly, carrying out pretreatment on an ethanol solution, and cleaning with deionized water; thirdly, carrying out alkali treatment, and cleaning with the deionized water until neutrality; fourthly, grafting; fifthly, swelling and sulfonating; and finally, putting a solution containing Fe<3+>, vibrating in a water bath to obtain the PVDF catalytic membrane. In the invention, the catalyst has high oxidation resistance and large specific surface area, and can not only purify difficultly degradable macromolecular dye substances but also effectively catalyze organic pollutants in H2O2 degradable water through using the interception function of the membrane, and the method is simple and convenient to operate; and simultaneously, wastewater comes up to the reuse standard, thereby having significance for the development of environmental sustainability.
Description
Technical field
The preparation method of type of the present invention relates to Fenton catalytic membrane.
Background technology
The Fenton oxidation has lot of advantages, and is simple like method, oxidation rate is fast, reagent concentration is low, economical and efficient etc., and reagent is environmentally friendly; Yet optimum pH value is 3.0～4.0, when the pH value greater than 4, iron will precipitate with the form of iron hydroxide; This greatly reduces reaction rate, and most biochemical system is in pH＜5.0 o'clock; Biologically active will be suppressed, and the pH value significantly reduces and also is not suitable for present soil and phreatic reparation.When preventing that the pH value from raising; The sedimentation problem of iron occurs, some strong complexing agents are added in the reaction system, to stablize iron ion; Therefore; Occurred being improvement (Modified) the Fenton system of catalyst and being Fenton-like (Fenton-like) system of catalyst with ferric complex compound with ferrous complex compound because the use of complexing agent, make Fenton reagent neutral or near neutral condition under use and become possibility.
At present, the complexing carrier of having studied stable iron ion both at home and abroad comprises Nafion film, polysiloxanes, silica gel, cationic ion-exchange resin, zeolite molecular sieve etc.Yet; Kynoar (PVDF) is as a kind of novel fluoro-carbon thermoplastic, has good mechanical strength, uvioresistant and weatherability, chemical stability is good, and at room temperature PVDF is not corroded by acid, alkali, strong oxidizer and halogen; Very stable to organic solvents such as aliphatic hydrocarbon, aromatic hydrocarbon, alcohols and aldehydes; In hydrochloric acid, nitric acid, sulfuric acid and rare, dense (40%) alkali lye and under up to 100 ℃ of temperature, its performance is constant basically, and gamma ray resistant, ultraviolet radiation.F in the PVDF molecule can make ferric iron stable, and its oxidation-reduction potential is reduced, and this is as the carrier of load iron and lays a good foundation.Yet, both at home and abroad the research of pvdf membrane being focused mostly on to its study on the modification of performances such as hydrophily, antipollution, water flux, magnetic, the report aspect the catalytic oxidation in water treatment is less, and biases toward TiO more
2The research of/PVDF photocatalysis performance also has the pvdf membrane of some article report modifications to can be used as the PEM of methanol fuel cell, but does not also see the report that is used for multiphase-fenton Fenton system as catalytic membrane.Existing method exists the difficult recovery of iron ion, H
2O
2Low and the little problem of range of application of utilization rate.
Summary of the invention
The objective of the invention is iron ion is loaded on the pvdf membrane, solved the difficult recovery of iron ion, H among the traditional F enton
2O
2Utilization rate is low to reach the little problem of range of application, and the preparation method of macromolecule multiphase-fenton Fenton catalyst-PVDF catalytic membrane is provided.The present invention improves H
2O
2Utilization rate makes the permineralization of pollutant ability, has widened the pH scope of using to a certain extent through catalytic oxidation.
The preparation method of macromolecule multiphase-fenton Fenton catalyst-PVDF catalytic membrane is that following step is carried out among the present invention: mix after one, taking by weighing 4～20 parts of Kynoar, 50～90 parts of solvents and 0.1～10 part of additive respectively by ratio of quality and the number of copies; Under 45 ℃～60 ℃, be stirred to dissolving fully then; Constant temperature leaves standstill 30min～30h under 30 ℃～55 ℃ conditions; Knifing on the glass plate of cleaning soaks 30min～24h again in coagulating bath then, promptly makes pvdf membrane; Two, it is ethanolic solution preliminary treatment 5min～120min of 50%～75% that the pvdf membrane that step 1 is made is put into volumetric concentration, handles 10min～120min with deionized water again; Three, will put into the aqueous slkali that the tetrabutyl phosphonium bromide ammonium concentration is 0.1～4mg/mL through the pvdf membrane that step 2 is handled, alkali treatment 5min～15min under 0 ℃～70 ℃ conditions cleans to neutral then; Four, will put into styrene and oxolane mixed liquor through the pvdf membrane that step 3 is handled, under 40 ℃～90 ℃ nitrogen protections, carry out graft reaction 30min～6h then, clean three to five times with chloroform again, obtain graft copolymer membrane; Five, the graft copolymer membrane that step 4 is obtained puts into 1; 20 ℃～70 ℃ following swelling 30min～2h in the 2-dichloroethanes add the graft copolymer membrane after swelling treatment in the concentrated sulfuric acid then, under 20 ℃～80 ℃ conditions, carry out sulfonation and handle 30min～6h; Water cleans to neutral, gets sulfonated membranes; Six, sulfonated membranes is put into the Fe that concentration is 0.1～1.0mol/L
3+In the solution, making macromolecule multiphase-fenton Fenton catalyst-PVDF catalytic membrane behind vibration 0.1h～12h under 25 ℃ of water-baths then.
The effective anchoring iron ion of method of the present invention and then also can be made into flat sheet membrane, tubular membrane or hollow-fibre membrane and corresponding membrane module.Catalyst is anti-oxidant among the present invention, specific area is big, utilizes the crown_interception of film, the big molecular dye material of the difficult degradation of can purifying, and effective catalysis H
2O
2Organic pollution in the degradation water, method is simple, be convenient to operation; Make waste water reach reuse standard simultaneously, significant to the sustainable development of environment.The preparation method is simple among the present invention, catalyst can be recycled, in case can also regenerate, be convenient to operation after losing efficacy, development is arranged in water treatment procedure very much.
Description of drawings
Fig. 1 is the stereoscan photograph that the specific embodiment ten step 1 prepare the section internal structure of pvdf membrane; Fig. 2 is the stereoscan photograph of section internal structure of the macromolecule multiphase-fenton Fenton catalyst-PVDF catalytic membrane of specific embodiment preparation; Fig. 3 is the contact angle figure of the pvdf membrane of the specific embodiment ten step 1 preparation; Fig. 4 is the contact angle figure of the macromolecule multiphase-fenton Fenton catalyst-PVDF catalytic membrane of the specific embodiment ten methods preparation; Fig. 5 is the influence figure of different catalysts system to orange N absorption and oxidation; Among Fig. 5-■-expression catalytic membrane ,-▲-expression H
2O
2,-●-expression catalytic membrane+H
2O
2Fig. 6 is a different catalysts system decomposing H
2O
2Design sketch, among Fig. 6-■-expression catalytic membrane+H
2O
2,-●-expression H
2O
2, Fig. 7 is the PVDF catalytic membrane recycling figure that influences to the orange N degraded, among Fig. 7-■-expression for the first time ,-● and-expression for the second time ,-▲-represent for the third time; Fig. 8 is that the recycling of PVDF catalytic membrane is to H
2O
2Decomposition rate influence figure, among Fig. 8-■-expression for the first time ,-● and-expression for the second time ,-▲-expression for the third time.
The specific embodiment
The specific embodiment one: the preparation method of macromolecule multiphase-fenton Fenton catalyst-PVDF catalytic membrane is that following step is carried out in this embodiment: mix after one, taking by weighing 4～20 parts of Kynoar, 50～90 parts of solvents and 0.1～10 part of additive respectively by ratio of quality and the number of copies; Under 45 ℃～60 ℃, be stirred to dissolving fully then; Constant temperature leaves standstill 30min～30h under 30 ℃～55 ℃ conditions; Knifing on the glass plate of cleaning then; In coagulating bath (distilled water), soak 30min～24h again, promptly make pvdf membrane; Two, it is ethanolic solution preliminary treatment 5min～120min of 50%～75% that the pvdf membrane that step 1 is made is put into volumetric concentration, handles 10min～120min with deionized water again; Three, will put into the aqueous slkali that the tetrabutyl phosphonium bromide ammonium concentration is 0.1～4mg/mL through the pvdf membrane that step 2 is handled, alkali treatment 5min～15min under 0 ℃～70 ℃ conditions cleans to neutral then; Four, will put into styrene and oxolane mixed liquor through the pvdf membrane that step 3 is handled, under 40 ℃～90 ℃ nitrogen protections, carry out graft reaction 30min～6h then, clean three to five times with chloroform again, obtain graft copolymer membrane; Five, the graft copolymer membrane that step 4 is obtained puts into 1; 20 ℃～70 ℃ following swelling 30min～2h in the 2-dichloroethanes add the graft copolymer membrane after swelling treatment in the concentrated sulfuric acid then, under 20 ℃～80 ℃ conditions, carry out sulfonation and handle 30min～6h; Water cleans to neutral, gets sulfonated membranes; Six, sulfonated membranes is put into the Fe that concentration is 0.1～1.0mol/L
3+In the solution, making macromolecule multiphase-fenton Fenton catalyst-PVDF catalytic membrane behind vibration 0.1h～12h under 25 ℃ of water-baths then.
The specific embodiment two: what this embodiment and the specific embodiment one were different is: step 1 is mixed after taking by weighing 8～15 parts of PVDF, 60～80 parts of solvents and 1～8 part of additive by ratio of weight and the number of copies respectively.Other step is identical with the specific embodiment one with parameter.
The specific embodiment three: what this embodiment and the specific embodiment one were different is: step 1 is mixed after taking by weighing 10 parts of PVDF, 70 parts of solvents and 5 parts of additives by ratio of weight and the number of copies respectively.Other step is identical with the specific embodiment one with parameter.
The specific embodiment four: what this embodiment was different with one of specific embodiment one to three is: the described solvent of step 1 is N, N-dimethylacetylamide, N, and dinethylformamide, dimethyl sulfoxide (DMSO), triethyl phosphate or N-methyl adjoin pyrrolidone.Other step is identical with one of specific embodiment one to three with parameter.
The specific embodiment five: what this embodiment was different with one of specific embodiment one to four is: the described additive of step 1 is lithium chloride, sodium nitrate, ammonium chloride, glycerine, phosphoric acid, water, polyvinylpyrrolidone or polyethylene glycol.Other step is identical with one of specific embodiment one to four with parameter.
The specific embodiment six: what this embodiment was different with one of specific embodiment one to five is: the mass concentration of alkali is 0.1～2.5mol/L in the said aqueous slkali of step 3.Other step is identical with one of specific embodiment one to five with parameter.
The specific embodiment seven: what this embodiment was different with one of specific embodiment one to six is: the said aqueous slkali of step 3 is potassium hydroxide solution or sodium hydroxide solution.Other step is identical with one of specific embodiment one to six with parameter.
The specific embodiment eight: what this embodiment was different with one of specific embodiment one to seven is: contain Fe in the step 5
3+Solution be ferric sulfate, iron chloride, ferric nitrate or ferric perchlorate's solution.Other step is identical with one of specific embodiment one to seven with parameter.
The specific embodiment nine: what this embodiment was different with one of specific embodiment one to eight is: step 1 adopts cladding process to carry out knifing.Other step is identical with one of practical implementation one to eight with parameter.
The specific embodiment ten: what this embodiment was different with one of specific embodiment one to nine is: at the described Fe of containing of step 5
3+Solution in add the copper ion or the manganese ion of 0.1%～5% (quality).Other step is identical with one of practical implementation one to nine with parameter.
The specific embodiment 11: the preparation method of macromolecule multiphase-fenton Fenton catalyst-PVDF catalytic membrane is that following step is carried out in this embodiment: one, take by weighing 18 parts of Kynoar, 78 parts of N by ratio of weight and the number of copies respectively; Mix behind N-dimethylacetylamide and 4 parts of lithium chlorides; Under 60 ℃, be stirred to dissolving fully then, constant temperature leaves standstill 24h under 55 ℃ of conditions, the liquid film of striking one deck 0.4mm on the glass plate of cleaning; Immediately immerse in distilled water together with glass plate liquid film; Film is peeled off glass plate after solidifying automatically, in distilled water, soaks 24h then, promptly makes pvdf membrane; Two, the pvdf membrane that step 1 is made is put into 70% preliminary treatment 120min, in deionized water, handles 90min under the room temperature again; Three, will put into the 0.1mol/L KOH solution that concentration is 3mg/mL TBAB (TBAB) through the pvdf membrane that step 2 is handled, alkali treatment 15min under 70 ℃ of conditions cleans to neutral then; Four, will put into styrene and oxolane mixed liquor through the pvdf membrane that step 3 is handled, under 78 ℃ of nitrogen protections, carry out graft reaction 6h then, clean three to five times with chloroform again, obtain graft copolymer membrane; Five, the graft copolymer membrane that step 4 is obtained puts into 1, and 80 ℃ of following swelling 2h in the 2-dichloroethanes add the graft copolymer membrane after swelling treatment in the concentrated sulfuric acid then, under 70 ℃ of conditions, carries out sulfonation and handles 100min, gets sulfonated membranes; Six, sulfonated membranes is put into the iron nitrate solution of 0.1mol/L, made macromolecule multiphase-fenton Fenton catalyst-PVDF catalytic membrane behind the vibration 10h under 25 ℃ of conditions of water-bath then.
The load capacity of iron is (15.5 ± 0.5) mgg in this embodiment
-1
The section internal structure of the macromolecule multiphase-fenton Fenton catalyst-PVDF catalytic membrane of pvdf membrane that this embodiment step 1 is made and the preparation of this embodiment method is carried out electron-microscope scanning; The result sees Fig. 1 and Fig. 2; Can find out by Fig. 1 and 2; Macromolecule multiphase-fenton Fenton catalyst-PVDF catalysis fenestra and hole connectedness that the inventive method makes are good, and hole density increases.
Adopt dynamic/Static Contact appearance to measure contact angle; Concrete grammar is following: with membrane sample to be measured after dried; Face up and entirely be fixed on the contact angle appearance sample stage; On film, drip a ultra-pure water drop again, observe then, shown in Fig. 3 and 4; The result shows: the pvdf membrane that the contact angle of the macromolecule multiphase-fenton Fenton catalyst-PVDF catalytic membrane of this embodiment method preparation makes less than this embodiment step 1, the reducing of contact angle explains that also the hydrophily of modification caudacoria improves.
Adopt the catalytic effect of the macromolecule multiphase-fenton Fenton catalyst-PVDF catalytic membrane of following this embodiment of verification experimental verification preparation: be applied to multiphase photocatalysis of hydrogen peroxide and remove orange N, adopting oxidant in the reaction is hydrogen peroxide; Technical parameter in the course of reaction is following: orange N initial concentration: 0.4mmol/L, the dosage of hydrogen peroxide are 10mmol/L, and pH is 6.1, and temperature is 25 ℃, reaction time 5min～4h.Test result is shown in Fig. 5-8, and Fig. 5 and Fig. 6 have investigated the influence of different catalysts system to orange N absorption and oxidation respectively, have investigated the percent of decolourization situation of change along with the prolongation orange N in reaction time.Can find out by Fig. 5, by H
2O
2Oxidation separately, the percent of decolourization of orange N is about 10% when 6h.In conjunction with Fig. 6, this explanation is not having under the condition of catalyst H
2O
2Resolution ratio very little, almost be not decomposed.Orange N is an anionic dye, so the PVDF catalytic membrane has certain suction-operated to orange N.H is being arranged
2O
2Under the condition that exists, the PVDF catalytic membrane is to H
2O
2Capacity of decomposition as shown in Figure 5.Fig. 5 shows that the PVDF catalytic membrane is catalysis H effectively
2O
2Decompose orange N.For investigating the stability of PVDF catalytic membrane, in the above conditions it is reused.Fig. 7 is the situation of 25 ℃ of following PVDF catalytic membrane recycling degraded orange Ns.Can be known that by Fig. 7 catalyst does not significantly decrease to the removal effect of orange N after reusing 3 times, this shows that also iron load on the PVDF catalytic membrane is firmly stable; The catalytic oxidation performance of system does not obviously descend.H when Fig. 8 has shown PVDF catalytic membrane recycling degraded orange N
2O
2The decomposition situation.
Claims (9)
1. the preparation method of macromolecule multiphase-fenton Fenton catalyst-PVDF catalytic membrane; The preparation method who it is characterized in that macromolecule multiphase-fenton Fenton catalyst-PVDF catalytic membrane is that following step is carried out: mix after one, taking by weighing 4～20 parts of Kynoar, 50～90 parts of solvents and 0.1～10 part of additive respectively by ratio of quality and the number of copies; Under 45 ℃～60 ℃, be stirred to dissolving fully then; Constant temperature leaves standstill 30min～30h under 30 ℃～55 ℃ conditions; Knifing on the glass plate of cleaning soaks 30min～24h again in coagulating bath then, promptly makes pvdf membrane; Two, it is ethanolic solution preliminary treatment 5min～120min of 50%～75% that the pvdf membrane that step 1 is made is put into volumetric concentration, soaks 10min～120min with deionized water again; Three, will put into the aqueous slkali that the tetrabutyl phosphonium bromide ammonium concentration is 0.1～4mg/mL through the pvdf membrane that step 2 is handled, alkali treatment 5min～15min under 0 ℃～70 ℃ conditions cleans to neutral then; Four, will put into styrene and oxolane mixed liquor through the pvdf membrane that step 3 is handled, under 40 ℃～90 ℃ nitrogen protections, carry out graft reaction 30min～6h then, clean three to five times with chloroform again, obtain graft copolymer membrane; Five, the graft copolymer membrane that step 4 is obtained puts into 1; 20 ℃～70 ℃ following swelling 30min～2h in the 2-dichloroethanes add the graft copolymer membrane after swelling treatment in the concentrated sulfuric acid then, under 20 ℃～80 ℃ conditions, carry out sulfonation and handle 30min～6h; Water cleans to neutral, gets sulfonated membranes; Six, sulfonated membranes is put into the Fe that concentration is 0.1～1.0mol/L
3+In the solution, making macromolecule multiphase-fenton Fenton catalyst-PVDF catalytic membrane behind vibration 0.1h～12h under 25 ℃ of water-baths then.
2. the preparation method of macromolecule multiphase-fenton Fenton catalyst according to claim 1-PVDF catalytic membrane is characterized in that mixing after step 1 takes by weighing 8～15 parts of PVDF, 60～80 parts of solvents and 1～8 part of additive by ratio of weight and the number of copies respectively.
3. the preparation method of macromolecule multiphase-fenton Fenton catalyst according to claim 1-PVDF catalytic membrane is characterized in that mixing after step 1 takes by weighing 10 parts of PVDF, 70 parts of solvents and 5 parts of additives by ratio of weight and the number of copies respectively.
4. the preparation method of macromolecule multiphase-fenton Fenton catalyst according to claim 1-PVDF catalytic membrane; It is characterized in that the described solvent of step 1 is N; N-dimethylacetylamide, N, dinethylformamide, dimethyl sulfoxide (DMSO), triethyl phosphate or N-methyl pyrrolidone.
5. the preparation method of macromolecule multiphase-fenton Fenton catalyst according to claim 4-PVDF catalytic membrane is characterized in that the described additive of step 1 is lithium chloride, sodium nitrate, ammonium chloride, glycerine, phosphoric acid, water, polyvinylpyrrolidone or polyethylene glycol.
6. the preparation method of macromolecule multiphase-fenton Fenton catalyst according to claim 5-PVDF catalytic membrane is characterized in that the said aqueous slkali of step 3 is potassium hydroxide solution or sodium hydroxide solution.
7. the preparation method of macromolecule multiphase-fenton Fenton catalyst according to claim 6-PVDF catalytic membrane is characterized in that containing in the step 6 Fe
3+Solution be ferric sulfate, iron chloride, ferric nitrate or ferric perchlorate's solution.
8. according to the preparation method of the described macromolecule multiphase-fenton of each claim Fenton catalyst-PVDF catalytic membrane among the claim 1-7, it is characterized in that step 1 adopts cladding process to carry out knifing.
9. the preparation method of macromolecule multiphase-fenton Fenton catalyst according to claim 8-PVDF catalytic membrane is characterized in that at the described Fe of containing of step 6
3+Solution in add the copper ion or the manganese ion of 0.1%～5% (quality).
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| CN102372355B (en) * | 2011-10-09 | 2014-01-08 | 广东省生态环境与土壤研究所 | Method for processing organic waste water |
| CN102910725A (en) * | 2012-11-20 | 2013-02-06 | 哈尔滨工业大学 | Method for removing organic pollutants in water through modified Fenton and Fenton-like systems |
| CN103626901B (en) * | 2013-11-29 | 2016-06-29 | 内蒙古科技大学 | A kind of method that Kynoar is powder-modified |
| CN104752737A (en) * | 2015-04-09 | 2015-07-01 | 深圳市万越新能源科技有限公司 | Preparation method of novel all-vanadium redox flow battery ion exchange membrane |
| CN105297108B (en) * | 2015-11-16 | 2017-08-25 | 哈尔滨工业大学 | A kind of utilization plasma electrolytic oxidation method prepares the methods and applications of ceramic film class fenton catalyst on Q235 carbon steels surface |
| CN107118477B (en) * | 2017-05-12 | 2019-06-14 | 合肥工业大学 | A kind of carbon-coated metallic nano-particles load pvdf membrane and its preparation method and application |
| CN109092083A (en) * | 2017-06-20 | 2018-12-28 | 闽南师范大学 | A kind of preparation and application of ferroso-ferric oxide/regenerated cellulose magnetism forward osmosis membrane |
| CN107308938B (en) * | 2017-06-29 | 2019-11-05 | 天津工业大学 | A kind of manufacturing method of threadiness heterogeneous Fenton catalyst |
| CN107973435A (en) * | 2018-01-19 | 2018-05-01 | 广州锦时环保设备有限公司 | A kind of ceramic sewage treatment device and method |
| CN109289542A (en) * | 2018-09-28 | 2019-02-01 | 南方科技大学 | Antipollution ultrafiltration membrane preparation method with lightwave CATV catalytic performance |
| CN109502731B (en) * | 2018-10-09 | 2021-12-10 | 东华大学 | Preparation method and application of PVDF/pyrite nanofiber membrane |
| CN110894125A (en) * | 2019-09-25 | 2020-03-20 | 镇江新纳环保材料有限公司 | Sewage treatment process for recycling N-methyl pyrrolidone |
| CN112295421B (en) * | 2020-10-20 | 2022-11-15 | 天津理工大学 | Surface-bonded TiO2/PVDF ultrafiltration membrane for photocatalysis |
| CN113426496A (en) * | 2021-07-15 | 2021-09-24 | 浙江蓝波新材料科技有限公司 | Preparation method of composite cation exchange membrane |
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| CN1318502C (en) * | 2005-03-29 | 2007-05-30 | 哈尔滨工业大学 | Modification film of polyvinylidene fluoride and preparation method thereof |
| CN101792510B (en) * | 2010-01-18 | 2012-04-04 | 苏州大学 | Method for carrying out controllable hydrophilic modification on polyvinylidene fluoride (PVDF) |
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